Title of Invention

ZNO VAPOR DEPOSITION MATERIAL, PROCESS FOR PRODUCING THE SAME, AND ZNO FILM

Abstract A ZnO vapor deposition material for use in the deposition of, e.g., a transparent conductive film. It consists mainly of a porous ZnO sinter which contains one or more first additive elements selected among Ce, La, Y, Pr, Nd, Pm, and Sm and one or more second additive elements selected among Al, Ga, Sc, and B. The content of the first additive elements is higher than that of the second additive elements, and the content of the first additive elements and the content of the second additive elements are in the ranges of 0.1-14.9 mass% and 0.1-10 mass%, respectively. The sinter has a porosity of 3-50%.
Full Text DESCRIPTION
ZnO VAPOR DEPOSITION MATERIAL, PROCESS FOR PRODUCING THE SAME,
AND ZnO FILM
TECHNICAL FIELD
[0001]
The present invention relates to a ZnO vapor deposition material for formation of,
for example, a transparent conductive film used for solar cells; a gas and vapor-resistant
film; a transparent electrode of a transparent piezoelectric sensor or a gas or
vapor-resistant film in liquid crystal displays, electroluminescence display devices, and
touch panel devices; and various films used in active matrix drivers constituting display
devices, antistatic conductive coatings, gas sensors, electromagnetic shielding panels,
piezoelectric devices, photoelectric converters, luminescence devices, thin film type
secondary cells, and the like, a process for producing a ZnO vapor deposition material, a
ZnO film formed of the ZnO vapor deposition material, and a process for producing a
ZnO film.
This application claims priority based on Japanese Patent Application Nos.
2007-252759, 2007-252760, 2007-252761, 2007-252762, 2007-252763, 2007-252764,
2007-252765, and 2007-252766 filed on September 27, 2007, and Japanese Patent
Application Nos. 2008-245299, 2008-245300, 2008-245301, 2008-245302, 2008-245303,
2008-245304, 2008-245305, and 2008-245306 filed on September 25, 2008, the
enclosures of which are incorporated herein by reference.
[0002]
In recent years, transparent conductive films have been indispensable when
manufacturing photoelectric converters, such as solar cells and the like. As a known
transparent conductive film, an ITO film (a tin-doped indium oxide film) is known. The
ITO film has the advantages of excellent transparency and low resistance.
[0003]
Meanwhile, there has been a need for cost reduction in solar cells or liquid crystal
displays. However, since indium is expensive, when the ITO film is used as a
transparent conductive film, there is a disadvantage in that the solar cell also inevitably
becomes expensive. In the case of manufacturing solar cells or the like, an amorphous
silicon film is formed on a transparent conductive film by a plasma CVD method or the
like. At this time, if the transparent conductive film is an ITO film, there is a problem
in that hydrogen plasma at the time of plasma CVD leads to deterioration of the ITO
film.
[0004]
In order to solve such problems, it has been proposed that a zinc oxide-based film
doped with a conductive active element, such as Al, B, Si, Ga, or Sc, which can be
prepared at low cost is used as a transparent conductive film for solar cells or the like,
and a zinc oxide-based sputtering target is used to form the zinc oxide-based film by
sputtering (for example, Patent Document 1). According to this zinc oxide-based
sputtering target, an extremely low resistance zinc oxide-based sintered body is obtained
by containing a predetermined amount of the conductive active element in zinc.
Sintering density and conductivity of the sintered body are improved if the raw powder is
fine and has high dispersibility.
[Patent Document 1] Japanese Unexamined Patent Application Publication No.
DISCLOSURE OF INVENTION
Technical Problem
[0005]
However, if sputtering is performed to form a film at high speed using the
conventional zinc oxide-based sputtering target while applying high voltage, there are
disadvantages in that abnormal discharge is likely to occur, the target is inhomogeneously
consumed because of an unstable discharge state, compositional shift occurs in the
resultant film, and it is difficult to obtain a low resistance film. On the other hand, if the
voltage is decreased by decreasing power to be applied, there are disadvantages in that
the speed of film formation is lowered and the efficiency of zinc oxide-based film
formation is significantly reduced.
[0006]
Further, since the conventional target material has low evaporation efficiency and
film formation efficiency, the lifespan of the target material replacement cycle is
shortened, and there is a need for a target material having good evaporation efficiency
and film formation efficiency so as to increase productivity. If the speed of film
formation increases, film density is lowered, so the refractive index and sputtering
resistance may be lowered, and discharge characteristics and insulation characteristics are
deteriorated.
[0007]
The present invention has been completed in order to solve the above-described
problems, and an object of the present invention is to provide a ZnO vapor deposition
material capable of forming a film having high conductivity like an ITO film at high
speed and forming a conductive film having excellent transparency and denseness, and a
ZnO film using the ZnO vapor deposition material. Another object of the present
invention is to provide a ZnO vapor deposition material capable of improving the speed
of film formation with a large amount of evaporation per unit energy, and a ZnO film
using the ZnO vapor deposition material.
Technical Solution
[0008]
A first aspect of the present invention has the following configuration.
[A1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a porous ZnO sintered body containing Ce and Al, wherein
the Ce content is higher than the Al content, the Ce content is in a range of 0.1 to 14.9%
by mass, the Al content is in a range of 0.1 to 10% by mass, and the sintered body has a
porosity of 3 to 50%.
[A2] The ZnO vapor deposition material described in [Al], wherein the total
content of Ce and Al is in a range of 0.2 to 15% by mass.
[A3] The ZnO vapor deposition material described in [Al] or [A2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 µm.
[A4] The ZnO vapor deposition material described in any one of [Al] to [A3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[A5] The ZnO vapor deposition material described in any one of [Al] to [A4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0009]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body contains a predetermined amount of the two elements Ce and Al at a
specific ratio, a ZnO film having high conductivity like an ITO film can be obtained by
using the ZnO vapor deposition material. Preferably, the total content of Ce and Al is in
a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and
spectroscopic properties are obtained.
[0010]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0011]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 (am, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0012]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
Ce and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can
be obtained.
[0013]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[A6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, Al2O3 powder in such an amount that the
Al content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a
binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by
mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying
the gas-containing slurry to obtain a porous granulation powder having an average grain
size of 50 to 300 µm, (IV) molding the porous granulation powder to obtain a porous
molded body, and (V) sintering the porous molded body at a predetermined temperature
to obtain a porous ZnO sintered body.
[0014]
[A7] The process for producing a ZnO vapor deposition material of [A6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0015]
[A8] The process for producing a ZnO vapor deposition material of [A6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 urn, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0016]
[A9] The processes for producing a ZnO vapor deposition material of any one of
[A6] to [A8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, CeO2 powder, and Al2O3 powder are used, and the
powders, a binder, and an organic solvent are mixed to prepare a slurry with a
concentration of 30 to 75% by mass.
[0017]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0018]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of+10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0019]
The present invention provides the following ZnO film and production of the
same.
[A10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [A1] to [A5], or a ZnO vapor deposition material produced by the
process described in any one of [A6] to [A9].
[A11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [A1] to [A5], or a ZnO vapor
deposition material produced by the process described in any one of [A6] to [A9] as a
target material.
[A12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [A1] to [A5], or a ZnO vapor
deposition material produced by the process described in any one of [A6] to [A9] as a
target material.
[0020]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0021]
The ZnO vapor deposition material of this aspect contains Ce and Al as additive
elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered
and aligned by adding Al having a small ion radius. Thus, a ZnO film having high
permeability is formed, such that a ZnO film having excellent denseness and high
durability can be formed. A film having excellent moisture resistance and gas and
vapor barrier properties can be obtained.
[0022]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0023]
Another aspect of the present invention has the following configuration.
[B1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a porous ZnO sintered body containing Ce and Ga, wherein
the Ce content is higher than the Ga content, the Ce content is in a range of 0.1 to 14.9%
by mass, the Ga content is in a range of 0.1 to 10% by mass, and the sintered body has a
porosity of 3 to 50%.
[B2] The ZnO vapor deposition material described in [B1], wherein the total
content of Ce and Ga is in a range of 0.2 to 15% by mass.
[B3] The ZnO vapor deposition material described in [B1] or [B2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 urn.
[B4] The ZnO vapor deposition material described in any one of [B1] to [B3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[B5] The ZnO vapor deposition material described in any one of [B1] to [B4],
wherein the porous ZnO sintered body is poly crystal or monocrystal.
[0024]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
contains a predetermined amount of the two elements Ce and Ga at a specific ratio, so a
ZnO film having high conductivity like an ITO film can be obtained by using the ZnO
vapor deposition material. Preferably, the total content of Ce and Ga is in a range of 0.2
to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic
properties are obtained.
[0025]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0026]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0027]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
Ce and Ga at a specific ratio, so a ZnO film having high conductivity like an ITO film
can be obtained.
[0028]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[B6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, Ga2O3 powder in such an amount that the
Ga content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a
binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by
mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying
the gas-containing slurry to obtain a porous granulation powder having an average grain
size of 50 to 300 urn, (IV) molding the porous granulation powder to obtain a porous
molded body, and (V) sintering the porous molded body at a predetermined temperature
to obtain a porous ZnO sintered body.
[0029]
[B7] The process for producing a ZnO vapor deposition material of [B6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0030]
[B8] The process for producing a ZnO vapor deposition material of [B6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 m, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0031]
[B9] The processes for producing a ZnO vapor deposition material of any one of
[B6] to [B8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, CeO2 powder, and Ga2O3 powder are used, and the
powders, a binder, and an organic solvent are mixed to prepare a slurry with a
concentration of 30 to 75% by mass.
[0032]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0033]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0034]
The present invention provides the following ZnO film and production of the
same.
[B10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [B1] to [B5], or a ZnO vapor deposition material produced by the
process described in any one of [B6] to [B9].
[B11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [B1] to [B5], or a ZnO vapor
deposition material produced by the process described in any one of [B6] to [B9] as a
target material.
[B12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [B1] to [B5], or a ZnO vapor
deposition material produced by the process described in any one of [B6] to [B9] as a
target material.
[0035]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0036]
The ZnO vapor deposition material of this aspect contains Ce and Ga as additive
elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered
and aligned by adding Ga having a small ion radius. Thus, a ZnO film having high
permeability is formed, such that a ZnO film having excellent denseness and high
durability can be formed. A film having excellent moisture resistance and gas and
vapor barrier properties can be obtained.
[0037]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0038]
Another aspect of the present invention has the following configuration.
[C1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a porous ZnO sintered body containing Ce and Sc, wherein
the Ce content is higher than the Sc content, the Ce content is in a range of 0.1 to 14.9%
by mass, the Sc content is in a range of 0.1 to 10% by mass, and the sintered body has a
porosity of 3 to 50%.
[C2] The ZnO vapor deposition material described in [C1], wherein the total
content of Ce and Sc is in a range of 0.2 to 15% by mass.
[C3] The ZnO vapor deposition material described in [C1] or [C2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 µm.
[C4] The ZnO vapor deposition material described in any one of [C1] to [C3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[C5] The ZnO vapor deposition material described in any one of [C1] to [C4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0039]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
contains a predetermined amount of the two elements Ce and Sc at a specific ratio, so a
ZnO film having high conductivity like an ITO film can be obtained by using the ZnO
vapor deposition material. Preferably, the total content of Ce and Sc is in a range of 0.2
to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic
properties are obtained.
[0040]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0041]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0042]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
Ce and Sc at a specific ratio, so a ZnO film having high conductivity like an ITO film can
be obtained.
[0043]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[C6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, SC2O3 powder in such an amount that the
Sc content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a
binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by
mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying
the gas-containing slurry to obtain a porous granulation powder having an average grain
size of 50 to 300 µm, (IV) molding the porous granulation powder to obtain a porous
molded body, and (V) sintering the porous molded body at a predetermined temperature
to obtain a porous ZnO sintered body.
[0044]
[C7] The process for producing a ZnO vapor deposition material of [C6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0045]
[C8] The process for producing a ZnO vapor deposition material of [C6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0046]
[C9] The process for producing a ZnO vapor deposition material of any one of
[C6] to [C8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, CeO2 powder, and Sc2O3 powder are used, and the
powders, a binder, and an organic solvent are mixed to prepare a slurry with a
concentration of 30 to 75% by mass.
[0047]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0048]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0049]
The present invention provides the following ZnO film and production of the
same.
[C10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [C1] to [C5], or a ZnO vapor deposition material produced by the
process described in any one of [C6] to [C9].
[C11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [C1] to [C5], or a ZnO vapor
deposition material produced by the process described in any one of [C6] to [C9] as a
target material.
[C12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [C1] to [C5], or a ZnO vapor
deposition material produced by the process described in any one of [C6] to [C9] as a
target material.
[0050]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0051]
The ZnO vapor deposition material of this aspect contains Ce and Sc as additive
elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered
and aligned by adding Sc having a small ion radius. Thus, a ZnO film having high
permeability is formed, such that a ZnO film having excellent denseness and high
durability can be formed. A film having excellent moisture resistance and gas and
vapor barrier properties can be obtained.
[0052]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0053]
Another aspect of the present invention has the following configuration.
[D1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a porous ZnO sintered body containing Ce and B, wherein the
Ce content is higher than the B content, the Ce content is in a range of 0.1 to 14.9% by
mass, the B content is in a range of 0.1 to 10% by mass, and the sintered body has a
porosity of 3 to 50%.
[D2] The ZnO vapor deposition material described in [D1], wherein the total
content of Ce and B is in a range of 0.2 to 15% by mass.
[D3] The ZnO vapor deposition material described in [D1] or [D2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 urn.
[D4] The ZnO vapor deposition material described in any one of [D1] to [D3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[D5] The ZnO vapor deposition material described in any one of [D1] to [D4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0054]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
contains a predetermined amount of the two elements Ce and B at a specific ratio, so a
ZnO film having high conductivity like an ITO film can be obtained by using the ZnO
vapor deposition material. Preferably, the total content of Ce and B is in a range of 0.2
to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic
properties are obtained.
[0055]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0056]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0057]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
Ce and B at a specific ratio, so a ZnO film having high conductivity like an ITO film can
be obtained.
[0058]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[D6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, B2O3 powder in such an amount that the B
content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a
binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by
mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying
the gas-containing slurry to obtain a porous granulation powder having an average grain
size of 50 to 300 µm, (IV) molding the porous granulation powder to obtain a porous
molded body, and (V) sintering the porous molded body at a predetermined temperature
to obtain a porous ZnO sintered body.
[0059]
[D7] The process for producing a ZnO vapor deposition material of [D6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0060]
[D8] The process for producing a ZnO vapor deposition material of [D6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0061]
[D9] The process for producing a ZnO vapor deposition material of any one of
[D6] to [D8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 (am, and a grain size distribution within a range
of ±10% of the average grain size, CeO2 powder, and B2O3 powder are used, and the
powders, a binder, and an organic solvent are mixed to prepare a slurry with a
concentration of 30 to 75% by mass.
[0062]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0063]
In the process of this aspect, since the powder having an average grain size of 10
to 500 urn and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0064]
The present invention provides the following ZnO film and production of the
same.
[D10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [D1] to [D5], or a ZnO vapor deposition material produced by the
process described in any one of [D6] to [D9].
[D11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [D1] to [D5], or a ZnO vapor
deposition material produced by the process described in any one of [D6] to [D9] as a
target material.
[D12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [D1] to [D5], or a ZnO vapor
deposition material produced by the process described in any one of [D6] to [D9] as a
target material.
[0065]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0066]
The ZnO vapor deposition material of this aspect contains Ce and B as additive
elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered
and aligned by adding B having a small ion radius. Thus, a ZnO film having high
permeability is formed, such that a ZnO film having excellent denseness and high
durability can be formed. A film having excellent moisture resistance and gas and
vapor barrier properties can be obtained.
[0067]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0068]
Another aspect of the present invention has the following configuration.
[E1] AZnO vapor deposition material for formation of a transparent conductive
film which is composed of a sintered body containing ZnO as a major component,
wherein the sintered body contains La as a first additive element and a second additive
element, the second additive element is one or more elements selected from the group
consisting of B, Al, Ga, and Sc, the La content is in a range of 0.1 to 14.9% by mass, the
content of the second additive element is in a range of 0.1 to 10% by mass, the La
content is higher than the content of the second additive element, and the sintered body is
a porous sintered body having a porosity of 3 to 50%.
[E2] The ZnO vapor deposition material described in [E1], wherein the total
content of La as a first additive element and the second additive element is in a range of
0.2 to 15% by mass.
[E3] The ZnO vapor deposition material described in [E1] or [E2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 urn.
[E4] The ZnO vapor deposition material described in any one of [E1] to [E3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[E5] The ZnO vapor deposition material described in any one of [E1] to [E4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0069]
In the ZnO vapor deposition material of this aspect, the porous sintered body
containing ZnO as a major component (hereinafter, simply referred to as porous ZnO
sintered body) contains La as a first additive element and the second additive element at a
specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained
by using the ZnO vapor deposition material. Specifically, the porous sintered body
contains one or more elements selected from the group consisting of B, Al, Ga, and Sc as
the second additive element, and the total content of La as a first additive element and the
second additive element is in a range of 0.2 to 15% by mass, so excellent effects in terms
of conduction properties and spectroscopic properties are obtained.
[0070]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0071]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 urn, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0072]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
La and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can
be obtained.
[0073]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[E6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, La2O3 powder in such an amount that the La content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive
element in such an amount that the content of the second additive element in the ZnO
vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic
solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas
into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing
slurry to obtain a porous granulation powder having an average grain size of 50 to 300 µm, (IV) molding the porous granulation powder to obtain a porous molded body, and
(V) sintering the porous molded body at a predetermined temperature to obtain a porous
ZnO sintered body.
[0074]
[E7] The process for producing a ZnO vapor deposition material of [E6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0075]
[E8] The process for producing a ZnO vapor deposition material of [E6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0076]
[E9] The process for producing a ZnO vapor deposition material of any one of
[E6] to [E8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, La2O3 powder, and oxide powder of the second
additive element are used, and the powders, a binder, and an organic solvent are mixed to
prepare a slurry with a concentration of 30 to 75% by mass.
[0077]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0078]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0079]
The present invention provides the following ZnO film and production of the
same.
[E10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [E1] to [E5], or a ZnO vapor deposition material produced by the
process described in any one of [E6] to [E9].
[E11] A ZnO film which is formed by an electron beam deposition method, an ion
plating method, a sputtering method, or a plasma deposition method with the ZnO vapor
deposition material described in any one of [E1] to [E5], or a ZnO vapor deposition
material produced by the process described in any one of [E6] to [E9] as a target
material.
[E12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [E1] to [E5], or a ZnO vapor
deposition material produced by the process described in any one of [E6] to [E9] as a
target material.
[0080]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0081]
The ZnO vapor deposition material of this aspect contains La as a first additive
element and the second additive element, and the second additive element is one or more
elements selected from the group consisting of B, Al, Ga, and Sc, so crystals distorted by
La having an ion radius greater than Zn are recovered and aligned by adding B, Al, or Ga
having an ion radius smaller than La, or Sc having high reactivity is added to form a film
having a regulated crystal structure. Thus, a ZnO film having high permeability is
formed, such that a ZnO film having excellent denseness and high durability can be
formed. A film having excellent moisture resistance and gas and vapor barrier
properties can be obtained.
[0082]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0083]
Another aspect of the present invention has the following configuration.
[F1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a sintered body containing ZnO as a major component,
wherein the sintered body contains Y as a first additive element and a second additive
element, the second additive element is one or more elements selected from the group
consisting of B, Al, Ga, and Sc, the Y content is in a range of 0.1 to 14.9% by mass, the
content of the second additive element is in a range of 0.1 to 10% by mass, the Y content
is higher than the content of the second additive element, and the sintered body is a
porous sintered body having a porosity of 3 to 50%.
[F2] The ZnO vapor deposition material described in [F1], wherein the total
content of Y as a first additive element and the second additive element is in a range of
0.2 to 15% by mass.
[F3] The ZnO vapor deposition material described in [F1] or [F2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 µm.
[F4] The ZnO vapor deposition material described in any one of [F1] to [F3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[F5] The ZnO vapor deposition material described in any one of [F1] to [F4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0084]
In the ZnO vapor deposition material of this aspect, the porous sintered body
containing ZnO as a major component (hereinafter, simply referred to as porous ZnO
sintered body) contains Y as a first additive element and the second additive element at a
specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained
by using the ZnO vapor deposition material. Specifically, the porous sintered body
contains one or more elements selected from the group consisting of B, Al, Ga, and Sc as
the second additive element, and the total content of Y as a first additive element and the
second additive element is in a range of 0.2 to 15% by mass, so excellent effects in terms
of conduction properties and spectroscopic properties are obtained.
[0085]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0086]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0087]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is poly crystal or monocrystal, and contains a predetermined amount of the two elements
Y and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can
be obtained.
[0088]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[F6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, Y2O3 powder in such an amount that the Y content in the ZnO vapor deposition
material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive
element in such an amount that the content of the second additive element in the ZnO
vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic
solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas
into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing
slurry to obtain a porous granulation powder having an average grain size of 50 to 300
µm, (IV) molding the porous granulation powder to obtain a porous molded body, and
(V) sintering the porous molded body at a predetermined temperature to obtain a porous
ZnO sintered body.
[F7] The process for producing a ZnO vapor deposition material of [F6] including,
instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw
powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 urn.
[F8] The process for producing a ZnO vapor deposition material of [F6] including,
instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be
volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an
additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a
granulation powder having an average grain size of 50 to 300 µm, (IV-3) molding the
granulation powder to obtain a molded body, and (V-3) sintering the molded body while
volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[F9] The process for producing a ZnO vapor deposition material of any one of
[F6] to [F8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 urn, and a grain size distribution within a range
of ±10% of the average grain size, Y2O3 powder, and oxide powder of the second
additive element are used, and the powders, a binder, and an organic solvent are mixed to
prepare a slurry with a concentration of 30 to 75% by mass.
[0089]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0090]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0091]
The present invention provides the following ZnO film and production of the
same.
[F10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [F1] to [F5], or a ZnO vapor deposition material produced by the
process described in any one of [F6] to [F9].
[Fl 1] A ZnO film which is formed by an electron beam deposition method, an ion
plating method, a sputtering method, or a plasma deposition method with the ZnO vapor
deposition material described in any one of [F1] to [F5], or a ZnO vapor deposition
material produced by the process described in any one of [F6] to [F9] as a target material.
[F12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [F1] to [F5], or a ZnO vapor deposition
material produced by the process described in any one of [F6] to [F9] as a target material.
[0092]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0093]
The ZnO vapor deposition material of this aspect contains Y as a first additive
element and the second additive element, and the second additive element is one or more
elements selected from the group consisting of B, Al, Ga, and Sc, so crystals distorted by
Y having an ion radius greater than Zn are recovered and aligned by adding B, Al, or Ga
having an ion radius smaller than Y, or Sc having high reactivity is added to form a film
having a regulated crystal structure. Thus, a ZnO film having high permeability is
formed, such that a ZnO film having excellent denseness and high durability can be
formed. A film having excellent moisture resistance and gas and vapor barrier
properties can be obtained.
[0094]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0095]
Another aspect of the present invention has the following configuration.
[G1] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a sintered body containing ZnO as a major component,
wherein the sintered body contains a first additive element and a second additive element,
the first additive element is one or more elements selected from the group consisting of
Pr, Nd, Pm, and Sm, the second additive element is one or more elements selected from
the group consisting of B, Al, Ga, and Sc, the content of the first additive element is in a
range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of
0.1 to 10% by mass, the content of the first additive element is higher than the content of
the second additive element, and the sintered body is a porous sintered body having a
porosity of 3 to 50%.
[G2] The ZnO vapor deposition material described in [Gl], wherein the total
content of the first additive element and the second additive element is in a range of 0.2
to 15% by mass.
[G3] The ZnO vapor deposition material described in [Gl] or [G2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 urn.
[G4] The ZnO vapor deposition material described in any one of [Gl] to [G3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 µm.
[G5] The ZnO vapor deposition material described in any one of [Gl] to [G4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0096]
In the ZnO vapor deposition material of this aspect, the porous sintered body
containing ZnO as a major component (hereinafter, simply referred to as porous ZnO
sintered body) contains the first additive element and the second additive element at a
specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained
by using the ZnO vapor deposition material. Specifically, the first additive element is
one or more elements selected from the group consisting of Pr, Nd, Pm, and Sm, and the
total content of the first additive element and the second additive element is in a range of
0.2 to 15% by mass, so excellent effects in terms of conduction properties and
spectroscopic properties are obtained.
[0097]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0098]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0099]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
the first additive element and Al at a specific ratio, so a ZnO film having high
conductivity like an ITO film can be obtained.
[0100]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[G6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, an oxide powder of a first additive element in such an amount that the content of
the first additive element in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, an oxide powder of a second additive element in such an amount that the
content of the second additive element in the ZnO vapor deposition material is in a range
of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a
concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a
gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous
granulation powder having an average grain size of 50 to 300 µm, (IV) molding the
porous granulation powder to obtain a porous molded body, and (V) sintering the porous
molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[0101]
[G7] The process for producing a ZnO vapor deposition material of [G6]
including, instead of the steps (II) and (HI), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 µm.
[0102]
[G8] The process for producing a ZnO vapor deposition material of [G6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0103]
[G9] The process for producing a ZnO vapor deposition material of any one of
[G6] to [G8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, and oxide powder of the first additive element and the
second additive element are used, and the powders, a binder, and an organic solvent are
mixed to prepare a slurry with a concentration of 30 to 75% by mass.
[0104]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0105]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0106]
The present invention provides the following ZnO film and production of the
same.
[G10] AZnO film which is formed using the ZnO vapor deposition material
described in any one of [G1] to [G5], or a ZnO vapor deposition material produced by the
process described in any one of [G6] to [G9].
[G11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [G1] to [G5], or a ZnO vapor
deposition material produced by the process described in any one of [G6] to [G9] as a
target material.
[G12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [G1] to [G5], or a ZnO vapor
deposition material produced by the process described in any one of [G6] to [G9] as a
target material.
[0107]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0108]
The ZnO vapor deposition material of this aspect contains the first additive
element and the second additive element, the first additive element is one or more
elements selected from the group consisting of Pr, Nd, Pm, and Sm, and the second
additive element is one or more elements selected from the group consisting of B, Al, Ga,
and Sc, so crystals distorted by the first additive element having an ion radius greater
than Zn are recovered and aligned by adding B, Al, or Ga, which is the second additive
element having an ion radius smaller than the first additive element, or Sc having high
reactivity is added to form a film having a regulated crystal structure. Thus, a ZnO film
having high permeability is formed, such that a ZnO film having excellent denseness and
high durability can be formed. A film having excellent moisture resistance and gas and
vapor barrier properties can be obtained.
[0109]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
[0110]
Another aspect of the present invention has the following configuration.
[HI] A ZnO vapor deposition material for formation of a transparent conductive
film which is composed of a ZnO sintered body having a ZnO purity equal to or greater
than 98%, wherein the sintered body contains one or more additive elements selected
from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, and the sintered body is
a porous sintered body having a porosity of 3 to 50%.
[H2] The ZnO vapor deposition material described in [H1], wherein the content
of the additive elements in the ZnO sintered body is in a range of 2 to 20% by mass.
[H3] The ZnO vapor deposition material described in [H1] or [H2], wherein the
porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 µm.
[H4] The ZnO vapor deposition material described in any one of [H1] to [H3],
wherein the porous ZnO sintered body is a sintered body of grains having an average
crystal grain size of 1 to 500 urn.
[H5] The ZnO vapor deposition material described in any one of [H1] to [H4],
wherein the porous ZnO sintered body is polycrystal or monocrystal.
[0111]
The ZnO vapor deposition material of this aspect is composed of a ZnO sintered
body having a ZnO purity equal to or greater than 98%, and the sintered body contains
one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd,
Pm, and Sm, so a ZnO film having good conductivity over a wide temperature range can
be obtained by using the ZnO vapor deposition material.
[0112]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor
deposition material is large, and the evaporation speed of the vapor deposition material
can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than
the conventional ZnO vapor deposition material.
[0113]
In the ZnO vapor deposition material of this aspect, since the porous ZnO
sintered body has pores having an average pore diameter of 0.1 to 500 µm, the
evaporation speed can be increased. The porous ZnO sintered body is a sintered body
of grains having an average crystal grain size of 1 to 500 µm, so the specific surface area
inside the vapor deposition material increases, thereby increasing the evaporation speed
of the vapor deposition material. The formed ZnO film has excellent film
characteristics.
[0114]
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body
is polycrystal or monocrystal, and contains a predetermined amount of the two elements
the first additive element and Al at a specific ratio, so a ZnO film having high
conductivity like an ITO film can be obtained.
[0115]
Another aspect of the present invention provides a process for producing a ZnO
vapor deposition material having the following configuration.
[H6] A process for producing a ZnO vapor deposition material, the process
including the steps of (I) mixing ZnO powder having a purity equal to or greater than
98%, an oxide powder of additive elements, a binder, and an organic solvent to prepare a
slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to
obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a
porous granulation powder having an average grain size of 50 to 300 urn, (IV) molding
the porous granulation powder to obtain a porous molded body, and (V) sintering the
porous molded body at a predetermined temperature to obtain a porous ZnO sintered
body.
[0116]
[H7] The process for producing a ZnO vapor deposition material of [H6]
including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in
raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the
foaming agent-containing slurry while spray-drying the foaming agent-containing slurry
to obtain a porous granulation powder having an average grain size of 50 to 300 urn.
[0117]
[H8] The process for producing a ZnO vapor deposition material of [H6]
including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which
will be volatized and dissolved at the time of calcination, in raw powder or slurry to
obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, (IV-3)
molding the granulation powder to obtain a molded body, and (V-3) sintering the molded
body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[0118]
[H9] The process for producing a ZnO vapor deposition material of any one of
[H6] to [H8], wherein in the step (I), ZnO powder having a purity equal to or greater than
98%, an average grain size of 10 to 500 µm, and a grain size distribution within a range
of ±10% of the average grain size, and oxide powder of the additive element are used,
and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a
concentration of 30 to 75% by mass.
[0119]
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition
material having a large amount of evaporation, and having excellent film formation
properties and denseness can be relatively easily produced. In particular, by the step (II)
blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming
agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor
deposition material having pores with predetermined porosity and average pore diameter,
and an average crystal grain size can be relatively easily produced.
[0120]
In the process of this aspect, since the powder having an average grain size of 10
to 500 µm and a grain size distribution within a range of ±10% of the average grain size
is used, fine grains do not substantially enter between grains, and thus a porous molded
body having a porosity of 3 to 50% can be easily obtained.
[0121]
The present invention provides the following ZnO film and production of the
same.
[H10] A ZnO film which is formed using the ZnO vapor deposition material
described in any one of [H1] to [H5], or a ZnO vapor deposition material produced by the
process described in any one of [H6] to [H9].
[H11] A ZnO film which is formed by an electron beam deposition method, an
ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [H1] to [H5], or a ZnO vapor
deposition material produced by the process described in any one of [H6] to [H9] as a
target material.
[H12] A process for forming a ZnO film by an electron beam deposition method,
an ion plating method, a sputtering method, or a plasma deposition method with the ZnO
vapor deposition material described in any one of [H1] to [H5], or a ZnO vapor
deposition material produced by the process described in any one of [H6] to [H9] as a
target material.
[0122]
The ZnO vapor deposition material of this aspect can be widely used in a vacuum
deposition method, such as an electron beam deposition method, an ion plating method, a
sputtering method, or a plasma deposition method. By using the ZnO vapor deposition
material of this aspect, for example, when a film is formed at the same speed of film
formation as the related art by an electron beam deposition method, the filament
replacement frequency can be reduced, and the speed of film formation can be increased,
thereby shortening the production time.
[0123]
The ZnO vapor deposition material of this aspect is composed of the ZnO
sintered body having a ZnO purity equal to or greater than 98%, and the sintered body
contains one or more additive elements selected from the group consisting of Y, La, Sc,
Ce, Pr, Nd, Pm, and Sm, so a ZnO film having good conductivity over a wide
temperature range can be obtained by using the ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the ZnO sintered body
contains the additive element(s), regardless of polycrystal or monocrystal, a ZnO film
having good conductivity over a wide temperature range can be obtained. Further, a
film having excellent moisture resistance, and gas and vapor barrier properties can be
obtained.
[0124]
The ZnO vapor deposition material of this aspect has porosity within a
predetermined range, and preferably, pores have an average pore diameter within a
specific range, and grains have an average crystal grain size within a predetermined
range, so the specific surface area inside the vapor deposition material increases, thereby
increasing the evaporation speed. Thus, a ZnO film having good film formation
efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of
this aspect is dense, and has high conductivity and excellent durability.
ADVANTAGEOUS EFFECTS
[0125]
According to the present invention, a ZnO film having high permeability,
excellent denseness, and high durability can be formed. Further, a film having excellent
moisture resistance, and gas and vapor barrier properties can be obtained.
Best Mode for Carrying Out the Invention
[0126]
Hereinafter, an aspect of the present invention will be described specifically.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed mainly of a
porous ZnO sintered body containing Ce and Al, wherein the Ce content is higher than
the Al content, the Ce content is in a range of 0.1 to 14.9% by mass, the Al content is in a
range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[0127]
The inventors have investigated in detail the effect on conductivity due to
additive species and its content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence due to the content ratio of the two elements of Ce and Al as the
additive elements in the porous ZnO sintered body. Based on the above-described
knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a
major component, and also contains both elements of Ce and Al, such that excess
electrons contributing to conduction are developed in large amounts and maintained,
thereby forming a ZnO film having high conductivity.
[0128]
As the ratio of the two elements of Ce and Al in the porous ZnO sintered body
increases within a predetermined range, the conductivity of the ZnO film becomes better,
and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically,
the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to
14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is
significantly lowered.
[0129]
The Al content in the ZnO vapor deposition material is appropriately in a range of
0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Al content is
lower than the lower limit value, 0.1 % by mass, the conductivity is significantly lowered.
If the Al content exceeds the upper limit value, 10% by mass, compositional shift at the
time of deposition occurs.
[0130]
The ZnO vapor deposition material of this aspect contains a larger amount of Ce
than Al, such that a dense crystal structure is maintained. If the Ce content is lower than
the Al content, the conductivity and permeability are lowered. The total content of Ce
and Al is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and Al
exceeds this range, the specific resistance and permeability of the ZnO vapor deposition
material are significantly lowered.
[0131]
When a very small amount of Ce and Al is contained in the ZnO vapor deposition
material, Ce and Al do not exist as granular precipitates in grain boundaries or grains in
the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is
considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as
CeO2 or Ce2O3, and Al is present as Al2O3.
[0132]
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent
or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier
electrons to be generated with respect to divalent Zn, such that high conductivity can be
ensured. When a rare earth element is added to the ZnO vapor deposition material,
compositional shift at the time of deposition is unlikely to occur, and a desired
composition ratio can be maintained when a film is formed.
[0133]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage, since
the ZnO vapor deposition material of this aspect contains Al as an additive element, high
conductivity like ITO can be obtained.
[0134]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%), more preferably
in a range of 10 to 30%>, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in manufacturing costs. If the porosity exceeds
50%, the strength of the porous sintered body is lowered, and it is difficult to obtain
sufficient mechanical strength. If the porosity is equal to or greater than 10%, the
evaporation speed can be improved. Further, if the porosity is equal to or greater than
20%, a vapor deposition material having an evaporation speed about 2.0 times higher
than the conventional ZnO vapor deposition material can be obtained.
[0135]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 urn. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0136]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0137]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m /g,
and at least one peak of the micropore distribution is present within a range of 1 to 100
urn. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0138]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 urn are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 urn.
[0139]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0140]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such
an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, Al2O3 powder in such an amount that the Al content in the ZnO vapor
deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent
to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to
obtain a granulation powder having an average grain size of 50 to 300 urn, molding the
granulation powder to obtain a porous molded body, and sintering the molded body at a
predetermined temperature to obtain a porous ZnO sintered body.
[0141]
The ZnO powder preferably has purity equal to or greater than 98%, and more
preferably, equal to or greater than 98.4%. If the ZnO powder has purity equal to or
greater than 98%, reduction of conductivity by the effect of impurities can be suppressed.
The average grain size of the ZnO powder is in a range of 0.1 to 10 µm. When the
average grain size of the ZnO powder is smaller than 0.1 µm, the powder is excessively
fine and aggregated, so there is a tendency that the handling of the powder becomes
worse, and it is difficult to prepare a high-concentration slurry. When the average grain
size exceeds 10 µm, there is a tendency that it is difficult to control the micro-structure,
and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is
adjusted to the above-described range, a desired sintered body is also obtained without
using a sintering auxiliary agent.
[0142]
With regard to the CeO2 powder, considering the prevention of maldistribution of
the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is
preferable to add cerium oxide grains whose primary grain size is of a nanometer scale.
The Al2O3 powder preferably has an average grain size of 0.01 to 1 µm, and still more
preferably, the average grain size is in a range of 0.05 to 0.5 µm. If the Al2O3 powder
having this average grain size is used, it is beneficial in terms of the uniform dispersion
of the CeO2 powder.
[0143]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0144]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0145]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0146]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0147]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0148]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0149]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, CeO2 powder, and Al2O3 powder, or may
be added upon slurry preparation.
[0150]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0151]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0152]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1
µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0153]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 urn can
obtain an evaporation speed about two times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0154]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of CeO2 powder and Al2O3 powder is significantly smaller than that of ZnO powder, and
the usage is smaller than that of ZnO powder, so CeO2 powder and Al2O3 powder may be
outside the limitation of the grain size distribution.
[0155]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 urn and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0156]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0157]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0158]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0159]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0160]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5x10-4 O cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an
ion radius larger than Zn are recovered and aligned by adding Al having a small ion
radius, such that the durability of the film is improved.
[0161]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0162]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, manufacturing costs can be reduced.
[0163]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed mainly of a
porous ZnO sintered body containing Ce and Ga, wherein the Ce content is higher than
the Ga content, the Ce content is in a range of 0.1 to 14.9% by mass, the Ga content is in
a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[0164]
The inventors have investigated in detail the effect on conductivity due to
additive species and its content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence due to the content ratio of the two elements of Ce and Ga as the
additive elements in the porous ZnO sintered body. Based on the above-described
knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a
major component, and also contains both elements of Ce and Ga, such that excess
electrons contributing to conduction are developed in large amounts and maintained,
thereby forming a ZnO film having high conductivity.
[0165]
As the ratio of the two elements of Ce and Ga in the porous ZnO sintered body
increases within a predetermined range, the conductivity of the ZnO film becomes better,
and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically,
the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to
14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is
significantly lowered.
[0166]
The Ga content in the ZnO vapor deposition material is appropriately in a range
of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Ga content
is lower than the lower limit value, 0.1% by mass, the conductivity is significantly
lowered. If the Ga content exceeds the upper limit value, 10% by mass, compositional
shift at the time of deposition occurs.
[0167]
The ZnO vapor deposition material of this aspect contains a larger amount of Ce
than Ga, such that a dense crystal structure is maintained. If the Ce content is lower
than the Ga content, the conductivity and permeability are lowered. The total content of
Ce and Ga is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and
Ga exceeds this range, the specific resistance and permeability of the ZnO vapor
deposition material are significantly lowered.
[0168]
When a very small amount of Ce and Ga is contained in the ZnO vapor
deposition material, Ce and Ga do not exist as granular precipitates in grain boundaries or
grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition
material. It is considered that, in the ZnO vapor deposition material, Ce is present as an
oxide, such as CeO2 or Ce2O3, and Ga is present as Ga2O3.
[0169]
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent
or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier
electrons to be generated with respect to divalent Zn, such that high conductivity can be
ensured. When a rare earth element is added to the ZnO vapor deposition material,
compositional shift at the time of deposition is unlikely to occur, and a desired
composition ratio can be maintained when a film is formed.
[0170]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage, since
the ZnO vapor deposition material of this aspect contains Ga as an additive element, high
conductivity like ITO can be obtained.
[0171]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in manufacturing costs. If the porosity exceeds
50%, the strength of the porous sintered body is lowered, and it is difficult to obtain
sufficient mechanical strength. If the porosity is equal to or greater than 10%, the
evaporation speed can be improved. Further, if the porosity is equal to or greater than
20%, a vapor deposition material having an evaporation speed about two times higher
than the conventional ZnO vapor deposition material can be obtained.
[0172]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0173]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0174]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m /g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0175]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0176]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0177]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such
an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, Ga2O3 powder in such an amount that the Ga content in the ZnO vapor
deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent
to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, molding the
granulation powder to obtain a porous molded body, and sintering the molded body at a
predetermined temperature to obtain a porous ZnO sintered body.
[0178]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 urn, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0179]
With regard to the CeO2 powder, considering the prevention of maldistribution of
the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is
preferable to add cerium oxide grains whose primary grain size is of a nanometer scale.
The Ga2O3 powder preferably has an average grain size of 0.01 to 1 µm, and still more
preferably, the average grain size is in a range of 0.05 to 0.5 µm. If the Ga2O3 powder
having this average grain size is used, it is beneficial in terms of the uniform dispersion
of the CeO2 powder.
[0180]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0181]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0182]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0183]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0184]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0185]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 urn can be obtained.
[0186]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, CeO2 powder, and Ga2O3 powder, or
may be added upon slurry preparation.
[0187]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 urn can be obtained.
[0188]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0189]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0190]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 urn can
obtain an evaporation speed about two times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0191]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 urn and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of CeO2 powder and Ga2O3 powder is significantly smaller than that of ZnO powder, and
the usage is smaller than that of ZnO powder, so CeO2 powder and Ga2O3 powder may
be outside the limitation of the grain size distribution.
[0192]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0193]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 urn, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0194]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0195]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0196]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0197]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5X10-4 O cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an
ion radius larger than Zn are recovered and aligned by adding Ga having a small ion
radius, such that the durability of the film is improved.
[0198]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0199]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, manufacturing costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed mainly of a
porous ZnO sintered body containing Ce and Sc, wherein the Ce content is higher than
the Sc content, the Ce content is in a range of 0.1 to 14.9% by mass, the Sc content is in a
range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[0200]
The inventors have investigated in detail the effect on conductivity due to
additive species and its content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence due to the content ratio of the two elements of Ce and Sc as the
additive elements in the porous ZnO sintered body. Based on the above-described
knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a
major component, and also contains both elements of Ce and Sc, such that excess
electrons contributing to conduction are developed in large amounts and maintained,
thereby forming a ZnO film having high conductivity.
[0201]
As the ratio of the two elements of Ce and Sc in the porous ZnO sintered body
increases within a predetermined range, the conductivity of the ZnO film becomes better,
and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically,
the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to
14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is
significantly lowered.
[0202]
The Sc content in the ZnO vapor deposition material is appropriately in a range of
0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Sc content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the Sc content exceeds the upper limit value, 10% by mass, compositional shift at the
time of deposition occurs.
[0203]
The ZnO vapor deposition material of this aspect contains a larger amount of Ce
than Sc, such that a dense crystal structure is maintained. If the Ce content is lower than
the Sc content, the conductivity and permeability are lowered. The total content of Ce
and Sc is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and Sc
exceeds this range, the specific resistance and permeability of the ZnO vapor deposition
material are significantly lowered.
[0204]
When a very small amount of Ce and Sc is contained in the ZnO vapor deposition
material, Ce and Sc do not exist as granular precipitates in grain boundaries or grains in
the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is
considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as
CeO2 or Ce2O3, and Sc is present as Sc2O3.
[0205]
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent
or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier
electrons to be generated with respect to divalent Zn, such that high conductivity can be
ensured. When a rare earth element is added to the ZnO vapor deposition material,
compositional shift at the time of deposition is unlikely to occur, and a desired
composition ratio can be maintained when a film is formed.
[0206]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage, since
the ZnO vapor deposition material of this aspect contains Sc as an additive element, high
conductivity like ITO can be obtained.
[0207]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in manufacturing costs. If the porosity exceeds
50%, the strength of the porous sintered body is lowered, and it is difficult to obtain
sufficient mechanical strength. If the porosity is equal to or greater than 10%, the
evaporation speed can be improved. Further, if the porosity is equal to or greater than
20%, a vapor deposition material having an evaporation speed about two times higher
than the conventional ZnO vapor deposition material can be obtained.
[0208]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 urn, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0209]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0210]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m /g,
and at least one peak of the micropore distribution is present within a range of 1 to 100
urn. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0211]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0212]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0213]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such
an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, Sc2O3 powder in such an amount that the Sc content in the ZnO vapor
deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent
to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, molding the
granulation powder to obtain a porous molded body, and sintering the molded body at a
predetermined temperature to obtain a porous ZnO sintered body.
[0214]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0215]
With regard to the CeO2 powder, considering the prevention of maldistribution of
the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is
preferable to add cerium oxide grains whose primary grain size is of a nanometer scale.
The Sc2O3 powder preferably has an average grain size of 0.01 to 1 µm, and still more
preferably, the average grain size is in a range of 0.05 to 0.5 urn. If the Sc2O3 powder
having this average grain size is used, it is beneficial in terms of the uniform dispersion
of the CeO2 powder.
[0216]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0217]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0218]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0219]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0220]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0221]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0222]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, CeO2 powder, and Sc203 powder, or
may be added upon slurry preparation.
[0223]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0224]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0225]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0226]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about two times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0227]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of CeO2 powder and SC2O3 powder is significantly smaller than that of ZnO powder, and
the usage is smaller than that of ZnO powder, so CeO2 powder and SC2O3 powder may be
outside the limitation of the grain size distribution.
[0228]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0229]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 urn, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0230]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0231]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0232]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0233]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5X10-4 O-cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an
ion radius larger than Zn are recovered and aligned by adding Sc having a small ion
radius, such that the durability of the film is improved.
[0234]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0235]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[0236]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed mainly of a
porous ZnO sintered body containing Ce and B, wherein the Ce content is higher than the
B content, the Ce content is in a range of 0.1 to 14.9% by mass, the B content is in a
range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[0237]
The inventors have investigated in detail the effect on conductivity due to
additive species and its content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence due to the content ratio of the two elements of Ce and B as the additive
elements in the porous ZnO sintered body. Based on the above-described knowledge,
the ZnO vapor deposition material according to this aspect contains ZnO as a major
component, and also contains both elements of Ce and B, such that excess electrons
contributing to conduction are developed in large amounts and maintained, thereby
forming a ZnO film having high conductivity.
[0238]
As the ratio of the two elements of Ce and B in the porous ZnO sintered body
increases within a predetermined range, the conductivity of the ZnO film becomes better,
and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically,
the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to
14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is
significantly lowered.
[0239]
The B content in the ZnO vapor deposition material is appropriately in a range of
0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the B content is
lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered.
If the B content exceeds the upper limit value, 10% by mass, compositional shift at the
time of deposition occurs.
[0240]
The ZnO vapor deposition material of this aspect contains a larger amount of Ce
than B, such that a dense crystal structure is maintained. If the Ce content is lower than
the B content, the conductivity and permeability are lowered. The total content of Ce
and B is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and B
exceeds this range, the specific resistance and permeability of the ZnO vapor deposition
material are significantly lowered.
[0241]
When a very small amount of Ce and B is contained in the ZnO vapor deposition
material, Ce and B do not exist as granular precipitates in grain boundaries or grains in
the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is
considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as
CeO2 or Ce2O3, and B is present as B2O3.
[0242]
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent
or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier
electrons to be generated with respect to divalent Zn, such that high conductivity can be
ensured. When a rare earth element is added to the ZnO vapor deposition material,
compositional shift at the time of deposition is unlikely to occur, and a desired
composition ratio can be maintained when a film is formed.
[0243]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage, since
the ZnO vapor deposition material of this aspect contains B as an additive element, high
conductivity like ITO can be obtained.
[0244]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in production costs. If the porosity exceeds 50%,
the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient
mechanical strength. If the porosity is equal to or greater than 10%, the evaporation
speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor
deposition material having an evaporation speed about two times higher than the
conventional ZnO vapor deposition material can be obtained.
[0245]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0246]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0247]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0248]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 |um, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 urn, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 urn, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 urn, and more preferably, in a range of 10 to 30 µm.
[0249]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0250]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such
an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, B2O3 powder in such an amount that the B content in the ZnO vapor
deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent
to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to
obtain a granulation powder having an average grain size of 50 to 300 µm, molding the
granulation powder to obtain a porous molded body, and sintering the molded body at a
predetermined temperature to obtain a porous ZnO sintered body.
[0251]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0252]
With regard to the CeO2 powder, considering the prevention of maldistribution of
the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is
preferable to add cerium oxide grains whose primary grain size is of a nanometer scale.
The B2O3 powder preferably has an average grain size of 0.01 to 1 µm, and still more
preferably, the average grain size is in a range of 0.05 to 0.5 µm. If the B2O3 powder
having this average grain size is used, it is beneficial in terms of the uniform dispersion
of the CeO2 powder.
[0253]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0254]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0255]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0256]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0257]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0258]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0259]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, CeO2 powder, and B2O3 powder, or may
be added upon slurry preparation.
[0260]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0261]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0262]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0263]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about two times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0264]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of CeO2 powder and B2O3 powder is significantly smaller than that of ZnO powder, and
the usage is smaller than that of ZnO powder, so CeO2 powder and B2O3 powder may be
outside the limitation of the grain size distribution.
[0265]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0266]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0267]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0268]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0269]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0270]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5x10-4 Ocm and high permeability with visible light
permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an
ion radius larger than Zn are recovered and aligned by adding B having a small ion radius,
such that the durability of the film is improved.
[0271]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0272]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[0273]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed of a sintered
body containing ZnO as a major component, wherein the sintered body contains La as a
first additive element and a second additive element, the second additive element is one
or more elements selected from the group consisting of B, Al, Ga, and Sc, the La content
is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a
range of 0.1 to 10% by mass, the La content is higher than the content of the second
additive element, and the sintered body is a porous sintered body having a porosity of 3
to 50%.
[0274]
The inventors have investigated in detail the effect on conductivity due to
additive species and its content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence on conductivity due to the species and content of La as an additive
element and B, Al, Ga, or Sc in the porous ZnO sintered body. Based on the
above-described knowledge, the ZnO vapor deposition material according to this aspect
contains ZnO as a major component, and also contains La as a first additive element and
the second additive element, such that excess electrons contributing to conduction are
developed in large amounts and maintained, thereby forming a ZnO film having high
conductivity.
[0275]
The ZnO vapor deposition material of this aspect contains La as a first additive
element and the second additive element together, and the second additive element is one
or more elements selected from B, Al, Ga, and Sc. Of the second additive elements, B,
Al, and Ga have an ion radius smaller than La as a first additive element, so crystals
distorted by the addition of La having an ion radius larger than Zn are recovered and
aligned by adding B, Al, or Ga, or the crystal structure distorted by the addition of La is
recovered and aligned by adding Sc having high reactivity as the second additive element.
For this reason, a ZnO film having high permeability, excellent denseness, high
conductivity, and excellent durability can be formed.
[0276]
As the ratio of La as a first additive element and the second additive element in
the porous ZnO sintered body increases within a predetermined range, the conductivity of
the ZnO film becomes better, and if the ratio is outside the range, the conductivity
adversely deteriorates. Specifically, the La content in the ZnO vapor deposition
material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of
3 to 6% by mass. If the La content is lower than the lower limit value, 0.1 % by mass,
the conductivity is significantly lowered. If the La content exceeds the upper limit
value, 14.9% by mass, the permeability is significantly lowered.
[0277]
The content of the second additive element in the ZnO vapor deposition material
is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3%
by mass. If the content of the second additive element is lower than the lower limit
value, 0.1% by mass, the conductivity is significantly lowered. If the content of the
second additive element exceeds the upper limit value, 10% by mass, compositional shift
at the time of deposition occurs.
[0278]
The ZnO vapor deposition material of this aspect contains a larger amount of La
as a first additive element than the second additive element, such that a dense crystal
structure is maintained. If the La content is lower than that of the second additive
element, the conductivity and permeability are lowered. The total content of Ce as a
first additive element and the second additive element is preferably in a range of 0.2 to
15% by mass. If the total content of La and the second additive element exceeds this
range, the specific resistance and permeability of the ZnO vapor deposition material are
significantly lowered.
[0279]
When a very small amount of La as a first additive element and the second
additive element is contained in the ZnO vapor deposition material, La as a first additive
element and the second additive element do not exist as granular precipitates in grain
boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor
deposition material. It is considered that, in the ZnO vapor deposition material, the first
additive element and the second additive element are present as oxides.
[0280]
The ZnO vapor deposition material of this aspect contains La, which is a trivalent
rare earth element, as a first additive element, and La causes excess carrier electrons to be
generated with respect to divalent Zn, such that high conductivity can be ensured.
When a rare earth element is added to the ZnO vapor deposition material, compositional
shift at the time of deposition is unlikely to occur, and a desired composition ratio can be
maintained when a film is formed.
[0281]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage by
the addition of La which is a rare earth element, since the ZnO vapor deposition material
of this aspect contains the second additive element, high conductivity like ITO can be
obtained.
[0282]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in production costs. If the porosity exceeds 50%,
the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient
mechanical strength. If the porosity is equal to or greater than 10%, the evaporation
speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor
deposition material having an evaporation speed about two times higher than the
conventional ZnO vapor deposition material can be obtained.
[0283]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0284]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0285]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m /g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0286]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0287]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0288]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, La2O3 powder in such
an amount that the La content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, an oxide powder of a second additive element in such an amount that the
content of the second additive element in the ZnO vapor deposition material is in a range
of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a
concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a
gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous
granulation powder having an average grain size of 50 to 300 µm, molding the porous
granulation powder to obtain a porous molded body, and sintering the porous molded
body at a predetermined temperature to obtain a porous ZnO sintered body.
[0289]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0290]
With regard to the La2O3 powder, considering the prevention of maldistribution
of the La powder, reactivity with a ZnO matrix, and the purity of a La compound, it is
preferable to add La oxide grains whose primary grain size is of a nanometer scale. The
oxide powder of the second additive element preferably has an average grain size of 0.01
to 1 µm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 µm.
If the oxide powder of the second additive element having this average grain size is used,
it is beneficial in terms of the uniform dispersion of the oxide powder of the second
additive element.
[0291]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0292]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0293]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0294]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0295]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0296]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0297]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, LaO2 powder, and Al2O3 powder, or may
be added upon slurry preparation.
[0298]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0299]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0300]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0301]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about two times. Therefore, a high speed of film formation
can be obtained.
[0302]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of oxide powder of the first additive element and the second additive element is
significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO
powder, so oxide powder of the first additive element and the second additive element
may be outside the limitation of the grain size distribution.
[0303]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0304]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0305]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0306]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0307]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0308]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5x10-4 O-cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO.
[0309]
In the ZnO vapor deposition material of this aspect, the crystal structure distorted
by the addition of La having an ion radius larger than Zn is recovered and aligned by
addition of the second additive element having a small ion radius, such as B, Al, or Ga,
or Sc having high reactivity is added to recover a film having a regulated crystal structure.
Therefore, a dense film can be formed, and the durability of the film can also be
improved.
[0310]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0311]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[0312]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed of a sintered
body containing ZnO as a major component, wherein the sintered body contains Y as a
first additive element and a second additive element, the second additive element is one
or more elements selected from the group consisting of B, Al, Ga, and Sc, the Y content
is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a
range of 0.1 to 10% by mass, the Y content is higher than the content of the second
additive element, and the sintered body is a porous sintered body having a porosity of 3
to 50%.
[0313]
The inventors have investigated in detail the effect on conductivity due to
additive species and the content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence on conductivity due to the species and content of Y as a first additive
element and the second additive element, such as B, Al, Ga, or Sc, in the porous ZnO
sintered body. Based on the above-described knowledge, the ZnO vapor deposition
material according to this aspect contains ZnO as a major component, and also contains
Y as a first additive element and the second additive element, such that excess electrons
contributing to conduction are developed in large amounts and maintained, thereby
forming a ZnO film having high conductivity.
[0314]
The ZnO vapor deposition material of this aspect contains Y as a first additive
element and the second additive element together, and the second additive element is one
or more elements selected from B, Al, Ga, and Sc. Of the second additive elements, B,
Al, and Ga have an ion radius smaller than Y as a first additive element, so crystals
distorted by the addition of Y having an ion radius larger than Zn are recovered and
aligned by adding B, Al, or Ga, or the crystal structure distorted by the addition of Y is
recovered and aligned by adding Sc having high reactivity as the second additive element.
For this reason, a ZnO film having high permeability, excellent denseness, high
conductivity, and excellent durability can be formed.
[0315]
As the ratio of Y as a first additive element and the second additive element in the
porous ZnO sintered body increases within a predetermined range, the conductivity of the
ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely
deteriorates. Specifically, the Y content in the ZnO vapor deposition material is
appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by
mass. If the Y content is lower than the lower limit value, 0.1% by mass, the
conductivity is significantly lowered. If the Y content exceeds the upper limit value,
14.9% by mass, the permeability is significantly lowered.
[0316]
The content of the second additive element in the ZnO vapor deposition material
is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3%
by mass. If the content of the second additive element is lower than the lower limit
value, 0.1% by mass, the conductivity is significantly lowered. If the content of the
second additive element exceeds the upper limit value, 10% by mass, compositional shift
at the time of deposition occurs.
[0317]
The ZnO vapor deposition material of this aspect contains a larger amount of Y as
a first additive element than the second additive element, such that a dense crystal
structure is maintained. If the Y content is lower than that of the second additive
element, the conductivity and permeability are lowered. The total content of Y as a first
additive element and the second additive element is preferably in a range of 0.2 to 15%
by mass. If the total content of Y and the second additive element exceeds this range,
the specific resistance and permeability of the ZnO vapor deposition material are
significantly lowered.
[0318]
When a very small amount of Y as a first additive element and the second
additive element is contained in the ZnO vapor deposition material, Y as a first additive
element and the second additive element do not exist as granular precipitates in grain
boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor
deposition material. It is considered that, in the ZnO vapor deposition material, the first
additive element and the second additive element are present as oxides.
[0319]
The ZnO vapor deposition material of this aspect contains Y, which is a trivalent
rare earth element, as a first additive element, and Y causes excess carrier electrons to be
generated with respect to divalent Zn, such that high conductivity can be ensured.
When a rare earth element is added to the ZnO vapor deposition material, compositional
shift at the time of deposition is unlikely to occur, and a desired composition ratio can be
maintained when a film is formed.
[0320]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage by
the addition of Y which is a rare earth element, since the ZnO vapor deposition material
of this aspect contains the second additive element, high conductivity like ITO can be
obtained.
[0321]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in production costs. If the porosity exceeds 50%,
the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient
mechanical strength. If the porosity is equal to or greater than 10%, the evaporation
speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor
deposition material having an evaporation speed about two times higher than the
conventional ZnO vapor deposition material can be obtained.
[0322]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0323]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0324]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0325]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0326]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0327]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, Y2O3 powder in such
an amount that the Y content in the ZnO vapor deposition material is in a range of 0.1 to
14.9% by mass, an oxide powder of a second additive element in such an amount that the
content of the second additive element in the ZnO vapor deposition material is in a range
of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a
concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a
gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous
granulation powder having an average grain size of 50 to 300 µm, molding the porous
granulation powder to obtain a porous molded body, and sintering the porous molded
body at a predetermined temperature to obtain a porous ZnO sintered body.
[0328]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0329]
With regard to the Y2O3 powder, considering the prevention of maldistribution of
the Y powder, reactivity with a ZnO matrix, and the purity of a Y compound, it is
preferable to add Y oxide grains whose primary grain size is of a nanometer scale. The
oxide powder of the second additive element preferably has an average grain size of 0.01
to 1 µm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 µm.
If the oxide powder of the second additive element having this average grain size is used,
it is beneficial in terms of the uniform dispersion of the oxide powder of the second
additive element.
[0330]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0331]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0332]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0333]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0334]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0335]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0336]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, YO2 powder, and Al2O3 powder, or may
be added upon slurry preparation.
[0337]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0338]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0339]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0340]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about two times. Therefore, a high speed of film formation
can be obtained.
[0341]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of oxide powder of the first additive element and the second additive element is
significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO
powder, so oxide powder of the first additive element and the second additive element
may be outside the limitation of the grain size distribution.
[0342]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0343]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0344]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0345]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0346]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0347]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5x10-4 O cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO.
[0348]
In the ZnO vapor deposition material of this aspect, the crystal structure distorted
by the addition of Y having an ion radius larger than Zn is recovered and aligned by
addition of the second additive element having a small ion radius, such as B, Al, or Ga,
or Sc having high reactivity is added to recover a film having a regulated crystal structure.
Therefore, a dense film can be formed, and the durability of the film can also be
improved.
[0349]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0350]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[0351]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed of a sintered
body containing ZnO as a major component, wherein the sintered body contains a first
additive element and a second additive element, the first additive element is one or more
elements selected from the group consisting of Pr, Nd, Pm, and Sm, the second additive
element is one or more elements selected from the group consisting of B, Al, Ga, and Sc,
the content of the first additive element is in a range of 0.1 to 14.9% by mass, the content
of the second additive element is in a range of 0.1 to 10% by mass, the content of the first
additive element is higher than the content of the second additive element, and the
sintered body is a porous sintered body having a porosity of 3 to 50%.
[0352]
The inventors have investigated in detail the effect on conductivity due to
additive species and the content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence on conductivity due to the species and content of one or more first
additive elements selected from the group consisting of Pr, Nd, Pm, and Sm and one or
more second additive elements selected from the group consisting of B, Al, Ga, and Sc in
the porous ZnO sintered body. Based on the above-described knowledge, the ZnO
vapor deposition material according to this aspect contains ZnO as a major component,
and also contains the first additive elements and the second additive elements, such that
excess electrons contributing to conduction are developed in large amounts and
maintained, thereby forming a ZnO film having high conductivity.
[0353]
The ZnO vapor deposition material of this aspect contains the first additive
element and the second additive element together, the first additive element is one or
more rare earth elements selected from the group consisting of Pr, Nd, Pm, and Sm, and
the second additive element is one or more elements selected from B, Al, Ga, and Sc.
Of the second additive elements, B, Al, and Ga have an ion radius smaller than the first
additive element (rare earth element), so crystals distorted by the addition of the first
additive element having an ion radius larger than Zn are recovered and aligned by adding
the second additive element, such as B, Al, or Ga, or the crystal structure distorted by the
addition of the first additive element is recovered and aligned by adding Sc having high
reactivity as the second additive element. For this reason, a ZnO film having high
permeability, excellent denseness, high conductivity, and excellent durability can be
formed.
[0354]
As the ratio of the first additive element and the second additive element in the
porous ZnO sintered body increases within a predetermined range, the conductivity of the
ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely
deteriorates. Specifically, the content of the first additive element in the ZnO vapor
deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in
a range of 3 to 6% by mass. If the content of the first additive element is lower than the
lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the
content of the first additive element exceeds the upper limit value, 14.9% by mass, the
permeability is significantly lowered.
[0355]
The content of the second additive element in the ZnO vapor deposition material
is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3%
by mass. If the content of the second additive element is lower than the lower limit
value, 0.1% by mass, the conductivity is significantly lowered. If the content of the
second additive element exceeds the upper limit value, 10% by mass, compositional shift
at the time of deposition occurs.
[0356]
The ZnO vapor deposition material of this aspect contains a larger amount of the
first additive element than the second additive element, such that a dense crystal structure
is maintained. If the content of the first additive element is lower than that of the
second additive element, the conductivity and permeability are lowered. The total
content of the first additive element and the second additive element is preferably in a
range of 0.2 to 15% by mass. If the total content of the first additive element and the
second additive element exceeds this range, the specific resistance and permeability of
the ZnO vapor deposition material are significantly lowered.
[0357]
When a very small amount of the first additive element and the second additive
element is contained in the ZnO vapor deposition material, the first additive element and
the second additive element do not exist as granular precipitates in grain boundaries or
grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition
material. It is considered that, in the ZnO vapor deposition material, the first additive
element and the second additive element are present as oxides.
[0358]
The ZnO vapor deposition material of this aspect contains the first additive
element, which is a trivalent or quadrivalent rare earth element, and the first additive
element causes excess carrier electrons to be generated with respect to divalent Zn, such
that high conductivity can be ensured. When a rare earth element is added to the ZnO
vapor deposition material, compositional shift at the time of deposition is unlikely to
occur, and a desired composition ratio can be maintained when a film is formed.
[0359]
According to the ZnO vapor deposition material of this aspect, the conductivity is
obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually,
oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film
composition is insufficient. At the time of transparent conductive film formation, a
technique is conventionally used in which resistance is lowered by generating oxygen
defect. However, in the case of adding a rare earth element, it is easy to control because
the element is excellent in evaporation performance. In addition to this advantage by
the addition of the first additive element which is a rare earth element, since the ZnO
vapor deposition material of this aspect contains the second additive element, high
conductivity like ITO can be obtained.
[0360]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in production costs. If the porosity exceeds 50%,
the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient
mechanical strength. If the porosity is equal to or greater than 10%, the evaporation
speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor
deposition material having an evaporation speed about two times higher than the
conventional ZnO vapor deposition material can be obtained.
[0361]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0362]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0363]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0364]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 µm, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 µm, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0365]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disc-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to
handle the vapor deposition material in an actual production process.
[0366]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of a
first additive element in such an amount that the content of the first additive element in
the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide
powder of a second additive element in such an amount that the content of the second
additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by
mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to
75% by mass, blowing gas into the slurry to obtain a gas-containing slurry, spray-drying
the gas-containing slurry to obtain a porous granulation powder having an average grain
size of 50 to 300 µm, molding the porous granulation powder to obtain a porous molded
body, and sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
[0367]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0368]
With regard to the oxide powder of the first additive element, considering the
prevention of maldistribution of powder of the first additive element, reactivity with a
ZnO matrix, and the purity of a compound of the first additive element, it is preferable to
add oxide grains whose primary grain size is of a nanometer scale. The oxide powder
of the second additive element preferably has an average grain size of 0.01 to 1 µm, and
still more preferably, the average grain size is in a range of 0.05 to 0.5 µm. If the oxide
powder of the second additive element having this average grain size is used, it is
beneficial in terms of the uniform dispersion of the oxide powder of the second additive
element.
[0369]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0370]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0371]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0372]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0373]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0374]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0375]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, oxide powder of the first additive
element, and Al2O3 powder, or may be added upon slurry preparation.
[0376]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0377]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0378]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0379]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about 2.5 times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0380]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of oxide powder of the first additive element and Al2O3 powder is significantly smaller
than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide
powder of the first additive element and Al2O3 powder may be outside the limitation of
the grain size distribution.
[0381]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0382]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0383]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0384]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0385]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0386]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material of this aspect, so the ZnO film has high conductivity with
specific resistance of 3 to 5X10-4 O cm and high permeability with visible light
permeability equal to or greater than 90%, like ITO.
[0387]
In the ZnO vapor deposition material of this aspect, the crystal structure distorted
by the addition of the first additive element (rare earth element) having an ion radius
larger than Zn is recovered and aligned by addition of the second additive element having
a small ion radius, such as B, Al, or Ga, or Sc having high reactivity is added to recover a
film having a regulated crystal structure. Therefore, a dense film can be formed, and
the durability of the film can also be improved.
[0388]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0389]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[0390]
Next, another aspect of the present invention will be described.
[ZnO vapor deposition material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition
material for formation of a transparent conductive film which is composed of a ZnO
sintered body having a ZnO purity equal to or greater than 98%, wherein the sintered
body contains one or more additive elements selected from the group consisting of Y, La,
Sc, Ce, Pr, Nd, Pm, and Sm, and the sintered body is a porous sintered body having a
porosity of 3 to 50%.
[0391]
The inventors have investigated in detail the effect on conductivity due to
additive species and the content in a ZnO vapor deposition material and a ZnO film
formed by using the vapor deposition material, and have found that there is a significant
level of influence on conductivity due to the species and content of one or more additive
elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm in the
porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor
deposition material according to this aspect contains ZnO as a major component, and also
contains the additive elements, such that excess electrons contributing to conduction are
developed in large amounts and maintained, thereby forming a ZnO film having high
conductivity.
[0392]
The ZnO vapor deposition material of this aspect is composed of a ZnO sintered
body having a ZnO purity equal to or greater than 98%, preferably equal to or greater
than 98.4%, and more preferably equal to or greater than 99 %. If the ZnO purity is
smaller than 98%, the conductivity is lowered by the effect of impurities. The ZnO
sintered body may be monocrystal or polycrystal.
[0393]
The ZnO sintered body contains one or more additive elements selected from the
group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm. The additive element includes a
misch metal (also indicated by Mm) which is a mixture with La, Ce, or Nd as a major
component.
[0394]
As the concentration of the additive elements in the porous ZnO sintered body
increases, the conductivity of the ZnO film becomes better, and if the concentration
further increases, the conductivity adversely deteriorates. Thus, there is an optimum
concentration range for obtaining a ZnO film having high conductivity. Specifically,
the content of the additive elements is appropriately in a range of 2 to 20% by mass, and
preferably, in a range of 3 to 6% by mass. If the content of the additive elements is
lower than 2% by mass, the conductivity is not improved. If the content of the additive
elements exceeds 20% by mass, the conductivity is lowered and the permeability is
deteriorated.
[0395]
Since a very small amount of the additive elements is contained, the additive
elements do not exist as granular precipitates in grain boundaries or grains in the ZnO
matrix but are uniformly dispersed in the ZnO sintered body. The additive elements
exist in the ZnO vapor deposition material as oxide. For example, Y is present as Y2O3,
and La is present as La2O3. Sc is present as SC2O3, and Ce is present as CeO2 or Ce2O3.
Pr is present as Pr6O11, and Nd is present as Nd2O3. Pm is present as Pm2O3, and Sm is
present as Sm2O3.
[0396]
The ZnO vapor deposition material of this aspect contains a tri- or quadri- or
more valent rare earth element, and the rare earth element can cause excess carrier
electrons to be generated with respect to divalent Zn. When a rare earth element is
added to the ZnO vapor deposition material, compositional shift at the time of deposition
is unlikely to occur, and a desired composition ratio can be maintained when a film is
formed.
[0397]
In general, as a mechanism for obtaining the conductivity, oxygen defect is used,
as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced
in a vapor deposition method, but generally oxygen in the film composition is
insufficient. At the time of transparent conductive film formation, a technique is
conventionally used in which resistance is lowered by generating oxygen defect.
However, in the case of adding a rare earth element, it is easy to control because the
element is excellent in evaporation performance. With this advantage, the present
invention uses an additive element other than Al or Ga, thereby obtaining conductivity
like ITO.
[0398]
The ZnO vapor deposition material of this aspect is composed of a porous ZnO
sintered body having a porosity of 3 to 50%. The porosity of the sintered body is
appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably
in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the
porosity is smaller than 3%, it is not preferable since, at the time of film formation by an
electron beam deposition method or an ion plating method, the evaporation speed of the
vapor deposition material does not increase, and as a result, the speed of film formation
decreases, which results in an increase in production costs. If the porosity exceeds 50%,
the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient
mechanical strength. If the porosity is equal to or greater than 10%, the evaporation
speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor
deposition material having an evaporation speed about two times higher than the
conventional ZnO vapor deposition material can be obtained.
[0399]
In the porous ZnO sintered body of this aspect, the pores preferably have an
average pore diameter of 0.1 to 500 µm. If the average pore diameter of the pores is
within the above-described range, the evaporation speed can be further increased. If the
pore diameter is smaller than 0.1 µm, there is no merit in the pores. If the pore diameter
exceeds 500 µm, it is not preferable because the strength of the sintered body is lowered,
which causes damages due to EB (electron beam) irradiation, that is, splash.
[0400]
The term "pore diameter" (the inner diameter of the pore) refers to, for example,
the maximum value of the internal dimensions in the pores when the sectional portion of
the vapor deposition material is observed by observation means, such as SEM or the like.
As the evaluation method of the pores, measurement of porosity by a substitution method,
measurement of porosity by microscopy, measurement of surface area and micropore
distribution by gas absorption, measurement of surface area and micropore distribution
by a mercury intrusion method, measurement of surface area by a gas permeation method,
or measurement of micropore distribution by an X-ray small-angle scattering method
may be used.
[0401]
The pores are preferably rounded, and in terms of improvement in the
evaporation speed, micropores are preferably formed at the surface of the pores. For the
evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g,
and at least one peak of the micropore distribution is present within a range of 1 to 100 µm. Portions (frame portion) other than the pores are preferably substantially sintered.
For example, the frame portion of the porous sintered body preferably has a density equal
to or greater than 98%.
[0402]
In the porous ZnO sintered body of this aspect, it is preferable that grains
preferably have an average crystal grain size of 1 to 500 µm, and rounded pores of about
0.1 to 500 µm are provided in the sintered body. The porous ZnO sintered body has a
fine crystal structure in which the average crystal grain size is within the above-described
range, and the occurrence of defects in the boundary of crystal grains can be reduced.
Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density,
thickness distribution, refractive index, sputtering resistance, discharge characteristics
(discharge voltage, discharge responsiveness, and the like), insulation characteristics, and
the like. If the average crystal grain size is smaller than 1 |am, the speed of film
formation is lowered. If the average crystal grain size exceeds 500 u.m, the deposition
rate of the additive element is not uniform. The average crystal grain size is preferably
in a range of 5 to 40 µm, and more preferably, in a range of 10 to 30 µm.
[0403]
The ZnO vapor deposition material of this aspect is preferably molded in the
form of disc-like or circular pellets. When the vapor deposition material has a circular
shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30
mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is
excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30
mm, it is difficult to handle the vapor deposition material in an actual production process.
When the vapor deposition material is disk-like, the diameter of the vapor deposition
material is appropriately in a range of 5 to 50 mm, and preferably, in a range of 5 to 10
mm. The height of the vapor deposition material is in a range of 1 to 30 mm, and
preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small
and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash
occurs, and if the diameter exceeds 50 mm or the height exceeds 30 mm, upon deposition,
a uniform film is not formed and the film formation speed is lowered due to the decrease
in the filling ratio to a hearth (vapor deposition material crucible).
[0404]
Hereinafter, a process for producing a ZnO vapor deposition material according
to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by
mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of
additive elements, a binder, and an organic solvent to prepare a slurry with a
concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a
gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous
granulation powder having an average grain size of 50 to 300 µm, molding the porous
granulation powder to obtain a porous molded body, and sintering the porous molded
body at a predetermined temperature to obtain a porous ZnO sintered body.
[0405]
The ZnO powder preferably has purity equal to or greater than 98%, more
preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater
than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of
conductivity by the effect of impurities can be suppressed. The average grain size of
the ZnO powder is in a range of 0.1 to 10 µm. When the average grain size of the ZnO
powder is smaller than 0.1 µm, the powder is excessively fine and aggregated, so there is
a tendency that the handling of the powder becomes worse, and it is difficult to prepare a
high-concentration slurry. When the average grain size exceeds 10 µm, there is a
tendency that it is difficult to control the micro-structure, and a dense pellet is hard to
obtain. If the average grain size of the ZnO powder is adjusted to the above-described
range, a desired sintered body is also obtained without using a sintering auxiliary agent.
[0406]
With regard to the oxide powder of the additive element, considering the
prevention of maldistribution of the powder, reactivity with a ZnO matrix, and the purity
of a compound of the additive element, it is preferable to add oxide grains whose primary
grain size is of a nanometer scale. The oxide powder of the additive element preferably
has an average grain size of 0.01 to 1 µm, and still more preferably, the average grain
size is in a range of 0.05 to 0.5 µm. If the oxide powder of the additive element having
this average grain size is used, it is beneficial in terms of the uniform dispersion of the
oxide powder of the additive element.
[0407]
Oxide powder is used in such an amount that the content of the additive elements
in the ZnO sintered body is in a range of 2 to 20% by mass, and preferably, in a range of
3 to 6% by mass, and oxide powder of the additive elements are mixed in ZnO powder to
prepare raw powder.
[0408]
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It
is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol,
propanol, or the like may be used.
[0409]
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry
with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the
slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system,
stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is
difficult to obtain a dense ZnO sintered body having a uniform composition. If the
slurry concentration is adjusted within the above-described range, the viscosity of the
slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray
drier can be performed stably. Further, the density of a molded body increases, such
that a dense sintered body can be obtained.
[0410]
Wet blending of raw powder, a binder, and an organic solvent, and in particular,
wet blending of raw powder and an organic solvent as a dispersion medium is preferably
performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the
wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls
having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If
the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the
diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the
blending time is long, up to 24 hours, impurities are hardly generated due to milling.
On the other hand, when a resin ball with a metal support is used in the wet ball mill, a
ball having a diameter of 10 to 15 mm is preferably used.
[0411]
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having
a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller
than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are
increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling
leads to the generation of impurities. Sufficient blending can be done within 1 hour.
Blending/granulation of powder and additives may be performed by a general tumbling
granulation method. In this case, it is not necessary to perform a separation operation
from the balls or the like after the process, and thus the process is simplified.
[0412]
In the production process of this aspect, as a first step for obtaining a porous
sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry.
Gas blowing and mixing is preferably performed by blowing using a mechanical pump,
gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like
may be used.
[0413]
The gas-containing slurry is spray-dried. The spray drying is preferably
performed at 150 to 250°C for 3 hours by using a spray drier. Since gas is blown into
the slurry, the granulation powder obtained by spray-drying the slurry is porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0414]
In the production process of this aspect, as a second step for obtaining a porous
sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming
agent, an organic foaming agent or an inorganic foaming agent may be used. For the
organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the
like is used, and for the inorganic foaming agent, carbonate or the like is used. The
foaming agent may be mixed with ZnO powder, oxide powder of the first additive
element, and Al2O3 powder, or may be added upon slurry preparation.
[0415]
The foaming agent-containing slurry is spray-dried. The spray drying is
preferably performed at 150 to 250°C for 3 hours by using a spray drier. The foaming
agent contained in the slurry is foamed and dissolved upon this spray drying, such that
resultant granulation powder is made porous. Through the spray drying, a porous
granulation powder having an average grain size of 50 to 300 µm can be obtained.
[0416]
In the production process of this aspect, as a third step for obtaining a porous
sintered body, a slurry is prepared in which an additive, which will be volatized and
dissolved upon sintering, is mixed. Examples of the additive include butyral capable of
being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a
polyester-based additive, a polyethylene-based additive, and the like capable of being
dissolved in an alcohol-based solvent. Examples of the additive which will not be
dissolved in the alcohol-based solvent include a starch-based additive and a
polystyrene-based additive having an average grain size of about several µm to 500 µm.
It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is
mixed in the slurry at about 20% by mass.
[0417]
If the slurry contains the additive, the additive is volatized and dissolved upon
sintering to form pores, thereby obtaining a porous sintered body. The diameter and
shape of the pores can be controlled by adjusting the kind and amount of the additive.
For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 µm to 10 µm order can be formed. When starch is used, pores having the same pore
diameter as the grain size of starch and the same shape as starch can be formed. Thus,
when starch is used, the pore diameter and shape of the pores can be more easily
controlled.
[0418]
Specifically, in the case of the ZnO vapor deposition material of this aspect, a
vapor deposition material using a butyral-based additive can obtain a deposition speed
about 1.3 times higher than the evaporation speed of the conventional ZnO vapor
deposition material having relative density equal to or greater than about 98%, and a
vapor deposition material using starch having an average grain size of 0.1 to 500 µm can
obtain an evaporation speed about 2.5 times higher than the evaporation speed of the
conventional ZnO vapor deposition material having relative density equal to or greater
than about 98%. Therefore, a high speed of film formation can be obtained.
[0419]
In the production process of this aspect, as a fourth step for obtaining a porous
sintered body, a slurry using ZnO powder having a grain size distribution within a
predetermined range is prepared. Specifically, ZnO powder having an average grain
size of 10 to 500 µm and a grain size distribution within a range of ±10% of the average
grain size is used. If the grain size distribution of ZnO powder is outside the range of
±10% of the average grain size, the porosity is lowered. More preferably, the grain size
distribution is within a range of ±5% of the average grain size. The preferred grain size
of oxide powder of the first additive element and Al2O3 powder is significantly smaller
than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide
powder of the first additive element and Al2O3 powder may be outside the limitation of
the grain size distribution.
[0420]
The slurry using ZnO powder with a controlled grain size distribution is
spray-dried. The spray drying is preferably performed at 150 to 250°C for 3 hours by
using a spray drier. In the slurry to be spray-dried, ZnO powder having an average
grain size of 10 to 500 µm and a grain size distribution within a range of ±10% of the
average grain size is used, and no fine ZnO powder is substantially contained. Thus,
there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps
between ZnO grains remain as pores, and granulation powder becomes porous.
Through the spray drying, a porous granulation powder having an average grain size of
50 to 300 µm can be obtained.
[0421]
After the slurry is spray-dried to obtain a granulation powder having an average
grain size of 50 to 300 µm, the granulation powder is molded under a predetermined
pressure. If the average grain size of the granulation powder is smaller than 50 µm,
moldability deteriorates, and if the average grain size is larger than 300 µm, the density
of the molded body is lowered, and the strength is likely to be insufficient.
[0422]
For a pressing molding device, a uniaxial press device, a cold isostatic press
(CIP) molding device, or other devices may be used. The molding pressure is
appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to
1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the
above-described range, such that the density of the molded body can be increased,
deformation after sintering can be suppressed, and postprocessing is not required.
[0423]
Next, the molded body is sintered. Before sintering, the molded body is
preferably degreased at a temperature of 350 to 620°C. Through this degreasing, spots
on the molded body after sintering can be suppressed. The degreasing is preferably
performed for a sufficient time.
[0424]
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a
reductive gas at a temperature equal to or higher than 1000°C, and preferably, at a
temperature of 1200 to 1400°C for 1 to 10 hours, and preferably, for 2 to 5 hours. The
sintering is performed under air pressure, but in the case of pressure sintering, such as hot
press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably
performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature
equal to or higher than 1000°C for 1 to 5 hours.
[0425]
A ZnO film is formed on the surface of the substrate by a vacuum film formation
method with a ZnO vapor deposition material composed of the resultant porous sintered
body as a target material. As the vacuum film formation method suitable for forming a
film using the ZnO vapor deposition material of this aspect, an electron beam deposition
method, an ion plating method, a sputtering method, or a plasma deposition method may
be used. A ZnO film of this aspect formed by the film formation method uses the ZnO
vapor deposition material containing the additive elements, so the ZnO film having high
conductivity and visible light permeability is obtained.
[0426]
According to the production process of this aspect, in any of the first step of
mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry,
the third step of preparing the slurry containing the additive which will be volatized and
dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder
having a grain size distribution within a predetermined range, the porosity, pore diameter,
and pore shape can be easily controlled. Therefore, a vapor deposition material having
optimum pores can be produced. As a result, even when a large number of pore states
are required by the production conditions or the like, an optimum vapor deposition
material can be provided to cope with the requirements.
[0427]
The ZnO vapor deposition material of this aspect is composed mainly of a porous
sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 µm, so
when a ZnO transparent conductive film is formed by an electron beam deposition
method or an ion plating method using the ZnO vapor deposition material, the
evaporation speed can be improved. That is, when film formation is performed with the
same electron beam energy, the speed of film formation increases, and the operation time
is shortened, thereby increasing the number of products for a predetermined time.
Further, when film formation is performed at the same film formation speed, electron
beam energy is reduced, and the replacement timing of a filament of an electron gun or
the like is delayed, such that the number of times of maintenance is reduced and
productivity is improved. As a result, production costs can be reduced.
[Examples]
[0428]
Hereinafter, Example A Group of the present invention will be described together
with Comparative Example A Group. In Example A and Comparative Example A,
commercially available ZnO powder (having a purity equal to or greater than 99% and an
average grain size of 0.3 µm), CeO2 powder (having a purity equal to or greater than 99%
and an average grain size of 0.3 µm), and Al2O3 powder (having a purity equal to or
greater than 99% and an average grain size of 0.3 µm) were used. In any case, a slurry
was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to
20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding
press device was used as the molding device, and molded bodies having an outer
diameter of 6.7 mmF and a thickness of 2.0 mm were molded under pressure of 100
kgf/cm (9.8 MPa). The molded bodies were put in an electric furnace and calcinated
under air pressure at 1300°C for 3 hours, thereby obtaining sintered body pellets.
[0429]
In Example A and Comparative Example A, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25 °C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0430]
[Example A1]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 91 g of ZnO powder, 6.2 g of CeO2 powder, and 2.8 g of Al2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and a molded body was calcinated, thereby producing
porous sintered body pellets (ZnO vapor deposition material). The porosity, average
pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
[0431]
[Example A2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
the same raw powder as in Example Al, 1% by mass of polyvinyl butyral as a binder was
added, and methylated alcohol was further added as a dispersion medium, thereby
obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For
the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine
were used, and for the inorganic foaming agent, carbonate was used. The foaming
agent-containing slurry was put in a ball mill, wet blending was performed, then, the
slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a
vacuum drier at 80°C, thereby obtaining porous granulation powder having an average
grain size of 200 µm. The granulation powder was molded under a predetermined
pressure and calcinated, thereby producing porous sintered body pellets (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 1.
[0432]
[Example A3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of the same raw powder as in Example Al, 1% by mass of polyvinyl butyral was
added as a binder, and methylated alcohol was further added as a dispersion medium,
thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by
mass. For the additive which will be volatized and dissolved upon calcination, 20% by
mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball
mill, wet blending was performed, then, the slurry was dry-comminuted after the
dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated such that the additive was volatized and dissolved, thereby producing porous
sintered body pellets (ZnO vapor deposition material). The porosity, average pore
diameter, and average crystal grain size of the sintered body are shown in Table 1.
[0433]
[Example A4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example A3 except that, for the additive which will be volatized
and dissolved upon calcination, 20% by mass of starch having a grain size of 50 µm was
used. The porosity, average pore diameter, and average crystal grain size of the sintered
body are shown in Table 1.
[0434]
[Example A5]
The same raw powder as in Example Al was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1 % by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 1.
[0435]
[Comparative Example A1 ]
The same raw powder as in Example Al was used, a slurry was prepared in the
same manner as in Example Al except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 1.
[0436]
[Comparative Example A2]
A slurry was prepared in the same manner as in Comparative Example Al except
that 100 g of ZnO powder containing no CeO2 powder and Al2O3 powder was used, and
the slurry was spray-dried, thereby obtaining granulation powder having an average grain
size of 200 µm. The granulation powder was molded under a predetermined pressure,
and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 1.
[0437]
[Deposition Test A]
A deposition test A was carried out using the ZnO vapor deposition materials of
Examples Al to A5 and the ZnO vapor deposition materials of Comparative Examples
Al and A2. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66X10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mm*)) was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 1. As shown in Table 1, in Examples A1 to A5, the deposition speed is about 1.1
to 2 times higher than in Comparative Examples A1 and A2, and the evaporation speed is
higher.
[0438]
[Moisture Resistance Test A]
For the samples of Examples A1 to A5 and Comparative Examples A1 and A2, a
moisture resistance test A was performed. In the moisture resistance test A, the
resistance value of a film was measured hourly for 2000 hours in an atmosphere of
humidity 60% and temperature 90°C. The results are shown in Table 2. As shown in
Table 2, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor
deposition material containing Ce and Al, the deterioration rate of specific resistance is
several times lower than a ZnO film containing no Ce and Al. This indicates that a ZnO
film containing Ce and Al is several times more stable .
[0439]
[Examples A6 to A8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example Al except that adjustment was done such that the Ce
content was 0.2% by mass, the Al content was 0.1% by mass, and the porosity was in a
range of 8 to 31%.
[0440]
[Examples A9 to A11 ]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example Al except that adjustment was done such that the Ce
content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a
range of 9 to 30%.
[0441]
[Comparative Example A3]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples A6 to A8 except that adjustment was done such that the
porosity was 2%.
[0442]
[Comparative Example A4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples A9 to Al 1 except that adjustment was done such that
the porosity was 2%.
[0443]
[Comparative Examples A5 to A8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example A1 except that adjustment was done such that the Ce
content was 20% by mass, the Al content was 15% by mass, and the porosity was in a
range of 2 to 29%.
[0444]
For the samples of Examples A6 to Al 1 and Comparative Examples A3 to A8, the
deposition test A was performed. The results are shown in Table 3. As shown in Table
3, similar to Table 1, in Examples A6 to Al 1, the ZnO vapor deposition material has a
high evaporation speed and excellent specific resistance, as compared with Comparative
Example A Group. On the other hand, in Comparative Examples A2, A3, A4, and A8
having a small porosity, the evaporation speed is considerably low at 13.0 to 14.7. In
Comparative Examples A5 to A8 in which the Ce content and the Al content are high, the
ZnO film has very large specific resistance and considerably low permeability.
[0448]
[Example B]
Hereinafter, Example B Group of this aspect will be described together with
Comparative Example B Group. In Example B and Comparative Example B,
commercially available ZnO powder (having a purity equal to or greater than 99% and an
average grain size of 0.3 µm), CeO2 powder (having a purity equal to or greater than 99%
and an average grain size of 0.3 µm), and Ga2O3 powder (having a purity equal to or
greater than 99% and an average grain size of 0.3 µm) were used. In any case, a slurry
was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to
20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding
press device was used as the molding device, and molded bodies having an outer
diameter of 6.7 mmF and a thickness of 2.0 mm were molded under pressure of 100
kgf/cm (9.8 MPa). The molded bodies were put in an electric furnace and calcinated
under air pressure at 1300°C for 3 hours, thereby obtaining sintered body pellets.
[0449]
In Example B and Comparative Example B, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25°C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0450]
[Example B1]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 91 g of ZnO powder, 6.2 g of CeO2 powder, and 2.8 g of Ga2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 4.
[0451]
[Example B2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
the same raw powder as in Example Bl, 1% by mass of polyvinyl butyral as a binder was
added, and methylated alcohol was further added as a dispersion medium, thereby
obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For
the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine
were used, and for the inorganic foaming agent, carbonate was used. The foaming
agent-containing slurry was put in a ball mill, wet blending was performed, then, the
slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a
vacuum drier at 80°C, thereby obtaining porous granulation powder having an average
grain size of 200 µm. The granulation powder was molded under a predetermined
pressure, and the molded bodies were calcinated, thereby producing porous sintered body
pellets (ZnO vapor deposition material). The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 4.
[0452]
[Example B3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of the same raw powder as in Example B1, 1% by mass of polyvinyl butyral was
added as a binder, and methylated alcohol was further added as a dispersion medium,
thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by
mass. For the additive which will be volatized and dissolved upon calcination, 20% by
mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball
mill, wet blending was performed, then, the slurry was dry-comminuted after the
dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated such that the additive was volatized and dissolved, thereby producing porous
sintered body pellets (ZnO vapor deposition material). The porosity, average pore
diameter, and average crystal grain size of the sintered body are shown in Table 4.
[0453]
[Example B4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example B3 except that, for the additive which will be volatized
and dissolved upon calcination, 20% by mass of starch having a grain size of 50 µm was
used. The porosity, average pore diameter, and average crystal grain size of the sintered
body are shown in Table 4.
[0454]
[Example B5]
The same raw powder as in Example B1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1 % by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 4.
[0455]
[Comparative Example B1]
The same raw powder as in Example B1 was used, a slurry was prepared in the
same manner as in Example B1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 4.
[0456]
[Comparative Example B2]
A slurry was prepared in the same manner as in Comparative Example B1 except
that raw powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO
powder, and no Ga2O3 powder was added, and the slurry was spray-dried, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material).
The porosity, average pore diameter, and average crystal grain size of the sintered body
are shown in Table 4.
[0457]
[Comparative Example B3]
A slurry was prepared in the same manner as in Comparative Example B1 except
that 100 g of ZnO powder containing no CeO2 powder and Ga2O3 powder was used, and
the slurry was spray-dried, thereby obtaining granulation powder having an average grain
size of 200 µm. The granulation powder was molded under a predetermined pressure,
and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 4.
[0458]
[Deposition Test B]
A deposition test B was carried out using the ZnO vapor deposition materials of
Examples Bl to B5 and the ZnO vapor deposition materials of Comparative Examples
B1 to B3. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 5.
[0459]
As shown in Tables 4 and 5, in Examples Bl to B5, the evaporation speed is high,
as compared with Comparative Example Bl. In Comparative Examples B2 to B3, the
evaporation speed is the same as in Example B5, but the specific resistance is large and
the conductivity is low.
[0460]
[Moisture Resistance Test B]
For the samples of Examples Bl to B5 and Comparative Examples Bl and B3, a
moisture resistance test B was performed. The moisture resistance test B was
performed for 2000 hours in an atmosphere of humidity 60% and temperature 90°C.
The specific resistance of a film was measured hourly. The results are shown in Table
6.
[0461]
As shown in Table 6, with regard to the moisture resistance of a ZnO film formed
of a ZnO vapor deposition material containing Ce and Ga, the deterioration rate of
specific resistance is several times lower than a ZnO film containing no Ce and Ga.
This indicates that a ZnO film containing Ce and Ga is several times more stable .
[0462]
[Examples B6 to B8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example B1 except that adjustment was done such that the Ce
content was 0.2% by mass, the Ga content was 0.1% by mass, and the porosity was in a
range of 8 to 30%.
[0463]
[Examples B9 to B11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example B1 except that adjustment was done such that the Ce
content was 14.9% by mass, the Ga content was 10% by mass, and the porosity was in a
range of 10 to 32%.
[0464]
[Comparative Example B4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples B6 to B8 except that adjustment was done such that the
porosity was 2%.
[0465]
[Comparative Example B5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples B9 to B11 except that adjustment was done such that
the porosity was 2%.
[0466]
[Comparative Examples B6 to B9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example B1 except that adjustment was done such that the Ce
content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a
range of 2 to 31%.
[0467]
For the samples of Examples B6 to B11l and Comparative Examples B4 to B9, a
deposition test B was performed. The results are shown in Table 7. As shown in Table
7, similar to Table 4, in Examples B6 to B11, the ZnO vapor deposition material has a
high evaporation speed and excellent specific resistance, as compared with Comparative
Example B. On the other hand, in Comparative Examples B4, B5, and B9 having a
small porosity, the evaporation speed is considerably low at 13.0 to 14.1. In
Comparative Examples B6 to B9 in which the Ce content and the Ga content are high,
the ZnO film has very large specific resistance and considerably low permeability.
[0472]
[Example C]
Hereinafter, Example C Group of this aspect will be described together with
Comparative Example C Group. In Example C and Comparative Example C,
commercially available ZnO powder (having a purity equal to or greater than 99% and an
average grain size of 0.3 µm), CeO2 powder (having a purity equal to or greater than 99%
and an average grain size of 0.3 µm), and SC2O3 powder (having a purity equal to or
greater than 99% and an average grain size of 0.3 µm) were used. In any case, a slurry
was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to
20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding
press device was used as the molding device, and molded bodies having an outer
diameter of 6.7 mmF and a thickness of 2.0 mm were molded under pressure of 100
kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated
under air pressure at 1300°C for 3 hours, thereby obtaining sintered body pellets.
[0473]
In Example C and Comparative Example C, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25°C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0474]
[Example C1]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 90.8 g of ZnO powder, 6.2 g of CeO2 powder, and 3.0 g of Sc2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 8.
[0475]
[Example C2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
the same raw powder as in Example C1, 1% by mass of polyvinyl butyral as a binder was
added, and methylated alcohol was further added as a dispersion medium, thereby
obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For
the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine
were used, and for the inorganic foaming agent, carbonate was used. The foaming
agent-containing slurry was put in a ball mill, wet blending was performed, then, the
slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a
vacuum drier at 80°C, thereby obtaining porous granulation powder having an average
grain size of 200 µm. The granulation powder was molded under a predetermined
pressure, and the molded bodies were calcinated, thereby producing porous sintered body
pellets (ZnO vapor deposition material). The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 8.
[0476]
[Example C3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of the same raw powder as in Example C1, 1% by mass of polyvinyl butyral was
added as a binder, and methylated alcohol was further added as a dispersion medium,
thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by
mass. For the additive which will be volatized and dissolved upon calcination, 20% by
mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball
mill, wet blending was performed, then, the slurry was dry-comminuted after the
dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated such that the additive was volatized and dissolved, thereby producing porous
sintered body pellets (ZnO vapor deposition material). The porosity, average pore
diameter, and average crystal grain size of the sintered body are shown in Table 8.
[0477]
[Example C4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example C3 except that, for the additive which will be volatized
and dissolved upon calcination, 20% by mass of starch having a grain size of 50 µm was
used. The porosity, average pore diameter, and average crystal grain size of the sintered
body are shown in Table 8.
[0478]
[Example C5]
The same raw powder as in Example C1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1 % by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 8.
[0479]
[Comparative Example C1]
The same raw powder as in Example C1 was used, a slurry was prepared in the
same manner as in Example C1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 8.
[0480]
[Comparative Example C2]
A slurry was prepared in the same manner as in Example C1 except that raw
powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO powder
and no SC2O3 powder was added, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 8.
[0481]
[Comparative Example C3]
A slurry was prepared in the same manner as in Example C1 except that 100 g of
ZnO powder containing no CeO2 powder and SC2O3 powder was used, and the slurry was
spray-dried, thereby obtaining granulation powder having an average grain size of 200 µm.
The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 8.
[0482]
[Deposition Test C]
A deposition test C was carried out using the ZnO vapor deposition materials of
Examples C1 to C5 and the ZnO vapor deposition materials of Comparative Examples
C1 to C3. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10+6 Torr) and O2 partial pressure
1.33x 10-2 Pa (1.0x 10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 9.
[0483]
As shown in Tables 8 and 9, in Examples C1 to C5, the evaporation speed is
higher than in Comparative Example C1. In Comparative Examples C2 and C3, the
evaporation speed is the same as in Example C5, but the specific resistance is large and
the conductivity is low.
[0484]
[Moisture Resistance Test C]
For the samples of Examples C1 to C5 and Comparative Examples C1 and C3, a
moisture resistance test C was performed. The moisture resistance test C was
performed for 2000 hours in an atmosphere of humidity 60% and temperature 90°C.
The specific resistance of a film was measured hourly. The results are shown in Table
10.
[0485]
As shown in Table 10, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing Ce and Sc, the deterioration rate of
specific resistance is several times lower than a ZnO film containing no Ce and Sc.
This indicates that a ZnO film containing Ce and Sc is several times more stable .
[0486]
[Examples C6 to C8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example C1 except that adjustment was done such that the Ce
content was 0.2% by mass, the Sc content was 0.1 % by mass, and the porosity was in a
range of 78 to 28%.
[0487]
[Examples C9 to C11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example C1 except that adjustment was done such that the Ce
content was 14.9% by mass, the Sc content was 10% by mass, and the porosity was in a
range of 9 to 30%.
[0488]
[Comparative Example C4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples C6 to C8 except that adjustment was done such that the
porosity was 2%.
[0489]
[Comparative Example C5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples C9 to C11 except that adjustment was done such that
the porosity was 2%.
[0490]
[Comparative Examples C6 to C9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example C1 except that adjustment was done such that the Ce
content was 20% by mass, the Sc content was 15% by mass, and the porosity was in a
range of 2 to 28%.
[0491]
For the samples of Examples C6 to C1 1 and Comparative Examples C4 to C9, a
deposition test C was performed. The results are shown in Table 11. As shown in
Table 11, similar to Table 8, in Examples C6 to C1 1, the ZnO vapor deposition material
has a high evaporation speed and excellent specific resistance, as compared with
Comparative Example C. On the other hand, in Comparative Examples C4, C5, and C9
having a small porosity, the evaporation speed is considerably low at 13.8 to 14.9. In
Comparative Examples C6 to C9 in which the Ce content and the Sc content are high, a
ZnO film has very large specific resistance and considerably low permeability.
I
[Example D]
Hereinafter, Example D Group of this aspect will be described together with
Comparative Example D Group. In Example D and Comparative Example D,
commercially available ZnO powder (having a purity equal to or greater than 99% and
average grain size of 0.3 µm), CeO2 powder (having a purity equal to or greater than 99%
and an average grain size of 0.3 µm), and B2O3 powder (having a purity equal to or
greater than 99% and an average grain size of 0.3 µm) were used. In any case, a slurry
was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to
20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding
press device was used as the molding device, and molded bodies having an outer
diameter of 6.7 mmF and a thickness of 2.0 mm were molded under pressure of 100
kgf/cm (9.8 MPa). The molded bodies were put in an electric furnace and calcinated
under air pressure at 1300°C for 3 hours, thereby obtaining sintered body pellets.
[0497]
In Example D and Comparative Example D, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25 °C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0498]
[Example Dl]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 90 g of ZnO powder, 6.2 g of CeO2 powder, and 3.8 g of B2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 12.
[0499]
[Example D2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
the same raw powder as in Example Dl, 1% by mass of polyvinyl butyral as a binder was
added, and methylated alcohol was further added as a dispersion medium, thereby
obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For
the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine
were used, and for the inorganic foaming agent, carbonate was used. The foaming
agent-containing slurry was put in a ball mill, wet blending was performed, then, the
slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a
vacuum drier at 80°C, thereby obtaining porous granulation powder having an average
grain size of 200 µm. The granulation powder was molded under a predetermined
pressure, and the molded bodies were calcinated, thereby producing porous sintered body
pellets (ZnO vapor deposition material). The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 12.
[0500]
[Example D3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of the same raw powder as in Example Dl, 1% by mass of polyvinyl butyral was
added as a binder, and methylated alcohol was further added as a dispersion medium,
thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by
mass. For the additive which will be volatized and dissolved upon calcination, 20% by
mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball
mill, wet blending was performed, then, the slurry was dry-comminuted after the
dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated such that the additive was volatized and dissolved, thereby producing porous
sintered body pellets (ZnO vapor deposition material). The porosity, average pore
diameter, and average crystal grain size of the sintered body are shown in Table 12.
[0501]
[Example D4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example D3 except that, for the additive which will be volatized
and dissolved upon calcination, 20% by mass of starch having a grain size of 50 µm was
used. The porosity, average pore diameter, and average crystal grain size of the sintered
body are shown in Table 12.
[0502]
[Example D5]
The same raw powder as in Example D1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1 % by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 12.
[0503]
[Comparative Example Dl]
The same raw powder as in Example D1 was used, a slurry was prepared in the
same manner as in Example D1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 12.
[0504]
[Comparative Example D2]
A slurry was prepared in the same manner as in Example D1 except that raw
powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO powder
and no B2O3 powder was added, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 12.
[0505]
[Comparative Example D3]
A slurry was prepared in the same manner as in Example D1 except that 100 g of
ZnO powder containing no CeO2 powder and B2O3 powder was used, and the slurry was
spray-dried, thereby obtaining granulation powder having an average grain size of 200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 12.
[0506]
[Deposition Test D]
A deposition test D was carried out using the ZnO vapor deposition materials of
Examples D1 to D5 and the ZnO vapor deposition materials of Comparative Examples D1 to D3. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 13.
[0507]
As shown in Tables 12 and 13, in Examples D1 to D5, the evaporation speed is
higher than in Comparative Example D1. In Comparative Examples D2 and D3, the
evaporation speed is the same as in Example D5, but the specific resistance is large and
the conductivity is low.
[0508]
[Moisture Resistance Test D]
For the samples of Examples D1 to D5 and Comparative Examples D1 and D3, a
moisture resistance test D was performed. The moisture resistance test D was
performed for 2000 hours in an atmosphere of humidity 60% and temperature 90°C.
The specific resistance of a film was measured hourly. The results are shown in Table
14.
[0509]
As shown in Table 14, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing Ce and B, the deterioration rate of
specific resistance is several times lower than a ZnO film containing no Ce and B. This
indicates that a ZnO film containing Ce and B is several times more stable .
[0510]
[Examples D6 to D8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example D1 except that adjustment was done such that the Ce
content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a
range of 9 to 30%.
[0511]
[Examples D9 to D11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example D1 except that adjustment was done such that the Ce
content was 14.9% by mass, the B content was 10% by mass, and the porosity was in a
range of 10 to 33%.
[0512]
[Comparative Example D4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples D6 to D8 except that adjustment wad done such that the
porosity was 2%.
[0513]
[Comparative Example D5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples D9 to D1 1 except that adjustment was done such that
the porosity was 2%.
[0514]
[Comparative Examples D6 to D9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example D1 except that adjustment was done such that the Ce
content was 20% by mass, the B content was 15% by mass, and porosity was in a range
of2to31%.
[0515]
For the samples of Examples D6 to D1 1 and Comparative Examples D4 to D9, a
deposition test D was performed. The results are shown in Table 15. As shown in
Table 15, similar to Table 12, in Examples D6 to D1 1, a ZnO vapor deposition material
has high evaporation speed and excellent specific resistance, as compared with
Comparative Example D. On the other hand, in Comparative Examples D4, D5, and D9
having a small porosity, the evaporation speed is considerably low at 14.0 to 14.5. In
Comparative Examples D6 to D9 in which the Ce content and the B content are high, a
ZnO film has very large specific resistance and considerably low permeability.
[0520]
[Example E]
Hereinafter, Example E Group of this aspect will be described together with
Comparative Example E Group. In Example E and Comparative Example E,
commercially available ZnO powder, La2O3 powder, B2O3 powder, Al2O3 powder, Ga2O3
powder, and Sc2O3 powder were used. Any powder has purity equal to or greater than
99% and an average grain size of 0.3 µm.
[0521]
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel
ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours.
In any case, a uniaxial molding press device was used as the molding device, and molded
bodies having an outer diameter of 6.7 mm(j) and a thickness of 2.0 mm were molded
under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric
furnace and calcinated under air pressure at 1300°C for 3 hours, thereby obtaining
sintered body pellets.
[0522]
In Example E and Comparative Example E, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25 °C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0523]
[Example El]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 90.4 g of ZnO powder, 5.8 g of La2O3 powder, and 3.8 g of B2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 16.
[0524]
[Example E2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
a raw powder containing 91.4 g of ZnO powder, 5.8 g of La2O3 powder, and 2.8 g of
Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated
alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity
200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent,
azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the
inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was
put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after
the dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining porous granulation powder having an average grain size of 200 µm. The
granulation powder was molded under a predetermined pressure, and the molded bodies
were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition
material). The porosity, average pore diameter, and average crystal grain size of the
sintered body are shown in Table 16.
[0525]
[Example E3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of a raw powder containing 91.4 g of ZnO powder, 5.8 g of La2O3 powder, and 2.8
g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and
methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry
(viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive
which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl
butyral was used. The additive-containing slurry was put in a ball mill, wet blending
was performed, then, the slurry was dry-comminuted after the dispersion medium in the
slurry was vaporized by a vacuum drier at 80°C, thereby obtaining granulation powder
having an average grain size of 200 µm. The granulation powder was molded under a
predetermined pressure, and the molded bodies were calcinated such that the additive
was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 16.
[0526]
[Example E4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example E3 except that 100 g of a raw powder containing 91.2 g
of ZnO powder, 5.8 g of La2O3 powder, and 3.0 g of SC2O3 powder was used and, for the
additive which will be volatized and dissolved upon calcination, 20% by mass of starch
having a grain size of 50 µm was used. The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 16.
[0527]
[Example E5]
The same raw powder as in Example E1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1 % by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 16.
[0528]
[Comparative Example E1]
The same raw powder as in Example E1 was used, a slurry was prepared in the
same manner as in Example E1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 16.
[0529]
[Comparative Example E2]
A slurry was prepared in the same manner as in Example E1 except that raw
powder was used in which 5.8 g of La2O3 powder was added to 95.2 g of ZnO powder
and no oxide powder of the second additive element was added, and the slurry was
spray-dried, thereby obtaining granulation powder having an average grain size of 200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 16.
[0530]
[Comparative Example E3]
A slurry was prepared in the same manner as in Example E1 except that 100 g of
ZnO powder containing no LaO2 powder as a first additive element and no oxide powder
of the second additive element was used, and the slurry was spray-dried, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material).
The porosity, average pore diameter, and average crystal grain size of the sintered body
are shown in Table 16.
[0531]
[Deposition Test E]
A deposition test E was carried out using the ZnO vapor deposition materials of
Examples E1 to E5 and the ZnO vapor deposition materials of Comparative Examples E1 to E3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm,
depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 17.
[0532]
As shown in Tables 16 and 17, in Examples E1 to E5, the evaporation speed is
higher than in Comparative Example El. In Comparative Examples E2 and E3, the
evaporation speed is the same as in Example E5, but the specific resistance is large and
the conductivity is low.
[0533]
[Moisture Resistance Test E]
For the samples of Examples E1 to E5 and Comparative Examples E1 and E3, a
moisture resistance test E was performed. The moisture resistance test E was performed
for 2000 hours in an atmosphere of humidity 60% and temperature 90°C. The specific
resistance of a film was measured hourly. The results are shown in Table 18.
[0534]
As shown in Table 18, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing La and B, Al, Ga, or Sc, the
deterioration rate of specific resistance is several times lower than a ZnO film containing
no elements described above. This indicates that a ZnO film containing La and B, Al,
Ga, or Sc is several times more stable .
[0535]
[Examples E6 to E8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example E1 except that adjustment was done such that the La
content was 0.2% by mass, the B content was 0.1 % by mass, and the porosity was in a
range of 10 to 28%.
[0536]
[Examples E9 to E11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example E1 except that adjustment was done such that the La
content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a
range of 8 to 32%.
[0537]
[Comparative Example E4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples E6 to E8 except that adjustment was done such that the
porosity was 2%.
[0538]
[Comparative Example E5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples E9 to E1 1 except that adjustment was done such that the
porosity was 2%.
[0539]
[Comparative Examples E6 to E9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example E1 except that adjustment was done such that the La
content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a
range of 2 to 30%.
[0540]
For the samples of Examples E6 to E11 and Comparative Examples E4 to E9, a
deposition test E was performed. The results are shown in Table 19. As shown in
Table 19, similar to Table 16, in Examples E6 to E11, the ZnO vapor deposition material
has a high evaporation speed and excellent specific resistance, as compared with
Comparative Example E. On the other hand, in Comparative Examples E4, E5, and E9
having a small porosity, the evaporation speed is considerably low at 13.0 to 14.1. In
Comparative Examples E6 to E9 in which the La content and the Ga content are high, a
ZnO film has very large specific resistance and considerably low permeability.
[0545]
[Example F]
Hereinafter, Example F Group of this aspect will be described together with
Comparative Example F Group. In Example F and Comparative Example F,
5 commercially available ZnO powder, Y2O3 powder, B2O3 powder, Al2O3 powder, Ga2O3
powder, and SC2O3 powder were used. Any powder has purity equal to or greater than
99% and an average grain size of 0.3 µm.
[0546]
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel
10 ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours.
In any case, a uniaxial molding press device was used as the molding device, and molded
bodies having an outer diameter of 6.7 mmF and a thickness of 2.0 mm were molded
under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric
furnace and calcinated under air pressure at 1300°C for 3 hours, thereby obtaining
15 sintered body pellets.
[0547]
In Example F and Comparative Example F, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
20 speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25°C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 ran) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0548]
[Example F1]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 91.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 3.8 g of B2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 20.
[0549]
[Example F2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
a raw powder containing 92.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 2.8 g of
Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated
alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity
200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent,
azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the
inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was
put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after
the dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining porous granulation powder having an average grain size of 200 µm. The
granulation powder was molded under a predetermined pressure, and the molded bodies
were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition
material). The porosity, average pore diameter, and average crystal grain size of the
sintered body are shown in Table 20.
[0550]
[Example F3]
An additive which will be volatized and dissolved upon calcination was added to
100 gofa raw powder containing 92.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 2.8
g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and
methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry
(viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive
which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl
butyral was used. The additive-containing slurry was put in a ball mill, wet blending
was performed, then, the slurry was dry-comminuted after the dispersion medium in the
slurry was vaporized by a vacuum drier at 80°C, thereby obtaining granulation powder
having an average grain size of 200 µm. The granulation powder was molded under a
predetermined pressure, and the molded bodies were calcinated such that the additive
was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 20.
[0551]
[Example F4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example F3 except that 100 g of a raw powder containing 92.0 g
of ZnO powder, 5.0 g of Y2O3 powder, and 3.0 g of Sc2O3 powder was used and, for the
additive which will be volatized and dissolved upon calcination, 20% by mass of starch
having a grain size of 50 µm was used. The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 20.
[0552]
[Example F5]
The same raw powder as in Example F1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distribution
within a range of 55 to 65 µm was obtained. 1% by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size of
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 20.
[0553]
[Comparative Example F1]
The same raw powder as in Example F1 was used, a slurry was prepared in the
same manner as in Example F1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 20.
[0554]
[Comparative Example F2]
A slurry was prepared in the same manner as in Example F1 except that raw
powder was used in which 5.0 g of Y2O3 powder was added to 95 g of ZnO powder and
no oxide powder of the second additive element was added, and the slurry was
spray-dried, thereby obtaining granulation powder having an average grain size of 200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 20.
[0555]
[Comparative Example F3]
A slurry was prepared in the same manner as in Example Fl except that 100 g of
ZnO powder containing no YO2 powder as a first additive element and no oxide powder
of the second additive element was used, and the slurry was spray-dried, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material).
The porosity, average pore diameter, and average crystal grain size of the sintered body
are shown in Table 20.
[0556]
[Deposition Test F]
A deposition test F was carried out using the ZnO vapor deposition materials of
Examples F1 to F5 and the ZnO vapor deposition materials of Comparative Examples F1 to F3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm,
depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x 10-2 Pa (1.0x 10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 21.
[0557]
As shown in Tables 20 and 21, in Examples F1 to F5, the evaporation speed is
higher than in Comparative Example F1. In Comparative Examples F2 and F3, the
evaporation speed is the same as in Example F5, but the specific resistance is large and
the conductivity is low.
[0558]
[Moisture Resistance Test F]
For the samples of Examples F1 to F5 and Comparative Examples F1 and F3, a
moisture resistance test F was performed. The moisture resistance test F was performed
for 2000 hours in an atmosphere of humidity 60% and temperature 90°C. The specific
resistance of a film was measured hourly. The results are shown in Table 22.
[0559]
As shown in Table 22, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing Y and B, Al, Ga, or Sc, the
deterioration rate of specific resistance is several times lower than a ZnO film containing
no elements described above. This indicates that a ZnO film containing Y and B, Al, Ga,
or Sc is several times more stable .
[0560]
[Examples F6 to F8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example F1 except that adjustment was done such that the Y
content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a
range of 9 to 30%.
[0561]
[Examples F9 to F11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example F1 except that adjustment was done such that the Y
content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a
range of 9 to 30%.
[0562]
[Comparative Example F4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples F6 to F8 except that adjustment was done such that the
porosity was 2%.
[0563]
[Comparative Example F5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples F9 to F1 1 except that adjustment was done such that the
porosity was 2%.
[0564]
[Comparative Examples F6 to F9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example F1 except that adjustment was done such that the Y
content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a
range of 5 to 29%.
[0565]
For the samples of Examples F6 to F1 1 and Comparative Examples F4 to F9, a
deposition test F was performed. The results are shown in Table 23. As shown in
Table 23, similar to Table 20, in Examples F6 to F1 1, the ZnO vapor deposition material
has a high evaporation speed and excellent specific resistance, as compared with
Comparative Example F. On the other hand, in Comparative Examples F4, F5, and F9
having a small porosity, the evaporation speed is considerably low at 14.2 to 14.4. In
Comparative Examples F6 to F9 in which the Ce content and the Ga content are high, a
ZnO film has very large specific resistance and considerably low permeability.
[0570]
[Example G]
Hereinafter, Example G Group of this aspect will be described together with
Comparative Example G Group. In Example G and Comparative Example G,
commercially available ZnO powder, Pr6O11 powder, B2O3 powder, Al2O3 powder, Ga2O3
powder, and SC2O3 powder were used. Any powder has purity equal to or greater than
99% and an average grain size of 0.3 µm.
[0571]
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel
ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours.
In any case, a uniaxial molding press device was used as the molding device, and molded
bodies having an outer diameter of 6.7 mmF and a thickness of 2.0 mm were molded
under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric
furnace and calcinated under air pressure at 1300°C for 3 hours, thereby obtaining
sintered body pellets.
[0572]
In Example G and Comparative Example G, the porosity was measured by a
substitution method. The measurement of the average pore diameter and the crystal
grain size was performed by SEM (Scanning Electron Microscopy). The evaporation
speed was measured by a quartz crystal thickness monitor provided obliquely above the
hearth. The specific resistance was measured by a four-terminal four-probe method
with the application of a constant current at 25 °C in an atmosphere by using Loresta
(trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5
mm pitch) as the measuring instrument. The visible light permeability was measured by
placing the substrate after film formation vertically to measurement light for a visible
wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by
Hitachi, Ltd. as the measuring instrument.
[0573]
[Example G1]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 91.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 3.8 g of B2O3 powder, and
methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry
with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was
blown into the slurry, and wet blending was performed, thereby obtaining a
gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in
the slurry was vaporized by a vacuum drier at 80°C, thereby obtaining porous granulation
powder having an average grain size of 200 µm. The granulation powder was molded
under a predetermined pressure, and the molded bodies were calcinated, thereby
producing porous sintered body pellets (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 24.
[0574]
[Example G2]
An organic foaming agent and an inorganic foaming agent were added to 100 g of
a raw powder containing 92.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 2.8 g of
Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated
alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity
200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent,
azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the
inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was
put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after
the dispersion medium in the slurry was vaporized by a vacuum drier at 80°C, thereby
obtaining porous granulation powder having an average grain size of 200 µm. The
5 granulation powder was molded under a predetermined pressure, and the molded bodies
were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition
material). The porosity, average pore diameter, and average crystal grain size of the
sintered body are shown in Table 24.
[0575]
10 [Example G3]
An additive which will be volatized and dissolved upon calcination was added to
100 g of a raw powder containing 92.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 2.8
g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and
methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry
15 (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive
which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl
butyral was used. The additive-containing slurry was put in a ball mill, wet blending
was performed, then, the slurry was dry-comminuted after the dispersion medium in the
slurry was vaporized by a vacuum drier at 80°C, thereby obtaining granulation powder
20 having an average grain size of 200 µm. The granulation powder was molded under a
predetermined pressure, and the molded bodies were calcinated such that the additive
was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 24.
[0576]
[Example G4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example G3 except that 100g of a raw powder containing 92.0 g
of ZnO powder, 5.0 g of Pr6O11 powder, and 3.0 g of Sc2O3 powder was used and, for the
additive which will be volatized and dissolved upon calcination, 20% by mass of starch
having a grain size of 50 µm was used. The porosity, average pore diameter, and
average crystal grain size of the sintered body are shown in Table 24.
[0577]
[Example G5]
The same raw powder as in Example G1 was used, and ZnO powder was filtered
such that ZnO powder having an average grain size of 60 µm and a grain size distributior
within a range of 55 to 65 µm was obtained. 1% by mass of polyvinyl butyral as a
binder and also 30% by mass of methylated alcohol as an organic solvent were added to
raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in
which the concentration of ZnO powder was 30% by mass. Next, the slurry was
spray-dried, thereby obtaining porous granulation powder having an average grain size o:
200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). The porosity, average pore diameter, and average crystal
grain size of the sintered body are shown in Table 24.
[0578]
[Comparative Example G1]
The same raw powder as in Example G1 was used, a slurry was prepared in the
same manner as in Example G1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity,
average pore diameter, and average crystal grain size of the sintered body are shown in
Table 24.
[0579]
[Comparative Example G2]
A slurry was prepared in the same manner as in Example Gl except that raw
powder was used in which 5.0 g of Pr6O11 powder was added to 95 g of ZnO powder and
no oxide powder of the second additive element was added, and the slurry was
spray-dried, thereby obtaining granulation powder having an average grain size of 200 µm. The granulation powder was molded under a predetermined pressure, and the
molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor
deposition material). The porosity, average pore diameter, and average crystal grain
size of the sintered body are shown in Table 24.
[0580]
[Comparative Example G3]
A slurry was prepared in the same manner as in Example Gl except that 100 g of
ZnO powder containing no oxide powder of the first additive element and no oxide
powder the second additive element was used, and the slurry was spray-dried, thereby
obtaining granulation powder having an average grain size of 200 µm. The granulation
powder was molded under a predetermined pressure, and the molded bodies were
calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material).
The porosity, average pore diameter, and average crystal grain size of the sintered body
are shown in Table 24.
[0581]
[Deposition Test G]
A deposition test G was carried out using the ZnO vapor deposition materials of
Examples G1 to G5 and the ZnO vapor deposition materials of Comparative Examples G1 to G3. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0.x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 25.
[0582]
As shown in Tables 24 and 25, in Examples G1 to G5, the evaporation speed is
higher than in Comparative Example G1. In Comparative Examples G2 and G3, the
evaporation speed is the same as in Example G5, but the specific resistance is large and
the conductivity is low.
[0583]
[Moisture Resistance Test G]
For the samples of Examples G1 to G5 and Comparative Examples G1 and G3, a
moisture resistance test G was performed. The moisture resistance test G was
performed for 2000 hours in an atmosphere of humidity 60% and temperature 90°C.
The specific resistance of a film was measured hourly. The results are shown in Table
26.
[0584]
As shown in Table 26, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing Pr and B, Al, Ga, or Sc, the
deterioration rate of specific resistance is several times lower than a ZnO film containing
no elements described above. This indicates that a ZnO film containing Pr and B, Al,
Ga, or Sc is several times more stable .
[0585]
[Examples G6 to G8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example G1 except that adjustment was done such that the Pr
content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a
range of 10 to 31%.
[0586]
[Examples G9 to G11]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example G1 except that adjustment was done such that the Pr
content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a
range of 9 to 32%.
[0587]
[Comparative Example G4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples G6 to G8 except that adjustment was done such that the
porosity was 2%.
[0588]
[Comparative Example G5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples G9 to G1 1 except that adjustment was done such that
the porosity was 2%.
[0589]
[Comparative Examples G6 to G9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example G1 except that adjustment was done such that the Pr
content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a
range of 2 to 31%.
[0590]
For the samples of Examples G6 to G1 1 and Comparative Examples G4 to G9, a
deposition test G was performed. The results are shown in Table 27. As shown in
Table 27, similar to Table 24, in Examples G6 to G11, the ZnO vapor deposition material
has a high evaporation speed and excellent specific resistance, as compared with
Comparative Example G. On the other hand, in Comparative Examples G4, G5, and G9
having a small porosity, the evaporation speed is considerably low at 14.2 to 14.4. In
Comparative Examples G6 to G9 in which the Pr content and the Ga content are high, a
ZnO film has very large specific resistance and considerably low permeability.
?
[Example H]
Hereinafter, Example H Group of this aspect will be described together with
Comparative Example H Group. In Example H and Comparative Example H,
commercially available ZnO powder, Ce oxide powder, Y oxide powder, La oxide
powder, Pr oxide powder, Nd oxide powder, Pm oxide powder, and Sm oxide powder
were used. Any powder has purity equal to or greater than 99% and an average grain
size of 0.3 µm.
[0596]
A slurry was prepared by using a ball mill (with a nylon-coated steel ball having a
diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a
uniaxial molding press device was used as a molding device, and a molded body was
molded under pressure of 100 kgf/cm (9.8 MPa). The molded bodies were put in an
electric furnace and calcinated under air pressure at 1300°C for 3 hours, thereby forming
a plate-shaped (vertical 5 mmxhorizontal 5 mmxthickness 2 mm) sintered body (ZnO
vapor deposition material). In Example H and Comparative Example H, the porosity
was measured by a substitution method. The measurement of the average pore diameter
and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The
evaporation speed upon film formation was measured by a quartz crystal thickness
monitor provided obliquely above the hearth.
[0597]
A ZnO film was formed of the ZnO vapor deposition material to have a thickness
of 200 nm on a glass substrate by an electron beam deposition method. The film
formation conditions were that an ultimate vacuum was 1.0x10-4 Pa, oxygen gas partial
pressure was 1.0x 10-2 Pa, and substrate temperature was 200°C. The evaporation speed
upon film formation was measured by a quartz crystal thickness monitor provided
obliquely above the hearth. The specific resistance and visible light permeability of the
formed ZnO film were measured. The specific resistance was measured by a
four-terminal four-probe method with the application of a constant current at a so-called
normal temperature of 25 °C in an atmosphere by using Loresta (trademark) from
Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the
measuring instrument. The permeability was measured by placing the substrate after
film formation vertically to measurement light for a visible wavelength band (380 to 780
nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the
measuring instrument. The results were shown in Tables 28 and 29.
[0598]
[Example HI]
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder
containing 93.8 g of ZnO powder and 6.2 g of CeO2 powder, and methylated alcohol as a
dispersion medium was further added, thereby obtaining a slurry with a concentration of
30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and
wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was
dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum
drier at 80°C, thereby obtaining porous granulation powder having an average grain size
of 200 µm. The granulation powder was molded under a predetermined pressure, and
the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO
vapor deposition material). A ZnO Film was formed of the ZnO vapor deposition
material.
[0599]
[Example H2]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.0 g of SC2O3 powder was used instead
of CeO2 powder, and a foaming agent was added instead of blowing air into the slurry.
A ZnO film was formed of the ZnO vapor deposition material.
[0600]
[Example H3]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.0 g of Y2O3 powder was used instead of
CeO2 powder, and a foaming agent was added instead of blowing air into the slurry. A
ZnO film was formed of the ZnO vapor deposition material.
[0601]
[Example H4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.8 g of La2O3 powder was used instead
of CeO2 powder, and an additive which will be volatized and dissolved upon calcination
was added instead of blowing air into the slurry. A ZnO film was formed of the ZnO
vapor deposition material.
[0602]
[Example H5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.0 g of Pr6O11 powder was used instead
of CeO2 powder, and starch was used as an additive, which will be volatized and
dissolved upon calcination, instead of blowing air into the slurry. A ZnO film was
formed of the ZnO vapor deposition material.
[0603]
[Example H6]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.0 g of Nd2O3 powder was used instead
of CeO2 powder, and an additive which will be volatized and dissolved upon calcination
was used instead of blowing air into the slurry. A ZnO film was formed of the ZnO
vapor deposition material.
[0604]
[Example H7]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that 5.0 g of Pr2O3 powder was used instead
of CeO2 powder, and a foaming agent was added instead of blowing air into the slurry.
A ZnO film was formed of the ZnO vapor deposition material.
[0605]
[Example H8]
5.0 g of Sm2O3 powder was used instead of CeO2 powder, and ZnO powder was
filtered such that ZnO powder having an average grain size of 60 µm and a grain size
distribution of 55 to 65 µm was obtained instead of blowing air into the slurry. 1% by
mass of polyvinyl butyral as a binder and 30% by mass of methylated alcohol as an
organic solvent were added to mixed raw powder of the ZnO powder and Sm oxide
powder and mixed, thereby preparing a slurry in which the concentration of ZnO powder
was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby producing porous sintered body pellets (ZnO vapor deposition material). A
ZnO film was formed of the ZnO vapor deposition material.
[0606]
[Comparative Example H1]
The same raw powder as in Example H1 was used, a slurry was prepared in the
same manner as in Example H1 except that introduction of air into the slurry, addition of
a foaming agent, and use of an additive which will be volatized and dissolved upon
calcination were not performed, and the slurry was spray-dried, thereby obtaining
granulation powder having an average grain size of 200 µm. The granulation powder
was molded under a predetermined pressure, and the molded bodies were calcinated,
thereby preparing a sintered body pellet (ZnO vapor deposition material). A ZnO film
was formed of the ZnO vapor deposition material.
[0607]
[Comparative Example H2]
A slurry was prepared in the same manner as in Example H1 except that 100 g of
ZnO powder was used and no oxide powder of the additive elements was added, and the
slurry was spray-dried, thereby obtaining granulation powder having an average grain
size of 200 µm. The granulation powder was molded under a predetermined pressure,
and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO
vapor deposition material). A ZnO film was formed of the ZnO vapor deposition
material.
[0608]
[Deposition Test]
A deposition test was carried out using the ZnO vapor deposition materials of
Examples H1 to H5 and the ZnO vapor deposition materials of Comparative Examples
H1 to H3. A vapor deposition material as a sample was put in the hearth (diameter 50
mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an
atmosphere of an ultimate vacuum 2.66x10-4 Pa (2.0x10-6 Torr) and O2 partial pressure
1.33x10-2 Pa (1.0x10-4 Torr), and an electron beam with an acceleration voltage of 10 kV
and a beam scan area of about 40 mmF was irradiated to heat the ZnO vapor deposition
material, thereby forming a ZnO film. The evaporation speed was measured by a quartz
crystal thickness monitor provided obliquely above the hearth. The results are shown in
Table 29.
[0609]
As shown in Tables 28 and 29, in Examples H1 to H5, the evaporation speed is
higher than in Comparative Example H1. In Comparative Examples H2 and H3, the
evaporation speed is the same as in Example H5, but the specific resistance is large and
the conductivity is low.
[0610]
[Moisture Resistance Test]
For the samples of Examples H1 to H5 and Comparative Examples H1 and H2, a
moisture resistance test was performed. The moisture resistance test was performed for
2000 hours in an atmosphere of humidity 60% and temperature 90°C. The specific
resistance of a film was measured hourly. The results are shown in Table 30.
[0611]
As shown in Table 30, with regard to the moisture resistance of a ZnO film
formed of a ZnO vapor deposition material containing Ce, Sc, Y, La, Pr, Nd, Pm, or Sm,
the deterioration rate of specific resistance is several times lower than a ZnO film
containing no elements described above. This indicates that a ZnO film containing Ce,
Sc, Y, La, Pr, Nd, Pm, or Sm is several times more stable .
[0612]
[Examples H6 to H8]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that adjustment was done such that the Ce
content was 0.2% by mass, the Nd content was 0.1% by mass, and the porosity was in a
range of 10 to 29%.
[0613]
[Examples H9 to H1 1]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that adjustment was done such that the Ce
content was 14.9% by mass, the Pm content was 10% by mass, and the porosity was in a
range of 10 to 31%.
[0614]
[Comparative Example H4]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples H6 to H8 except that adjustment was done such that the
porosity was 2%.
[0615]
[Comparative Example H5]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Examples H9 to H1 1 except that adjustment was done such that
the porosity was 2%.
[0616]
[Comparative Examples H6 to H9]
A porous sintered body pellet (ZnO vapor deposition material) was produced in
the same manner as in Example H1 except that adjustment was done such that the Ce
content was 20% by mass, the Sm content was 15% by mass, and the porosity was in a
range of 8 to 30%.
[0617]
For the samples of Examples H6 to H11 and Comparative Examples H4 to H9, a
deposition test was performed. The results are shown in Table 31. As shown in Table
31, similar to Table 28, in Examples H6 to H11, the ZnO vapor deposition material has a
high evaporation speed and excellent specific resistance, as compared with Comparative
Example H. On the other hand, in Comparative Examples H4, H5, and H9 having a
small porosity, the evaporation speed is considerably low at 14.8 to 14.9. In
Comparative Examples H6 to H9 in which the Ce content and the Sm content are high, a
ZnO film has very large specific resistance and considerably low permeability.
Industrial Applicability
[0622]
According to the present invention, it is possible to form a ZnO film having high
permeability, excellent denseness, and high durability. Further, it is possible to obtain a
film having excellent moisture resistance and gas and vapor barrier properties.
Therefore, the present invention is industrially applicable.
CLAIMS
1. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a porous ZnO sintered body containing Ce and Al,
wherein the Ce content is higher than the Al content, the Ce content is in a range
of 0.1 to 14.9% by mass, the Al content is in a range of 0.1 to 10% by mass, and the
sintered body has a porosity of 3 to 50%.
2. A process for producing a ZnO vapor deposition material, the process comprising the
steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2
powder in such an amount that the Ce content in the ZnO vapor deposition material is in
a range of 0.1 to 14.9% by mass, Al2O3 powder in such an amount that the Al content in
the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an
organic solvent to prepare a slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
3. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a porous ZnO sintered body containing Ce and Ga,
wherein the Ce content is higher than the Ga content, the Ce content is in a range
of 0.1 to 14.9% by mass, the Ga content is in a range of 0.1 to 10% by mass, and the
sintered body has a porosity of 3 to 50%.
4. A process for producing a ZnO vapor deposition material, the process comprising the
steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2
powder in such an amount that the Ce content in the ZnO vapor deposition material is in
a range of 0.1 to 14.9% by mass, Ga2O3 powder in such an amount that the Ga content in
the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an
organic solvent to prepare a slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
5. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a porous ZnO sintered body containing Ce and Sc,
wherein the Ce content is higher than the Sc content, the Ce content is in a range
of 0.1 to 14.9% by mass, the Sc content is in a range of 0.1 to 10% by mass, and the
sintered body has a porosity of 3 to 50%.
6. A process for producing a ZnO vapor deposition material, the process comprising the
steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2
powder in such an amount that the Ce content in the ZnO vapor deposition material is in
a range of 0.1 to 14.9% by mass, Sc2O3 powder in such an amount that the Sc content in
the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an
organic solvent to prepare a slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
7. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a porous ZnO sintered body containing Ce and B,
wherein the Ce content is higher than the B content, the Ce content is in a range
of 0.1 to 14.9% by mass, the B content is in a range of 0.1 to 10% by mass, and the
sintered body has a porosity of 3 to 50%.
8. A process for producing a ZnO vapor deposition material, the process comprising the
steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2
powder in such an amount that the Ce content in the ZnO vapor deposition material is in
a range of 0.1 to 14.9% by mass, B2O3 powder in such an amount that the B content in
the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an
organic solvent to prepare a slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
9. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a sintered body containing ZnO as a major component,
wherein the sintered body contains La as a first additive element and a second
additive element, the second additive element is one or more elements selected from the
group consisting of B, Al, Ga, and Sc, the La content is in a range of 0.1 to 14.9% by
mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the
La content is higher than the content of the second additive element, and the sintered
body is a porous sintered body having a porosity of 3 to 50%.
10. A process for producing a ZnO vapor deposition material, the process comprising
the steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, La2O3
powder in such an amount that the La content in the ZnO vapor deposition material is in
a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such
an amount that the content of the second additive element in the ZnO vapor deposition
material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a
slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
11. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a sintered body containing ZnO as a major component,
wherein the sintered body contains Y as a first additive element and a second
additive element, the second additive element is one or more elements selected from the
group consisting of B, Al, Ga, and Sc, the Y content is in a range of 0.1 to 14.9% by mass,
the content of the second additive element is in a range of 0.1 to 10% by mass, the Y
content is higher than the content of the second additive element, and the sintered body is
a porous sintered body having a porosity of 3 to 50%.
12. A process for producing a ZnO vapor deposition material, the process comprising
the steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, Y2O3
powder in such an amount that the Y content in the ZnO vapor deposition material is in a
range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an
amount that the content of the second additive element in the ZnO vapor deposition
material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a
slurry with a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
13. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a sintered body containing ZnO as a major component,
wherein the sintered body contains a first additive element and a second additive
element, the first additive element is one or more elements selected from the group
consisting of Pr, Nd, Pm, and Sm, the second additive element is one or more elements
selected from the group consisting of B, Al, Ga, and Sc, the content of the first additive
element is in a range of 0.1 to 14.9% by mass, the content of the second additive element
is in a range of 0.1 to 10% by mass, the content of the first additive element is higher
than the content of the second additive element, and the sintered body is a porous
sintered body having a porosity of 3 to 50%.
14. A process for producing a ZnO vapor deposition material, the process comprising
the steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, an oxide
powder of a first additive element in such an amount that the content of the first additive
element in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an
oxide powder of a second additive element in such an amount that the content of the
second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10%
by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to
75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.
15. A ZnO vapor deposition material for formation of a transparent conductive film
comprising:
a ZnO sintered body having a ZnO purity equal to or greater than 98%,
wherein the sintered body contains one or more additive elements selected from
the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, and the sintered body is a
porous sintered body having a porosity of 3 to 50%.
16. A process for producing a ZnO vapor deposition material, the process comprising
the steps of:
(I) mixing ZnO powder having a purity equal to or greater than 98%, an oxide
powder of the additive elements, a binder, and an organic solvent to prepare a slurry with
a concentration of 30 to 75% by mass;
(II) blowing gas into the slurry to obtain a gas-containing slurry;
(III) spray-drying the gas-containing slurry to obtain a porous granulation powder
having an average grain size of 50 to 300 µm;
(IV) molding the porous granulation powder to obtain a porous molded body; and
(V) sintering the porous molded body at a predetermined temperature to obtain a
porous ZnO sintered body.




A ZnO vapor deposition material for use in the deposition of, e.g., a transparent conductive film. It consists mainly
of a porous ZnO sinter which contains one or more first additive elements selected among Ce, La, Y, Pr, Nd, Pm, and Sm and one
or more second additive elements selected among Al, Ga, Sc, and B. The content of the first additive elements is higher than that of
the second additive elements, and the content of the first additive elements and the content of the second additive elements are in the
ranges of 0.1-14.9 mass% and 0.1-10 mass%, respectively. The sinter has a porosity of 3-50%.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=EyKoR5gGzzXpx+sM9Kha5A==&loc=wDBSZCsAt7zoiVrqcFJsRw==


Patent Number 269631
Indian Patent Application Number 1088/KOLNP/2010
PG Journal Number 45/2015
Publication Date 06-Nov-2015
Grant Date 29-Oct-2015
Date of Filing 24-Mar-2010
Name of Patentee MITSUBISHI MATERIALS CORPORATION
Applicant Address 3-2, OTEMACHI 1-CHOME, CHIYODA-KU, TOKYO 100-8117, JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 MAYUZUMI, YOSHITAKA C/O MITSUBISHI MATERIALS CORPORATION, CENTRAL RESEARCH INSTITUTE, 1002-14, MUKOHYAMA, NAKA-SHI, IBARAKI 311-0102 JAPAN
PCT International Classification Number C23C 14/24
PCT International Application Number PCT/JP2008/067685
PCT International Filing date 2008-09-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2007-252759 2007-09-27 Japan
2 2008-245299 2008-09-25 Japan