Title of Invention

"SPUTTERING TARGET AND MANUFACTURING METHOD THEREFOR, AND RECORDABLE OPTICAL RECORDING MEDIUM"

Abstract SPUTTERING TARGET AND MANUFACTURING METHOD THEREFOR, AND RECORDABLE OPTICAL RECORDING MEDIUM To provide a sputtering target for preparing a recordable optical recording medium characterized by comprising Bi and B and a manufacturing method thereof, a recordable high density optical recording medium using the sputtering target, and a sputtering target which is capable of improving a speed of the film formation for the improvement of productivity, which has a high intensity at the time of the film formation and which has a heightened packing density.
Full Text

BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a sputtering target and a
manufacturing method thereof, the target being used for forming a film of an
oxide layer which is a constitution layer of a recordable optical recording
medium. Furthermore, the present invention relates to a recordable optical
recording medium manufactured by using the sputtering target, in particular,
a recordable optical recording medium which enables a high density
recording even in a blue laser wavelength area.
Description of the Related Art
In order to provide a recordable optical recording medium which
enables recording and reproduction using a laser beam with a wavelength the
same or less than that of a blue laser beam, extensive development is
underway for blue laser beams which enable ultra-high density recording,
along with development of recordable optical recording media to which
such blue laser beams can be used.
The present inventors propose the validity of a recording layer
containing as a main component a metal or a half metal oxide, in particular
bismuth oxide (see Japanese Patent Application Laid-Open (JP-A) Nos.
20O3-48375, 2005-161831, and 2005-108396) as a recordable optical
recording medium which enables high density recording at a wavelength the.

same as or less than the wavelength of the blue laser.
The applicant of the present invention discloses in the prior
application (Japanese Patent Application Laid-Open (JP-A) No.
2006-247897) a recordable optical recording medium which has a recording
layer containing as a main component of the constituent element bismuth
and containing bismuth oxide, the recording layer containing one or more
elements X selected from B, P, Ga, As, Se, Tc, Pd, Ag, Sb, Te, W, Re, Os, Ir,
Pt, Au, Hg, Tl, Po, At, and Cd. The applicant also discloses that the
recordable optical recording medium using a film including Bi, B, and oxide
has excellent characteristics, and that a sputtering method can be also used
as a method for forming this layer.
The sputtering method has been widely known as one of the
vapor-phase deposition techniques for thin film deposition. The method is
also used in an industrial thin film deposition. In the sputtering method, a
target material which has the same component as a film to be deposited is
prepared. Normally, argon gas ion which is generated by means of glow
discharge in the target material is then allowed to collide with this target
material with the result that the constituent atoms of the target material are
hammered out, and atoms are accumulated on the substrate with the result
that a film is formed. Since oxides generally have high melting points in
particular, a method such as vapor deposition is not favorable and thus a
radio frequency sputtering that involves application of a high frequency is

often used.
Sputtering has produced many results in the manufacturing process
and is favorable in a point of through-put. However, in the case where a
film made of material containing two or more elements is to be deposited,
the resultant film often has a different composition than its sputtering target,
thus requiring a consideration for determining the composition of the target.
Furthermore, the structure and the quality of the film often differ depending
on the form in which the compound constituting the target is contained; thus,
it is also required to consider this point.
Furthermore, it is also required to further improve the film
deposition rate from the viewpoint of the production cost. For increased
film deposition rate, it is required to introduce a large power. In this case as
well, it is required to improve the target strength so as to avoid destruction of
the target.
As a known technology, for example, Japanese Patent Application
Laid-Open (JP-A) No. 11-92922 discloses a Bi-based oxide target as a
sputtering target for the formation of a dielectric film. However, this
document does not describe a target containing B. If the kinds of
constituent elements are different, so is the relationship between the
composition and constituent compounds of the aforementioned target and
the structure and composition of the deposited film. Consequently, it is
required to change the composition of the target. The information

disclosed in this document does not constitute a reference of the present
invention.
Furthermore, the Publication of the Japanese Patent Application
Laid-Open (JP-A) No. 2005-264206 discloses a description of a Bi2O3-based
glass-like target containing B2O3. However, the invention in this document
inevitably contains SiO2 and is associated with the glass-like target with the
result that the invention in the document is different from the present
invention.
SUMMARY OF THE INVENTION
In order to realize a recordable optical recording medium which
enables high density recording, a film which contains Bi ,B and oxygen and
which has a stable composition and structure is required. For this purpose,
an appropriate sputtering target is required. However, the form and the
structure of a compound constituting the target, impurities, etc., affect the
composition and the crystallinity of the film to be formed. For this reason,
it is required that the compound constituting a target be one which is suitable
for the characteristics of the required film. Consequently, an object of the
present invention is to provide a sputtering target and a manufacturing
method thereof, the sputtering target being suitable for the realization of the
recordable optical recording medium which enables high density recording
having such favorable recording characteristics as low jitter, a high density

recordable optical recording medium using the sputtering target.
Furthermore, another object of the present invention is to provide a
sputtering target which realizes increased film deposition rate for improved
productivity, shows high strength upon film deposition, and has high
packing density.
Furthermore, a recordable recording medium containing Bi and B in
the recording layer is disclosed. It is also disclosed that the ratio of the
number of Bi atoms to the number of B atoms, B/Bi, is set to 1.25 or less.
However, as a result of extensive studies made particularly for the recording
layer containing Bi and B, the range of their relative proportions within
which excellent characteristics - particularly archibability — can be obtained
has been established. It has been established that adding B to a recordable
optical recording medium containing Bi and B in the recording layer
improves archibability. Since the appropriate layer structure is different
between a disc for conducting recording and reproduction by allowing light
to be incident thereon from the side of a substrate as seen in so-called HD
DVD and a disc for conducting recording and reproduction by allowing light
to be incident thereon from the side of a cover layer as seen in so-called
Blu-ray disc, the appropriate composition of the recording layer tends to be
different. In consideration of productivity or the like, it is preferable that
the composition of the recording layer be in the same range. Therefore, an
object of the present invention is to provide a recordable optical recording

medium which has favorable characteristics in a disc having a different layer
structure and which has particularly improved archibability by causing both
the atomic ratio of Bi to B and the content of O, which have not been
contemplated in the related art, to fall within their optimal ranges.
The sputtering target of the present invention for preparing a
recordable optical recording medium comprises Bi and B.
The method of the present invention for manufacturing a sputtering
target comprising Bi and Bi for preparing a recordable optical recording
medium adopts a sintering method.
The recordable optical recording medium of the present invention
comprises a film which comprises as main components Bi, B and oxygen, the
film being deposited by using a sputtering target comprising Bi and Bi for
preparing a recordable optical recording medium.
The recordable optical recording medium of the present invention
comprises a substrate, and recording layer formed over the substrate, the
recording layer containing at least Bi, B and O as main components, and the
ratio of Bi to B in the recording layer being set to 3/7 BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 is a graph of atomic ratio Bi/B vs. jitter value.
FIG. 2 shows the measurement result of X-ray refraction spectrum
of the sputtering target 12.

FIG. 3 shows jitter values and increase amounts of jitter values after
100 hours of the storage test.
FIG. 4 is a graph of atomic ratio Bi/B vs. jitter value.
FIG. 5 is a view used for explaining Example 25.
FIG. 6 is a graph of oxygen amount vs. recording power.
FIG. 7 is a graph of oxygen amount vs. archibability.
FIG. 8 is a graph of thickness of the first protection layer vs. PRSNR
value.
FIG. 9 is a graph of thickness of the recording layer vs. PRSNR
value.
FIG. 10 is a graph of thickness of the second protection layer vs.
PRSNR value.
FIG. 11 is a graph of storage test time vs. PRSNR value.
FIG. 12 is a graph of thickness of the reflection layer vs. PRSNR
value.
FIG. 13 is a graph of thickness of the second protection layer vs.
jitter value.
FIG. 14 is a graph of thickness of the first protection layer vs. jitter
value.
FIG. 15 is a graph of thickness of the recording layer vs. jitter value.

DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the present invention described above will be explained.
According to a first aspect of the present invention, there is provided
a sputtering target containing as main components Bi and B. According to
a second aspect of the present invention, there is provided a sputtering target
containing as main components Bi, B and oxygen. Bi and B can assume a
form wherein they are included as a single element, a form wherein they are
included as an oxide, and a form wherein they are included as other
compounds. In the case where the sputtering target is used for the
deposition of a recording layer of a optical recording medium, the sputtering
target is used as an oxide. Consequently, preferably Bi and B are included in
the form of single element or oxide. When Bi and B are each included as a
single element, it is required that oxygen be added upon film deposition to
form an oxide film. When a target including oxygen is used as shown in the
second aspect of the present invention, it is not required to add oxygen at the
time of film deposition. Note that the main component in first aspect of the
present invention and the second aspect of the present invention refer to
inclusion of about 90 atom% or more of the aforementioned elements.
Normally, except for impurity elements and slight amounts of the
component elements in the eighth aspect of the present invention which will
be described later, the sputtering target consists only of the aforementioned
elements.

According to the third aspect of the present invention 3, there is
provided a sputtering target which is crystalline. When the target is
amorphous, the target temperature rises in the midst of the film deposition
with the result that the target becomes partially or entirely crystalline.
Since the strength of the atom bond or the like differs between non-crystals
and crystals, a difference is generated in the properties and the composition
of the deposited film. When the target is crystalline, the change with the
lapse of time can be suppressed. Furthermore, crystal particle diameters or
crystal size are made uniform and the crystals are made fine, with the result
that the composition shift and disuniformity of the crystal structure can be
suppressed.
According to the fourth aspect of the present invention, there is
provided a sputtering target in which the atomic ratio of Bi to B is such that
0.6 deposited film undergoes crystallization. Consequently, the recording
characteristics and the archivability are deteriorated and cracking of the
target is likely to occur, with the result that the productivity becomes worse.
On the other hand, when Bi is reduced in quantity, the recording
characteristics become worse. Jitters of optical recording media with a
recording layer deposited by sputtering of the target having the
aforementioned atomic ratio range are favorable (see Example 7 to be
described later). In the case where the atomic ratio is smaller than 0.6, it

results in an increase in jitter. In the case where the atomic ratio is larger
than 7.0, it results in a undesirable archivability reduction.
According to a fifth aspect of the present invention, there is provided
a sputtering target including a complex oxide of Bi and B. Assuming a form
of the complex oxide enables stable presence of crystals, thereby increasing
the target strength. Complex oxides include Bi4B2O9, BiBO3, and Bi3B5O12.
Inclusion of the compound comprising three elements of Bi-B-O heightens
the target strength, which is favorable.
According to a sixth aspect of the present invention, there is
provided a sputtering target including Bi4B2O9 as the complex oxide.
Bi4B2O9 offers excellent film deposition rate and strength among other
complex oxides, with the result that an optical recording medium having
favorable recording characteristics after film deposition can be realized.
Judgment as to whether or not Bi4B2O9 is included is made by X-ray
diffraction. In the X-ray diffraction analysis, the lattice constant changes
due to variations in measurement temperature, the inner stress of the film,
variations in the wavelength of the X-ray, or composition shift, and thus shift
is generated in an angle at which the refraction peak is generated. With
respect to known substances, a response to a question as to at which angle
the peak of the X-ray diffraction is generated can be found through the
retrieval of the ASTM (American Society for Testing and Material) card and
the JCPDS. At the time of identifying the peak of the X-ray diffraction by

analyzing the specimen, the ASTM card and "JCPDS card chart" are widely
used. Incidentally, the "JCPDS" is an abbreviation for the "Joint
Committee on Powder Diffraction Standards". The JCPDS refers to a chart
of the X-ray diffraction which is distributed by an organization called the
International Centre for Diffraction Data. Currently, the chart of many
standard substances is stored for retrieval. The X-ray diffraction chart of
specimen whose component is not unknown is compared with a chart of the
aforementioned standard substance with the result that it is judged as to
which chart of the standard substance is constituent with or is approximate
to the chart of the substance whose component is unknown and the
specimen is identified in the judgment. An identification method which is
conducted by using the "JCPDS card chart" is a method which is widely
used in the world as shown in the "general rule of the X-ray diffraction" and
an "analysis of the general rule of the X-ray diffraction,"(Japanese
Industrial Standards) and an "X-ray diffraction analysis" of the ceramic
basic standard 3 edited by the Tokyo Institute of Technology. It is
investigated as to whether the specimen whose component is unknown is
consistent with or is approximate to the chart of the standard substance to
identify the substance.
In the identification of the substance, a surface interval is
determined by using the Bragg's Law from each measured peak to identify
the corresponding crystal structure. Furthermore, in a material in which a

specific crystal surface is oriented, it is possible to identify the substance
from the peak ratio of a plurality of peaks corresponding to the crystal
surface. In the X-ray diffraction, the lattice constant changes because of
causes such as the measured temperature, the inner stress of the film, an
error of the wavelength of the X-ray, and a composition shift or the like with
the result that a shift is generated in the angle in which the diffraction peak is
generated. Consequently, when the peak is present in the vicinity of the
angle which is generated at the diffraction peak, it is possible to say that the
substance is the corresponding substance.
With respect to a shift is generated in the diffraction peak, for
example, a peak from the peak having a surface interval of 3.101A is
referenced from the standard chart of Bi4B2O9 (reference code: 25-1089)
and the measured result is compared with respect to the other target which is
prepared in the same preparation method. Thus, the surface interval of
reference data is 3.1010A while there is a slight shift in the measurement
result such as 3.1058, 3.0952 and the like. However, such degree of shift is
generated within the scope of error when the measurement is repeated with
the result that it is possible to say that any one includes Bi4B2O9.
According to a seventh aspect of the present invention, there is
provided a sputtering target whose packing density is 72% to 100%.
Increasing the packing density leads to an improvement in the target's

strength thereby increasing the film deposition rate. When the packing
density is lowered, the film deposition rate slows down. In addition, the
target itself becomes fragile with the result that many problems such as the
generation of cracking in the formed film or the like occur. Incidentally, the
packing density described herein refers to a value obtained by determining in
calculation a weight when the target volume is occupied by 100% material
substance, and determining the weight as a density in comparison with the
weight of the target which is actually prepared. As shown in Example 8
which will be described later, a favorable sputtering target has a packing
density of 72% or more. Furthermore, the film deposition rate becomes 1.5
times as fast as the case of 72% when the packing density is 93% or more.
Since the packing density becomes still larger in the case of approximately
100%, the advantage is large.
According to an eighth aspect of the present invention, there is
provided a sputtering target including at least one element selected from Li,
Al, Fe, Mg, NA, and Si. By adding these elements, it becomes easy to
increase the packing density. Furthermore, since the connection between
crystals can be made strong, it becomes possible to realize a target of high
strength. It is preferable that the addition amount be as small as possible.
At most, the amount may be about 10 atomic%. When the addition amount
is too large, it results in a lost of property as a sputtering target containing as
main components Bi and B, or Bi, B and oxygen is lost, which is not

favorable.
According to a ninth aspect of the present invention, there is
provided a sputtering target in which oxygen is smaller in quantity than the
stoichimetric composition. It is possible to improve recording characteristics
of the optical recording medium by decreasing the oxygen amount than in
the stoichiometric composition. Even when oxygen is small in quantity, it
becomes possible to add oxygen at the time of film deposition by sputtering
using gas including oxygen. Thus, there is no problem. Furthermore,
decreasing oxygen increases the bonding force of crystals thereby providing
an effect of improving a target density, improving target's strength, and
increasing film deposition rate.
According to a tenth aspect of the present invention, there is
provided a sputtering target including at least one of Bi oxide and B oxide.
When the B oxide, particularly, B2O3 oxide exists, the sensitivity at the
recording time can be improved because B2O3 has a low melting point.
Furthermore, when at least one of the Bi oxide and B oxide is contained, it
results in the deposition of a film that contains as main components Bi, B
and oxygen, showing favorable recording characteristics.
According to an eleventh aspect of the present invention, there is
provided a method for fabricating a sputtering target using a sintering
method. Use of the sintering method enables favorable preparation of a
sputtering target having an oxide having a high melting point.

According to a twelfth aspect of the present invention, there is
provided a method comprising a step of removing moisture from material
powders in the sintering method. The step of removing moisture refers to a
step of removing moisture from material powders with such a method as
vacuum drying prior to weight measurement. It is also possible to use a step
of heating each kind of the material powders at a temperature lower than
their melting point but at 100°C or higher. In the case of oxide at this time,
the heat treatment in the atmosphere is enabled.
For example, B2O3 absorbs moisture with ease with the result that
the measurement error of the quantity of the materials can be decreased by
adding the step of removing the moisture and the reproduction of the
composition is heightened.
According to a thirteenth aspect of the present invention, mere is
provided a manufacturing method of a sputtering target that involves
sintering of Bi2O3 and B2O3 powders. Since Bi2O3 and B2O3 powders can be
easily obtained, the manufacturing costs are low. Furthermore, since these
powders have relatively low melting points, it is relatively easy to increase
the packing density and to readily provide a target with a high strength.
Since B2O3 has water absorption properties, these powders are smashed by
means of a drying method or in an organic solvent and classified with the
result that powders having a uniform diameter are provided. Subsequently,
the powders are mixed together and molded to have a certain shape, followed

by sintering. Sintering is performed by placing the molded article at 420°C
in the atmosphere. It is possible to improve the strength of the target by
repeating the cycle of the step of again smashing, molding, and heating the
sintered article. In the second and subsequent sintering steps, the sintering
temperature can be raised up to about 630°C. When B2O3 is present in the
target, it absorbs moisture, resulting in a high moisture absorption rate and
the quality of the target is deteriorated in some cases. In order to avoid this,
the powders are mixed in the condition where no moisture is absorbed, and
the powders are sintered at a temperature equal to or less than the melting
point of B2O3. The obtained powders are smashed and a target is prepared
by conducting heating and pressing type sintering with the result that a target
having a high uniformity can be obtained and the advantage is large.
Furthermore, the particles may be smashed by sintering particles at a
temperature equal to or less than the melting point of B2O3. In particular, it
is important to provide a step in which no B2O3 is left in the resultant target.
Furthermore, the fact that time for sintering at a low temperature of 420° C
or less is prolonged and complex compound of Bi and B is sintered followed
by raising the temperature to about 630°C for short time sintering has a large
effect.
A sputtering target can be obtained by bonding the target which has
been sintered as described above to an oxygen-free copper backing plate by
means of metal bonding or resin bonding.

In an overall flow of the manufacturing process of the sputtering
target, it is possible to use a step of weighing materials, dry type ball mill
mixing, hot pressing, mold processing and bonding. Furthermore, a step of
weighing materials, moisture type ball mill mixing, spray drying, hot
pressing, mold processing and bonding can be used.
According to a fourteenth aspect of the present invention, the
invention relates to an optical recording medium having a film containing as
main components Bi, B and oxygen by using a sputtering target described in
any of the first to the tenth aspects of the present invention. A required film
is formed on a resin substrate such as a polycarbonate substrate to provide an
optical recording medium. A groove or a pit may be formed on the resin
substrate for control of tracking or the like. An argon gas is introduced into
a vacuum and a high frequency power is applied with the result that a film is
formed which contains as main components Bi, B and oxygen. In addition,
a metal film as a reflection layer, or a protection layer for improving
characteristics may be provided.
According to the first to fourteenth aspects of the present invention,
a sputtering target, a manufacturing method thereof and a high density
recordable optical recording medium using the sputtering target can be
provided, the sputtering target being suitable to the realization of a
recordable optical recording medium which has such favorable recording
characteristics as low jitter and which enables high density recording.

Furthermore, the present invention can provide a sputtering target which
enables the improvement in the film deposition rate for the improvement of
the productivity and which has a high strength at the time of the film
deposition and has an increased packing density.
According to a fifteen aspect of the present invention, the invention
relates to a recordable optical recording medium wherein a recording layer
containing at least Bi, B and O is provided on a substrate and the atomic
ratio of Bi to B in the recording layer is such that 3/7 where the atomic ratio Bi/B is larger than 8, the archivability is reduced.
Although the cause thereof is not clear, it is thought that the recording mark
is formed of a Bi single metal, and oxides of Bi and B or the like in the case
of the optical recording medium of the present invention. When the
proportion of Bi becomes too large, it becomes highly likely that the single
metal of Bi is produced and thus it occupies a large area of a recording mark.
With Bi single metal, deterioration such as oxidation or the like is likely to
occur. It is thought that archivability is reduced in the case where the
atomic ratio Bi/B is greater than 8. There is provided an advantage in that
the presence of a large area of Bi single metal becomes rare by the addition
of B and the area of the Bi single metal is divided into small areas. As a
consequence, the recording characteristics and archivability are improved.
It is thought that the archivability of the recordable optical recording
medium is excellent in the case where the atomic ratio Bi/B is smaller than

3/7. However, it is thought that the recording sensitivity is lowered and the
recording becomes insufficient because the phase separation such as
separation of Bi occurs with more difficulty. Furthermore, with respect to
the target for the formation of the recording layer, the melting point is
lowered in the composition containing a large amount of Bi, and the target
becomes vulnerable to the thermal change, reducing the target's strength.
In addition, with respect to the compound target of Bi-B-0 added with B or
the like, a ternary compound such as B14B2O9 comprising three elements can
be easily prepared with the result that the connection between atoms
becomes strong and the target's strength is improved. However, since the
boron oxide has a low melting point on the order of 450°C, it becomes
difficult to conduct sintering at a high temperature when B increases.
Consequently, a low temperature sintering is required. In the low
temperature sintering, the connection strength between particles can be
hardly raised with the result that the preparation of the target becomes
difficult and the strength is lowered. The content of Bi, B and O as a whole
is 100%, namely, it is not required to include other element except for
impurities. Furthermore, other clement(s) may be added in amounts up to
10%.
Upon determination of the atomic ratio Bi/B, the amounts of Bi, B
and O are measured under conditions as shown in Tables 1 and 2 by means
of the Rutherford Backward Scattering (RBS) and Nuclear Reaction

Analysis (NRA). The composition which is determined with this method
includes an error such that Bi is +0.5 atomic%, B is +2.0 atomic%, and O is
±3.0 atomic%. The atomic ratio Bi/B and the atomic ratio O/B ratio are
measured in the same manner.




According to a fifteen aspect of the present invention, a recordable
optical recording medium excellent in recording characteristics and
archiavability can be provided by providing a recording layer containing at
least Bi, B and O on the substrate, and by setting the atomic ratio of Bi to B
in the recording layer such that 3/7 According to a sixteenth aspect of the present invention, the

invention relates to an optical recordable recording medium in which the
ratio of O to B in the recording layer is set such that 2.2 been made clear that the quantity of oxygen in the recording layer largely
affects the recording characteristics. When the quantity of oxygen is small,
the recording sensitivity is heightened. However, since the coefficient of
the thermal conductivity of the recording layer is heightened, the heat
generated by the light application at the recording time is likely to be
widened with the result that it becomes difficult to conduct high density
recording. Furthermore, when the quantity of oxygen is too large, the
recording sensitivity is lowered, and the recording becomes insufficient with
the result that favorable characteristics cannot be easily obtained.
An optimal oxygen amount differs in different atomic ratios Bi/B, so
an optimal value of O/B changes accordingly. For example, in the case
where the atomic ratio Bi/B is 2/1, it is preferable that O/B be larger than
3.8. Furthermore, when O/B exceeds 4.5, sensitivity is lowered.
Therefore, it is preferable that O/Bbe 4.5 or less.
As considered from the atomic ratio Bi/B, sensitivity is improved
with increasing Bi amount, so that there is a tendency that archivability is
deteriorated. Consequently, the composition containing too much Bi is not
favorable. It becomes possible to improve archivability by increasing the
quantity of oxygen even when the atomic ratio Bi/B is the same. That is,
when the value of atomic ratio O/B is large, there is a tendency that

archivability is improved. Furthermore, when the quantity of oxygen is too
large, sensitivity is lowered. It is possible to increase sensitivity by
increasing the quantity of Bi.
Furthermore, when the Bi/B=Z is given at the atomic ratio, the case
is preferable in which a relation of 0.8 x (Z+l) x 1.5 is established, For example, each of the characteristics of the specimens is
shown in Table 3 from disc 1 through disc 5.

Since the state of Bi, B and Bi2O3 and B2O3 is stable in an ideal state,
the relation of 0=(Bi+B) x 1.5 is established. That is, 0/B=((Bi/B)+l) x
1.5 is set. However, the composition of the actual film depends on the state
of the target, the property of being easily sputtered in respective elements, an
electric power at the time of the film formation, and the flow rate of argon.
There are many cases in which the target composition and the composition
of the formed film are different. It is required to consider the shift of the
composition. Table 4 shows the composition of various Bi-B-0 target and
the composition of the formed Bi-B-O film which is formed at the target.


As shown above, it is required to consider a shift in composition
resulting from a difference in the condition at the time of the film formation.
As a result of the investigation of the composition of the atomic ratio of
various Bi/B, it has been made clear that the case in which the relation of the
aforementioned equation is set is most preferable in consideration of the
shift in composition from the ideal state of O/B. This consequence is
shown in Table 3. When an ideal value of the atomic ratio of O/B, namely
0/B=((Bi/B)+l) x 1.5 is determined from the measured value of the atomic
ratio of Bi/B from the disc 1 to disc 5, values in the table are provided.
When a disuniformity in values are seen by comparing this value with the
value of the atomic ratio of O/B which is a measured value, the values exists
within the scope between an ideal atomic ratio of O/B x 0.8 and an ideal
atomic ratio of O/B x 1.1. Consequently, the composition scope in which
this relation is set is preferable. From disk 1 to disk 5, the property is
favorable. What corresponds to the scope of the aforementioned equation
ranges from disk 1 to disk 4. The jitter values on all the disks from disk 1 to

disk 5 assume a value within the scope of 4 to 6 with the result that a
favorable property is shown. It is shown that when the optimum record
power is high, the sensitivity is inferior; when the optimum power is low, the
sensitivity is high. With respect to disk 5, the sensitivity is the highest.
When numbers are attached thereto in an order from the highest
archiavability to the lowest, the results shown in Table 3 is given.
Furthermore, when the reproduction optical deterioration endurance is
observed, the disk 5 is the worst. When all the disks are generally observed,
the scope from the disk 1 to the disk 4 is the most favorable. The disks 1
through 5 are prepared in the same manner as those in Examples 13 through
20 which will be described later.
According to a sixteenth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and archivability can be provided by setting the atomic ratio
of O to B in the recording layer to 2.2≤O/B≤13.
According to a seventeenth aspect of the present invention, the
invention relates to a recordable optical recording medium wherein the
proportion of O in the total amount of elements constituting the recording
layer is set to the scope of 50% to 67% at the atomic ratio. It is preferable
that the scope of 50% to 60% in which the quantity of oxygen is on the
smaller side. These facts are apparent from the fact shown in Example 26.
It is thought that the recording layer is in the state of oxygen deficiency in

the scope in which the quantity of oxygen is small, particularly in the scope
of less than 60%. In the state of oxygen deficiency, the phase separation is
likely to occur with the result that the recording sensitivity is improved.
Furthermore, the heat conductivity of the recording layer is lowered when
the quantity of oxygen becomes too small because heat tends to expand,
with the result that a small recording mark is formed with difficulty which is
unfavorable for high density recording. In addition, when oxygen is
deficient, Bi is likely to exist in the metal state. Thus, the state becomes
unstable as compared with oxide. Consequently, there is a tendency that
the archiavability becomes worse. In the scope from 50% to 60%, it is
thought that there is almost no problem. When the quantity of oxygen
increases, the archiavability becomes favorable. However, the sensitivity
becomes worse with the result that a favorable recording becomes difficult.
That is, from the aspect of the sensitivity, the case in which the quantity of
oxygen is smaller than 67% is preferable.
According to the seventeenth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and the archiavability can be provided by optimizing the
occupation ratio of O in the all the quantity of elements constituting the
recording layer.
According to an eighteenth aspect of the present invention, the
invention relates to a recordable optical recording medium provided with a

protection layer positioned adjacent to the both surfaces of the recording
layer. Since the recording layer is an oxide, the incoming and outgoing of
oxygen affect the property. In order to suppress the incoming and the
outgoing of oxygen, an attempt can be made to improve the archiavability by
providing a protection layer on both surfaces of the recording layer. As a
protection layer, normally a material is preferable which does not causes
decomposition, sublimation, voids or the like due to heat from the recording
layer during recording. For example, simple oxide type oxides such as
A12O3, MgO, ZrO2, SiO2, SnO2, ZnO, Sm2O3 or the like, and a combination
of these oxides, nitrides such as silicon nitride, aluminum nitride, nitrides of
B and Ti, and the like, carbon-based non-oxides such as SiC, B4C, TiC, WC
and the like, borides such as LaB6 TiB2, ZrB2 and the like, sulfides such as
ZnS, CdS, MoS2, silicides such as MoSi2, amorphous carbon, graphite,
diamond and the like can be used. Furthermore, it is also possible to use
organic materials.
For example, from the viewpoint of the transparency and the
productivity with respect to the recording and reproduction light, the fact
that SiO2 or ZnS-SiO2 are used as main components is cited as a favorable
example. In addition, in order to obtain a sufficient heat insulation effect, it
is preferable to use ZrO2 mainly (as a main component). In addition, since
the stability is high, silion nitrides, aluminum nitrides and aluminum oxides
are also preferable. Furthermore, an oxide comprising ZnS, ZrO2, Y2O3,

and SiO2 or an oxide comprising ZrO2, TiO2, SiO2 and X (where X is at least
one species selected from Y2O3, CeO, A12O3 MgO, Nb2O5 and rare earth
oxides) is preferable. Here, the main component refers to approximately
90% or more approximately in terms of the mol ratio. For example, with
respect to ZnS-SiO2, the film can be formed by means of a direct current
sputtering by allowing the material to have conductivity by adding carbon
and transparent conductive material. In addition, such method of adding
ZnO, GeO or the like and mixing oxide and nitride can be used for the
adjustment of heat conductivity.
As a preferable layer structure, in the case of the structure of the
so-call HD DVD or the like for applying light through a substrate from the
side of the substrate, a layer structure can be cited wherein on the substrate a
protection layer (referred to as a first protection layer), a recording layer, a
protection layer (referred to as a second protection layer) and reflection layer
are formed in this order. Furthermore, in the case of Blu-ray disc or the like,
a structure which comprises a substrate, a reflection layer, a protection layer
(a second protection layer), a recording layer, a protection layer (a first
protection layer) and a cover layer in this order is preferable. In addition, in
the case where data items are recorded by using near-field light, a relatively
hard layer with a high index of refraction such as a silicon nitride, a diamond
carbon or the like is provided on the outermost surface on the side on which
light is incident. A layer structure which comprises a substrate, a reflection

layer, a protection layer (a second protection layer), a recording layer, and a
protection layer (a first protection layer) is preferable. Preferably a
lubricant layer is provided on the outermost surface.
According to an eighteenth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and archiavability can be provided by using a configuration in
which a protection layer is adjacent to both surfaces of the recording layer.
According to a nineteenth aspect of the present invention, the
invention relates to a recordable optical recording medium wherein the
protection layer contains as a main component ZnS-SiO2, silicon nitride, or
aluminum oxide. Using as the protection layer ZnS-SiO2, a silicon nitride,
or an aluminum oxide provides a large effect of preventing the incoming and
the outgoing of oxygen and moisture and a large effect of improving
archiavability. Furthermore, with respect to ZnS-SiO2, preferably a stress
of the film becomes approximately zero when the ratio of ZnS to SiO2 is set
to 80mol%: 20mol%. In particular, the optical recording medium having a
layer structure wherein a film is formed only on one surface of the substrate
such as a BD-R or the like is not preferable because the substrate is bent
when a stress applied on the film is large. In addition, in a mutually
deposited type optical recording medium such as HD-R or the like as well
the fact that the stress is small means that the peeling off of the film is caused
with difficulty and archivability is excellent and such recording medium is

preferable.
According to a nineteenth aspect of the present invention, a
recordable optical recording medium can be provided which is excellent in
the recording characteristics and archiavability, by allowing the protection
layer to contain as a main component, ZnS-SiO2, silicon nitride or aluminum
oxide.
According to a twentieth aspect of the present invention, the
invention relates to an optical recordable recording medium wherein at least
a first protection layer, a recording layer, a second protection layer, a
reflection layer are sequentially provided on the substrate, the first protection
layer comprising aluminum oxide, the second protection layer comprising
ZnS-SiO2. The first protection layer serves to protect the recording layer
from oxygen and moisture which come in and go out through the substrate.
The archiavability can be improved by sandwiching the recording layer with
the first protection layer and the second protection layer. For the
coexistence of the recording characteristics and the archiavability, providing
a protection layer using an aluminum oxide on the substrate side of the
recording layer, and providing a protection layer comprising ZnS-SiO2 on the
opposite side thereof enables providing optically and thermally an optimum
condition which provides favorable characteristics.
According to a twentieth aspect of the present invention, a
recordable optical recording medium can be provided which is excellent in

recording characteristics and archiavability by providing a layer structure in
which at least a first protection layer, a recording layer, a second protection
layer, and a reflection layer are sequentially deposited on the substrate, the
first protection layer comprising an aluminum oxide, the second protection
layer comprising ZnS-SiO2.
According to a twenty-first aspect of the present invention, the
invention relates to a recordable optical recording medium wherein at least a
reflection layer, a second protection layer, a recording layer, a first protection
layer and a cover layer are sequentially deposited, the second protection
layer comprising a silicon nitride, the first protection layer comprising
ZnS-SiO2. As a protection layer on the side of the reflection layer of the
recording layer, silicon nitride is provided. As a protection layer on the
opposite side, ZnS-SiO2 is provided with the result that a recordable optical
recording medium can be realized which shows favorable recording
characteristics and archiavability. Silicon nitride prevents oxygen and
moisture and has a relatively large thermal conductivity with the result that
heat generated at the time of the recording on the recording layer can be
immediately dissipated to the reflection layer. The silicon nitride allows
heat to reside and expand in the recording layer thereby serving to prevent
the generation of troubles in the formation of small recording marks.
Furthermore, ZnS-SiO2 prevents incoming in and outgoing of oxygen and
moisture while serving to prevent the deformation to the side of the cover

layer. When the thermal conductivity is too high, the recording becomes
insufficient. Thus, ZnS-SiO2 is preferable which has a relatively low
thermal conductivity.
As to the material of the substrate, there is no particular limitation
thereto as long as the material has thermally and mechanically excellent
property and has an excellent light transmitting property in the case where
recording and reproduction is conducted from the side of the substrate
(through the substrate).
Specific examples include polycarbonate, polymethylmethacrylate,
amorphous polyolefin, cellulose acetate, and polyethylene terephthalate.
However, polycarbonate and amorphous polyolefin are preferable. The
thickness of the substrate differs depending on the usage thereof. There is
no particular limitation thereto.
As a material of the reflection layer, a material having a sufficiently
high reflectance at a wavelength of the reproduction light can be used. For
example, metals such as Au, Al, Ag, Cu, Ti, Cr, Ni, Pt, Ta, Pd and the like
can be used as a single metal or an alloy thereof can be used. Among such
metals, Au, Al and Ag have high reflectance and are appropriate as a
reflective material. Furthermore, the material may contain other elements
while containing the aforementioned metals as a main component. Other
elements include metals and half metals such as Mg, Se. Hf, V, Nb, Ru, W,
Mn, Re, Fe, Co, Rh, Ir, Zn, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi and the like.

Among such metals and half metals, the material containing as a main
component Ag are particularly preferable from the viewpoint of low cost
and high reflectance. A low diffraction layer and a high diffraction layer are
alternately deposited to each other with materials other than the metal to
form a multi-layer film which can be also used as a reflection layer. For
example, a method for forming the reflection layer includes a sputtering
method, an ion plating method, a chemical vapor deposition method, and a
vacuum vapor deposition method. A preferable thickness of the reflection
layer is 20nm to 300nm.
In addition, for the improvement of reflectance, the improvement of
the recording characteristics, the improvement of the adhesiveness or the
like, a known inorganic species or an organic species an upper coating layer,
a lower coating layer or an adherent layer can be provided on the substrate or
beneath the reflection layer.
A material of an environment endurance protection layer which is
formed on the reflection layer and an interference layer is not particularly
limited as long as the protection layer serves to protect the reflection layer
and the interference layer from an external force. Organic materials include
thermoplastic resins, thermosetting resins, electron beam curable resins, and
UV curable resins. In addition, inorganic materials include SiO2, SiN4,
MgF2, and SnO2. The thermoplastic resin and the thermosetting resin can
be formed by coating and drying a coating liquid which is dissolved in an

appropriate solvent. The UV curable resin can be formed by coating a
coating liquid as it is or a coating liquid which is dissolved in a solvent and
applying UV light thereto to cure the resin. The UV curable resin includes
acrylic resins such as urethane acrylate, epoxyacrylate, polyester acrylate or
the like. These materials may be used singly or in combination. Instead of
a single layer, a multi-layer may be formed. As a method for forming the
protection layer, a coating method such as a spin coat method, a cast method
or the like, a sputtering method, and a chemical vapor deposition method
can be used as with the recording layer. Among such methods, the spin coat
method is preferable. The thickness thereof is generally within the range of
O.lµm to 100µm. In the present invention, the range of 3µm to 30µm is
preferable.
In addition, a substrate may be further bonded to the surface of the
reflection layer or the interference layer. In addition, the reflection layer
and the interference layer surface are allowed to be located opposite to each
other with the surfaces thereof being set as inner surfaces with the result that
two optical recording media may be deposited to each other. On the mirror
finished surface of the substrate, a UV curable resin layer, an inorganic layer
may be formed for the surface protection and the prevention of the sticking
of dusts or the like.
The cover layer becomes necessary in the case where a lens with a
high NA is used in an attempt of increasing recording density. For example,

when the NA is heightened, it is required to reduce the thickness of a portion
which allows the penetration of the reproduction light. This is because
along with the heightening of the NA an allowed quantity of an aberration
decreases which is generated with an angle (which is proportional to a
square of a product of a so-called tilt angle, a reverse number of a
wavelength of the light source, a numeric aperture of an object lens) at
which the disc surface is shifted from a vertical direction with respect to a
light axis of an optical pickup. This is also because the tilt angle tends to be
affected by an aberration resulting from a thickness of the substrate.
Consequently, the thickness of the substrate is reduced so that the influence
of the aberration with respect to the tilt angle is reduced as much as possible.
Therefore, there is proposed an optical recording medium wherein
dents and projections are formed, for example, on the substrate to form a
recording layer, a reflection layer is provided on the recording layer followed
by providing a light penetration cover layer which allows the penetration of
light on the reflection layer with the result that information on the recording
layer is reproduced by applying reproduction light from the side of the cover
layer; and there is provided an optical recording medium, a recording layer is
formed thereon, and an optically transparent cover layer is provided therein,
wherein the information in the recording layer is reproduced by applying
reproduction light from the side of the cover layer.
By means of such procedure, it is possible to achieve an increased

NA of the object lens by thinning the cover layer. That is, it is possible to
achieve a further increase in the recording density by providing a thin cover
layer and by conducting recording and reproduction from the side of the
cover layer.
Incidentally, such a cover layer is generally formed of polycarbonate
sheet and UV curable resin. Furthermore, the cover layer according to the
present invention may include a layer for bonding the cover layer.
According to a twenty-first aspect of the present invention, a
recordable optical recording medium can be provided which is excellent in
the recording characteristics and archiavability by providing a layer structure
in which at least a reflection layer, a second protection layer, a recording
layer, a first protection layer, and a cover layer are sequentially provided on
the substrate, the second protection layer comprising silicon nitride, the first
protection layer comprising ZnS-SiO2.
According to a twenty-second aspect of the present invention, the
invention relates to a recordable optical recording medium wherein the
reflection layer comprises Al alloy. In particular, when the layer structure is
formed in such a manner that the reflection layer and ZnS-SiO2 layer are
located adjacent to each other, Al alloy is preferable for preventing the
deterioration of the reflection layer. The reflection layer preferably
comprises Ag or an Ag alloy in many cases. Although the Al alloy is
inferior to Ag, the Al alloy has a high thermal conductivity and a high

reflectance which means that the Al alloy shows a favorable property. Since
Ag has a high thermal conductivity, there is a tendency that the sensitivity
becomes worse. Furthermore, there is also a tendency that the reflectance
also becomes too high, Al alloy is preferable. For example, in the case
where the reflection layer is Ag-In alloy in an optical recording medium
which has a layer structure comprising a cover layer/ a ZnS-SiO2 (10nm)/ a
Bi-B-0 (16nm)/SiN (12nm)/ a reflection layer (35nm)/ a polycarbonate
substrate, the jitter value is 5.8%. However, in the case where AlTi alloy is
used, the jitter value is 5.2%. Since the Al alloy has a higher sensitivity and
the recording characteristics is favorable, the Al alloy is more preferable.
According to a twenty-second aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and archiavability can be provided by limiting the material of
the reflection layer.
According to a twenty-third aspect of the present invention, the
invention relates to a recordable optical recording medium wherein at least a
first protection layer, a recording layer, a second protection layer, and a
reflection layer are sequentially deposited on the substrate, the thickness of
the first protection layer being set to 10nm to 80nm, the thickness of the
recording layer being set to 6nm to 30nm, the thickness of the second
protection layer being set to 8nm to 35nm, the thickness of the reflection
layer being set to 20nm to 100nm. When the thickness of the fist protection

layer is not 10nm or more, moisture or oxygen comes in and goes out from
the recording layer through the substrate with the result that archivability is
deteriorated. Furthermore, the sensitivity is improved with an increase in
the thickness thereof. However, when the thickness exceeds 80nm, the
heat radiation becomes worse; the recording mark is widened with the result
that the recording characteristics is deteriorated. With respect to the
recording layer, when the thickness becomes thinner than 6nm, the
sensitivity is deteriorated, and the recording characteristics such as PRSNR
or the like is also deteriorated. When the thickness exceeds 30nm, the
reflection is lowered. Although the sensitivity is improved, the recording
characteristics is deteriorated. When the second protection becomes
thinner than 8nm, the reflection layer is located at a nearer place with the
result that the heat radiation is increased too much and the sensitivity is
deteriorated. In an area thicker than 35nm, the heat radiation becomes
worse and the recording mark is widened. When the reflection layer
becomes thinner than 20nm, the reflectance is lowered and the tracking or
the like becomes precarious. When the thickness becomes thicker than
100nm, the sensitivity becomes worse and the recording characteristics is
deteriorated.
According to a twenty-fourth aspect of the present invention, the
invention related to a recordable optical recording medium wherein at least a
reflection layer, a second protection layer, a recording layer, a first protection

layer, and a cover layer are sequentially deposited on the substrate, the
thickness of the first protection layer being set to 7nm to 30nm, the thickness
of the recording layer being set to 6nm to 30nm, the thickness of the second
protection layer being set to 5nm to 30nm, the thickness of the reflection
layer being set to 30nm to 80nm. It has been found that the storage property
is deteriorated in the case where the first protection layer is thinner than 7nm.
When the first protection layer is thicker than 30nm, the heat radiation, and
the recording characteristics becomes worse becomes worse because marks
tend to expand. When the first protection layer is thinner than 6nm, the
sensitivity becomes worse, and the recording characteristics such as PRSNR
or the like also becomes worse. When the thickness of the recording layer
becomes thicker than 30nm, the reflectance is also lowered. Although the
sensitivity of the recording layer is improved, the recording characteristics is
deteriorated. When the second protection layer becomes thinner than 5nm,
the reflection layer is located at a nearer place with the result that the heat
radiation is too good and the sensitivity is deteriorated. When the second
protection layer becomes thicker than 30nm, the heat radiation becomes
worse, and the recording mark is widened. When the reflection layer
becomes thinner than 30nm, the heat radiation effect becomes insufficient
with the result that the jitter values rise and the recording characteristics is
deteriorated. When the reflection layer becomes thicker than 80nm, the
reflectance becomes worse and the recording characteristics is deteriorated.

According the twenty-third and the twenty fourth aspect of the
present invention, a recordable optical recording medium can be provided
which is excellent in the recording characteristics and the archiavability by
optimizing the thickness of each layer.
According to a twenty-fifth aspect of the present invention, the
invention relates to a recordable optical recording medium wherein a
recording layer containing Bi, B and O comprises an oxide which is in the
state of oxygen deficiency in which oxygen is smaller in quantity than the
stoichiometric composition. Stoichiometry refers to a theory showing a
quantitative relation of elements in chemical reactions used in the world of
chemistry. Here, stoichiometric composition is defined in the following
manner. Stoichiometry refers to a composition of elements of compounds
which can be formed by stable compounds which each of the constituent
elements constitute. For example, here, it is defined that a composition
which compounds such as Bi2O3, B2O3, Bi4B2O9 which exist in a stable state
at a normal temperature and at a normal pressure will be referred to as a
stoichiometric composition. The oxygen deficiency state in which oxygen
is small in quantity than the stoichiometric composition refers to a case in
which x case where there is no state of oxygen deficiency, BiO1.5 is provided. In the
same manner, BiO1.45Bi4B2O8.9 shows a state of oxygen deficiency. In other
words, it can be judged there is no state of oxygen deficiency when Bi exists

in the trivalent state. It can be said that there is a state of oxygen deficiency
when the monovalent state or the bivalent state is included. The same thing
holds true for other elements. A state of a mixture thereof, or a state of a
single element which is not an oxide, and a state mixed with the oxide are
also included in the present invention. When the oxide in the state of
oxygen deficiency exists, the oxide either captures oxygen from the outside,
or separates in phase with the result that the oxide will change to a stable
state. When BiO1.45 exists, the phase separation into two phases; Bi2O3 and
Bi is stable. In the state in which the recording layer is sandwiched between
the protective layers to be shielded from the outside, a recording light is
applied and a temperature rises so that the recording layer in the state of
oxygen deficiency is separated in phase, Bi metal is deposited and condensed
to form a recording mark. In the state with no state of oxygen deficiency, or
the state of an excessive quantity of oxygen, the phase separation occurs
with difficulty, and the sensitivity becomes worse with the result that a
favorable recording becomes difficult. In this manner, including oxygen in
the state of oxide deficiency in which oxide is smaller in quantity than the
stoichiometric composition provides a large effect. As a state in which the
recording layer is constituted, any of the following states may be preferably
taken; the state of comprising only oxides in the state of oxygen deficiency,
the state of a mixture of an oxide in the state of oxygen deficiency and an
oxide which is not in the state of oxygen deficiency, or the state of the

mixture of oxide in the state of oxygen deficiency and a single element, and
the state of a mixture of an oxide in the state of oxygen deficiency, an oxide
which is not in the state of oxygen deficiency, and a single element.
According to a twenty-fifth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and the archiavability can be provided by the fact that the
recording layer containing Bi, B and O including an oxide in the state of
oxygen deficiency in which oxygen is smaller in quantity than the
stoichiometric composition.
According to a twenty-sixth aspect of the present invention, the
invention relates to a recordable optical recording medium wherein the
recording layer containing Bi, B and O includes Bi oxide which is in the state
of oxygen deficiency in which oxygen is smaller in quantity than the
stoichiometric composition. Since Bi is likely to be reduced, Bi is likely to
be separated in phase with the result that Bi is preferable for the formation of
the recording mark. It is preferable that the proportion of Bi oxide which is
in the state of oxygen deficiency be 50% to 80% in the total amount of
existing Bi. When the proportion is approximately 100%, an effect is
provided. A judgment on the state of oxygen deficiency can be made by
measuring a vicinity of the energy area of Bi4f in the measurement by
means of the X-ray photoelectron spectral analysis (XPS). For example, an
element in the trivalent state of Bi is considered to be Bi2O3. It can be said

that the state is free from the oxygen deficiency. In the case where Bi is
bivalent, it can be considered that there is a state of oxygen deficiency
according to the present invention in the state, the metal state of Bi can be
measured. Since the present invention has the same effect when only two
kinds of the state of single element of Bi and the Bi oxide exist which is not
in the state of oxygen deficiency in which oxygen is smaller in quantity than
the stoichiometric composition such as Bi2O3 or the like, such states can be
included in the present invention.
According to the twenty-sixth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and the archiavability can be provided by the fact that the
recording layer containing Bi, B and O includes Bi oxide in the state of
oxygen deficiency in which oxygen is smaller in quantity than the
stoichiometric composition.
According to a twenty-seventh aspect of the present invention, the
invention relates to a recordable optical recording medium wherein a
recording mark recorded by light application includes a single element
which is not an oxide. Although the details are not clear, the following
point can be considered as a formation principle of the recording mark.
The recording layer containing elements of Bi, B and O is thought to be in
either of the states; the state in which the recording layer exists all in the
state of oxides in unrecorded state, or the state in which the single state of

respective elements excluding oxygen and the state of oxides are mixed. In
the case of this state, the temperature of the recording layer rises when light
is applied at the recording time with the result that the stability of the film
constituting the recording layer decreases. The state of oxide free from the
oxygen deficiency at that time has a high stability so that recording cannot be
conducted in a favorable manner. However, when the unrecorded state
exists in the state of oxygen deficiency, the state is changed to a stable state
by applying recording light. Changing from the state of oxygen deficiency
to a state of mixture of oxide free from oxygen deficiency and a single
element facilitates the formation of recording marks. With respect to this
recording mark, a difference in the optical property with the unrecorded
portion is enlarged by the deposition of the single element thereby enabling
enlarging a difference in the reflectance. As a consequence, the amplitude
of a reproduction signal is enlarged and a more favorable property can be
shown. Furthermore, in the case where the single element and the oxide
exist in the unrecorded state, a rise in the temperature of the recording layer
by the application of the recording light allows the oxide to separate oxygen
with the result that a form of a single element can be provided. At a portion
where the recording light is applied, the oxide decreases and the single
element increases. Alternately, the oxide and the single element are
respectively condensed with the result that a phase separation-like state is
realized. In the state in which fine single elements are mixed in the oxide,

recording light is applied with the result that there is provided a state in
which the single element is grown and the single element is condensed in the
oxide and is distributed. This provides a recording mark. With respect to
the recording mark, a difference in the optical property with the unrecorded
portion is enlarged by the deposition of the single element thereby enabling
enlarging a difference in the reflectance. As a consequence, the amplitude
of a reproduction signal is enlarged and a more favorable property can be
shown. In particular, it is preferable that the Bi oxide easily separates
oxygen. It is preferable that in the unrecorded state, the Bi oxide exists in
the state of oxygen deficiency, and application of the recording light serve to
separate in phase the single element of Bi and exists in the recording mark
with the result that the recording mark is formed. In addition, it is also
preferable in the non-recorded state that fine Bi exist as a single entity mixed
with an oxide thereof, and recording marks are formed in such a manner that
Bi is grown and is deposited. It is also preferable that the other oxides be
deposited, and recording marks are formed in the mixed state.
According to the twenty-seventh aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and the archiavability by the fact that the recording mark
recorded by light application includes a single element which is not an oxide.
According to a twenty-eighth aspect of the present invention, the
invention relates to a recordable optical recording medium wherein the

recording mark recorded by light application does not show any distinct
crystal structures. Optical recording is made by means of the change in the
optical property such as deformation, a change in a crystal structure or the
like in many cases. However, the present invention is characterized by the
fact that the recording mark does not show any distinct crystal structures,
but is amorphous as determined by X-ray diffraction in the same manner as
the unrecorded state. When the crystal structure of the recording mark is
measured by X-ray diffraction, a crystal peak is not measured and is
amorphous. Although we can only speculate the cause of the crystal
structure in the recording mark, the absence of distinct crystal structures
may enable suppressing of the deformation of the portion of the recording
mark to provide favorable characteristics.
According to the twenty-eighth aspect of the present invention, a
recordable optical recording medium excellent in the recording
characteristics and the archiavability can be provided by the fact that the
recording marks recorded by light application show no distinct crystal
structures
As has been described above, according to the fifteenth to the
twenty-eighth aspects of the present invention, there can be provided a
recordable optical recording medium having excellent recording
characteristics and archivability, in particular, an excellent recordable
optical recording medium which conforms to the HD DVD-R standard, or

the BD-R standard.
Examples
Hereinafter, the present invention will be further specifically
explained with reference to Examples and Comparative Examples.
However, the present invention is not limited by these Examples
(Examples 1 and 2)
Powders of Bi2O3 and B2O3 were weighed in the state free from
moisture adsorption in such a manner that the atomic ratio of B to Bi was set
to 2:1. After dry mixture with the ball mill for one hour, the powders were
sintered for one hour at 420°C (Example 1). Furthermore, in a separate
manner, while conducting a dry mixture for one hour with the ball mill, the
powders were sintered for one hour at 420°C (Example 2). Next, a
sputtering target was prepared by press molding the powders at 100MPa
through 200MPa and sintering the powders for 5 hours at 600°C in the
atmosphere.
The target is formed into a disc-like configuration having a diameter
of 200mm and a thickness of 6mm. These targets were bonded to
oxygen-free copper-made backing plate by means of metal bonding to obtain
sputtering targets 1 and 2. The packing density of these targets was 98%
and 96%, respectively.
(Examples 3 and 4)

Recordable optical recording media according to Examples 3 and 4
were prepared by using the sputtering targets 1 and 2 prepared in Examples 1
and 2.
On a polycarbonate substrate (product name: ST3000 manufactured
by Teijin Bayer Polytec Co.Ltd.) having a guide groove (with a groove depth
of 21nm, a groove width of 0.16□ m, and a track pitch of 0.32µm), by the
sputtering method an AlTi alloy (Ti: 10 weight%) film having a thickness of
35nm, a ZnS-SiO2 (80: 20 mol%) film having a thickness of 20nm, and a film
(Bi-B-O film) having a thickness of 15nm and comprising Bi, B and oxygen
were sequentially provided, followed by further laminating thereon a
polycarbonate sheet (manufactured by Teijin Kasei; Pure Ace) to a thickness
of 75µm by using a UV curable resin (manufactured by Nippon Kayaku
DVD0O3) to provide a light transmitting layer with the result that a
recordable optical recording medium (an recordable optical recording
medium that meets the requirement of the so-called Blu-ray standard)
according to the present invention was prepared to a thickness of about
1.2mm.
With respect to these recordable optical recording media, recording
and reproduction are conducted from the side of the light transmitting layer
by using an optical disc evaluation device DDU-1000 (wavelength: 405nm,
NA: 0.85) manufactured by Pulstec Industrial Co., Ltd. to measure jitters at
that time. Example 3 showed a jitter of 5.8%, and Example 4 showed a

jitter of 5.9%. These values were favorable. The recording conditions
were given as follows. The reproduction power was set to 0.2mW.
0 Modulation method: 1-7 modulation
□ Recording linear density: shortest mark length 2T=0.149 (µm)
□ Recording linear velocity: 4.9 (m/s)
□ Waveform equalization: limit equalizer
□ Recording power: 6.1mW
(Example 5)
Powders of Bi and B were mixed by wet method for one hour with a
ball mill in such a manner that the atomic ratio thereof became 2 to 1
followed by sintering the powders for eight hours at 250°C in the atmosphere
while pressing and molding the powders at 100 to 200MP with the result that
a sputtering target was prepared by means of hot pressing.
The target was formed into a disc-like configuration having a
diameter of 200mm and a thickness of 6mm. This target was bonded to a
packing plate made of oxygen-free copper by means of metal bonding to
obtain a sputtering target 3. The packing density of this target was 96%.
(Example 6)
Except for the fact that the Bi-B-0 film was prepared in the midst of
mixed gas of argon and oxygen (Ar: oxygen =40:6; by volume) by using a
sputtering target 3 which was prepared in Example 5, a recordable optical
recording medium was prepared in the same manner as Example 3 and

jitters were measured to show 4.8%, which was favorable.
(Example 7)
Except for the fact that the atomic ratio of Bi: B in Bi2O3, and B2O3
were changed, the sputtering targets 4 through 10 were prepared in the same
manner as that in Example 1. Except for the fact that the recording layer
was formed into a film by using these targets, the recordable optical
recording medium was prepared in the same manner as that in Example 3.
The result of jitter measurement by conducting recording reproduction is
shown in FIG. 1. Incidentally, the atomic ratio of Bi/B at each point and
jitters (%) in FIG. 1 are shown in Table 5.


From FIG 1, it can be seen that favorable jitters can be obtained
within the range of 0.6≤Bi/B≤7.0.
(Example 8)
Except for the fact that the sintering conditions were changed, the
sputtering target was prepared in the same manner as that in Example 1, the
packing density, the validity of the preparation, and the film deposition rate
for the sputtering target (the film was formed with the sputtering device
(DVD Sprinter) manufactured by the Unaxis Co. Ltd.) are shown in Table 6.
The DVD Sprinter is used for manufacture of optical recording media.
As can be seen from Table 6, in the case where the packing density is
50% or less, the material is fragile, and the target could not be prepared.
Furthermore, in the case where packing density was 64%, the target was
successfully prepared, but the film deposition rate was insufficient. When
power applied at the time of film deposition was increased, the film

deposition rate was improved. However, the target was damaged with the
result that a sufficient film deposition rate was not obtained. In contrast, it
succeeded in obtaining a sufficient film deposition rate in the case where
packing density was 72%.

(Example 9)
Powders of Bi2O3 and B were weighed in such a manner that the
atomic ratio of Bi and B were set to 3:1 and the powders are wetted and
mixed with a ball mill for one hour followed by sintering the powders for
eight hours at 420°C in the atmosphere while pressing and molding the
powders at 100 MPa to 200MPa and hot pressing the powders to prepare a
sputtering target. The sputtering target is formed in a disc-like
configuration in such a manner that the diameter is 200mm and the
thickness is 6mm. This target is bonded to a packing plate made of
oxygen-free copper with metal bonding to obtain a sputtering target 11. The

packing density of this target was 98%. The present Example corresponds
to a case in which oxygen is smaller in quantity than the stoichiometric
composition.
(Example 10)
Except for the fact that a sputtering target 11 prepared in Example 9
was used to prepare a Bi-B-O film in the midst of mixed gas of argon and
oxygen (Ar: oxygen: 20: 1; by volume), a recordable optical recording
medium was prepared in the same manner as that of Example 3 and jitters
are measured to show 5.1% which means that favorable characteristics can
be obtained.
(Example 11)
Except for the fact that a step of subjecting the powders of Bi2O3 and
B2O3 to vacuum drying for 24 hours at 150°C to remove moisture was added
as a step before the weight measurement, the sputtering target 12 was
prepared in the same step as that in Example 1. The vacuum degree at the
time of vacuum drying was about 10Pa to 100OPa at which the vacuum
drawing is conducted with a normal rotary pump. The packing density of
this target was 99%.
The recordable optical recording medium was prepared in the same
manner as that in Example 3 by using the aforementioned sputtering target
12 to conduct recording and reproduction with the result that jitters was
measured to be 5.3%.

(Example 12)
An X-ray diffraction pattern of the sputtering target 12 prepared in
Example 11 was measured. The measurement condition is shown in Table
7. The measurement result is shown in FIG. 2.
Retrieval was made for identifying the position of the diffraction
peak obtained in this measurement to refer to known substance. The upper
stage of FIG. 2 shows a diffraction pattern of the sputtering target 12 while
the lower stage thereof shows with known data items a position where the
diffraction peak of Bi4B2O9. For the X-ray diffraction a database is
constructed which tells where the diffraction line of the known substance
appears and the intensity of that diffraction line. Comparing the peaks of
an analyte with those of the known substance makes it possible to identify
the analyte. As a result of retrieval by means of comparison with the
Bi4B2O9 data items shown in the lower stage and the measured data items
shown in the upper stage, it was confirmed that almost all the peaks were the
peaks for Bi4B2O9 and that this sputtering target primarily comprises Bi4B2O9
compound.
That is, as a result of the X-ray diffraction shown in FIG. 2, a distinct
peak was detected and the peak was consistent with the peak position
calculated at the time when it was supposed that a crystalline substance of
Bi4B2O9 existed, it can be said that a crystal of Bi4B2O9 exists. Thus, it can be
exemplified that the substance is preferable in the case where the target is

crystalline.

(Comparative Example 1)
Bi2O3 and MoO3 are mixed at 70: 30 (mol ratio) and sintered, and a
sputtering target having a diameter of 76.2mm and thickness of 4mm was
prepared, followed by deposition of a film. BiMoO contains as main
components Bi and Mo and oxygen. An applied power and an intensity of
the target at that time were measured, and a result thereof is shown in Table
8. A case in which the film was normally formed is shown by symbol O.
On the other hand, a case in which the target was damaged is shown by
symbol x.

For a comparison purpose, data for an article obtained by mixing Bi2O3 and
B2O3 powders in proportions of 2:1 followed by sintering are shown.

(Example 13 through Example 22)
On a polycarbonate substrate (product name: ST3000 manufactured
by Teijin Bayer Polytec Co. Ltd.) having a thickness of 1.1mm and a
diameter of 120mm and having a guide groove (with a groove depth of 21nm
and a track pitch of 0.32pm) by sputtering, an AlTi alloy (Ti: 1.0 weight%)
layer having a thickness of 35nm. a ZnS-SiO2 (80:20mol%) layer having a
thickness of 10nm, a layer comprising Bi, B and O (a Bi-B-O layer) having
a thickness of 16nm, a ZnS-SiO2 (80:20 mol%) layer having a thickness of
10nm are sequentially provided followed by further depositing thereon a
polycarbonate sheet (manufactured by Teijin Kasei; Pure Ace)having a
thickness of 75µm by using a UV curable resin (manufactured by Nippon

Kayaku DVD0O3) to form a light transparent layer with the result that a
recordable optical recording medium of the present invention (a recordable
optical recording medium corresponding to the standard of a so-called
Blu-ray disc) was prepared.
With respect to the recordable optical recording in a condition
corresponding to the recordable Blu-ray disc standard (BD-R version
l.l)medium according to Examples 13 through 22 in Tables 9 and 10,
recording is conducted by using an optical disc evaluation device ODU-1000
(wavelength: 405nm, NA: 0.85) manufactured by Pulse Tec Industries Co.
Ltd. to evaluate jitter values.


FIG. 3 shows evaluation results of Examples 13 through 17 and 21.
Jitter values after conducting the storage test for 100 hours in the
environment at temperature of 80°C and moisture of 85% and an increase
amount of jitter value before and after the storage test are shown. At an
atomic ratio of Bi/B=9, jitter values significantly increased. Incidentally, it
is regulated that the standard values of jitters of BD-R were 6.5% or less.

Up to the atomic ratio of at atomic ratio of Bi/B =8, the increase amount of
jitter value was small and favorable characteristics are shown. Up to the
atomic ratio of 0/B=12.7, favorable characteristics are shown, but the jitter
value showed a significant increase at 14.2.
FIG. 4 shows the results of Example 18 through Example 20 and 22.
At the atomic ratio of Bi/B and the atomic ratio of O/B that shows at
Example 22, jitter values significantly increased. In a composition in which
the atomic ratio Bi/B was small, the difference in jitter value before and after
the storage test became small.
In addition, when the atomic ratio Bi/B is smaller than 0.8, the
sensitivity tends to become relatively decrease, with the result that it is
preferable that the atomic ratio Bi/B be 0.8 or more.
(Example 23)
On a polycarbonate substrate having a guide groove (with a groove
depth of 26nm and a track pitch of 0.4µm), by the sputtering method a
ZnS-SiO2 layer with a thickness of 15nm (ZnS:SiO2 = 80:20 mol%), a
Bi-B-0 layer with a thickness of 15nm which serves as a recording layer,
and a ZnS-SiO2 layer with a thickness of 20nm (ZnS: SiO2=80:20mol%) are
sequentially deposited. As the Bi-B-0 layer, a layer having an atomic ratio
of Bi/B of 7.9 and the atomic ratio O/B of 13.2 was used. Then, an AlTi
alloy (Ti:1.0 weight%) layer was provided to a thickness of 40nm by the

sputtering method, and an organic protection layer comprising an UV
curable resin (manufactured by San Nopco Co., Ltd.: Nopco Cure 134) was
provided to a thickness to about 5 µm on the AlTi alloy layer by spin coating
followed laminating the layers with a dummy substrate having a thickness of
0.6mm, and the UV-curable resin to provide a recordable optical recording
medium. Recording is conducted in a condition in conformity with the HD
DVD-R standard (DVD specifications for high density recordable disc (HD
DVD-R) version 1.0) by using an optical disc evaluation device ODU-1000
(wavelength: 405nm, NA:0.65) manufactured by Pulstec Industrial Co. Ltd.
with respect to this recordable optical recording medium to measure PRSNR
with the result that a favorable value of 22.0 (standard value: 15 or more)
was obtained. Furthermore, the PRSNR after the storage test for 300 hours
at a temperature of 80 degrees C and a moisture of 85% became 16.0 and a
favorable property was shown.
(Example 24)
On a polycarbonate substrate having a guide groove (a groove depth
of 26nm and track pitch of 0.4pm), by the sputtering method an aluminum
oxide layer (A12O3) layer with a thickness of 15nm, a Bi-B-0 layer with a
thickness of 15nm which serves as a recording layer and a ZnS-SiO2 (ZnS:
SiO2=80:20mol%) layer with a thickness of 20nm were sequentially

deposited. As the Bi-B-0 layer, a layer having an atomic ratio Bi/B of 1.75
and an atomic ratio O/B of 4.5 was used.
Next, an AlTi alloy (Ti: 1.0 weight%) layer having a thickness of
40nm was provided by the sputtering method, and an organic protection
layer made of UV curable resin (Sun Nopco Co., Ltd.: Nopco Cure 134) and
having a thickness of about 5□m was provided by spin coating.
Furthermore, the dummy substrate having a thickness of 0.6mm was bonded
to the protection layer to provide a recordable optical recording medium.
Recording was conducted in a condition in conformity with the standard of
HD DVD-R (DVD specifications for high density recordable disc (HD
DVD-R) version 1.0) by using an optical disc evaluation device ODU-1000
(wavelength: 405nm, NA: 0.65) manufactured by Pulstec Industrial CO., Ltd.
with respect to this recordable optical recording medium to measure PRSNR
with the result that a favorable value of 29.0 (standard value: 15 or more)
was obtained. Furthermore, the PRSNR after the storage test for 300 hours
at a temperature of 80°C and a moisture of 85% became 23.0 and a favorable
property was shown. It was made clear that in the case where the
aluminum oxide layer was replaced with the ZnS-SiO2 layer (ZnS:
SiO2=80:20mol%), the value of PRSNR was 24.0, and decreased to 19.0
after the storage test, and the value of the PRSNR in the case of using an
aluminum oxide layer was further higher.
(Example 25)

On a polycarbonate substrate (product name: ST3000 manufactured
by Teijin Bayer Polytec Co., Ltd) having a guide groove (with a groove
depth of 21nm and a track pitch of 0.32µm ) and having a thickness of
1,1mm and diameter of 120mm by the sputtering method a AlTi alloy (Ti:
1.0 weight%) layer serving as a reflection layer and having a thickness of
35nm, a silicon nitride layer serving as a second protection layer and having
a thickness of 10nm, a layer (Bi-B-0 layer) comprising Bi, B and oxygen
and having a thickness of 16nm and a ZnS-SiO2 (80: 20mol%) layer of 12nm
thickness were sequentially provided followed by laminating thereon a
polycarbonate sheet (manufactured by Teijin Kasei; Pure Ace) having a
thickness of 75µm by using UV-curable resin (manufactured by Nippon
Kayaku; DVD0O3) to provide a light transmitting layer having a thickness of
1,2mm thereby preparing a recordable optical recording medium of the
present invention (a recordable optical recording medium which
corresponds to the standard of the so-called Blu-ray disc). As the Bi-B-0
layer, a layer having the atomic ratio Bi/B of 1.75 and the atomic ratio O/B
of 4.5 was used. Recording was conducted in a condition in conformity
with the standard of the recordable Blu-ray disc (BD-R version 1.1) by using
the optical disc evaluation device ODU-1000 (wavelength: 405nm, NA:
0.85) manufactured by Pulstec Industrial Co., Ltd. with respect to this
recordable optical recording medium to measure jitter values. The jitter
value before the storage test was 5.1%. The jitter after 300 hour-storage

test at a temperature of 80oC and moisture of 85% was 6.1%. It was
established that favorable characteristics could be obtained. Furthermore,
as shown in FIG. 5, it was made clear that with respect to the reproduction
signal after storage, a disc using silicon nitride had a smaller noise and
preferably the silicon nitride was used as the second protection layer.
(Example 26)
Example 26 is an example corresponding to claim 17. On a
polycarbonate substrate (product name: ST3000 manufactured by Teijin
Bayer Polytec Co., Ltd.) having as a guide groove (a groove depth of 21nm,
a track pitch of 0.32µm) and having a thickness of 1.1mm and a diameter of
120mm, by means of the sputtering method, an AlTi alloy (Ti: 1.0 weight%)
serving as a reflection layer and having a thickness of 35nm, a ZnS-SiO2
(80:20 mol%) layer serving as a second protection layer and having a
thickness of 10nm, a layer (Bi-B-0 layer) comprising Bi, B and O and
having a thickness of 16nm, and a ZnS-SiO2 (8.0:20. mol%) layer having a
thickness of 10nm were sequentially provided, followed by laminating
thereon a polycarbonate sheet (manufactured by Teijin Kasei; Pure Ace)
having a thickness of 75 µm by using a UV curable resin (manufactured by
Nippon Kayaku; DVD0O3) to provide a light penetration layer with the
result that a recordable optical recording medium of the present invention (a
recordable optical recording medium which corresponds to the standard of a

so-called Blu-ray disc) was prepared. With respect to this recordable
optical recording medium, recording was conducted in a condition
corresponding to the standard of the recordable blue-ray disc (BD-R version
1.1) by using an optical disc evaluation device ODU-1000 (wavelength:
405nm, NA: 0.85) manufactured by Pulstec Industrial Co., Ltd. to evaluate
the recording characteristics. The relationship between the quantity of
oxygen in the Bi-B-0 layer and the optimum recording power is shown in
FIG. 6. When the quantity of oxygen is within this scope, the optimum
recording power was restricted to a scope of the standard value and shows a
favorable power. In a scope less than 60 atomic % of the quantity of
oxygen, a particularly favorable value is shown. Furthermore, a result of
the investigation as to what degree the jitter values increased before and
after storage test is shown in FIG. 7. A variation quantity of the jitter
values before and after the storage test is shown by the ratio of the jitter
values before the storage test. Values after 300 hours storage test were
used. It can be seen that when the quantity of oxygen is 50% or more, the
increase amounts of jitter value were relatively small, which is preferable.
It can be seen that when the quantity of oxygen is 55% or more, virtually no
change was shown, which is more preferable.
Furthermore, the same recording is conducted on the recordable
optical recording medium which is identical to that described above except

that an AlTi alloy (Ti: 1.0 weight%) layer serving as a reflection layer and
having a thickness of 35nm, a ZnS-SiO2 (80: 20mol%) layer serving as a
second protection layer and having a thickness of 25nm, and a layer (Bi-B-0
layer of oxygen 68 atom%) layer comprising Bi, B and oxygen and having a
thickness of 16nm are sequentially formed followed by laminating thereon a
polycarbonate sheet (manufactured by Teijin Kasei; Pure Ace) having a
thickness of 75µm by using a UV curable resin (manufactured by Nippon
Kayaku; DVD00O3) to provide a light transmitting layer. At a recording
power of 5.6mW, a jitter of 5.8% was obtained. However, it was made clear
that when the recording linear velocity was doubled (2X recording) the jitter
value became 6.5% or less only in the case where the record light was
7.2mW and the sensitivity decreased and was out of the standard.
(Example 27)
On a polycarbonate substrate having a guide groove (with a groove
depth of 26nm and a track pitch of 0.4pm), by using the sputtering method,
a ZnS-SiO2 layer (ZnS: SiO2=80: 20mol%) serving as the first protection
layer, a Bi-B-0 layer serving as the recording layer, a ZnS-SiO2 layer (ZnS:
SiO2=80: 20mol%) serving as the second protection layer, and a AlTi alloy
(Ti:1.0 weight%) layer serving as the reflection layer were sequentially
deposited. As the Bi-B-0 layer, a layer having a composition of Bi
27.0-B 13. 1-059.9 was used. Next, an organic protection layer comprising

a UV curable resin (manufactured by San Nopco Co., Ltd; Nopco Cure
134) and having a thickness of about 5µm was provided on the AlTi alloy
laer by spin coating, followed by further laminating a dummy substrate
having a thickness of 0.6mm and a UV curable resin to obtain a recordable
optical recording medium. Recording was conducted in a condition corresponding to the HD DVD-R standard (DVD specifications for high
density recordable disc (HD DVD-R) version 1.0) by using an optical disc
evaluation device ODU-1000 (wavelength: 405nm, NA: 0.65) manufactured
by Pulstec Industrial Co., Ltd. with respect to this recordable optical
recording medium. Example 27 is an example corresponding to claim 23.
FIG. 8 shows a value of PRSNR of the optical recording medium in which
the recording layer was formed to a thickness of 17nm, the second
protection layer was formed to a thickness of 20nm, and the reflection layer
was formed to a thickness of 40nm by changing the thickness of the first
protection layer serving as a ZnS-SiO2 layer. Values of PRSNR in the
vicinity of 60nm show the highest value. FIG. 9 shows a value of PRSNR
of the optical recording medium in which the ZnS-SiO2 layer serving as the
first protection layer is formed to a thickness of 60nm, the thickness of the
recording layer was changed, the second protection layer was changed to a
thickness of 20nm, and the reflection layer was formed to a thickness of
40nm. Values of PRSNR in the vicinity of 17nm show the highest values.
FIG. 10 shows a value of PRSNR of the optical recording medium in which

the ZnS-SiO2 layer serving as the first protection layer is formed to a
thickness of 60nm, the recording layer was formed to a thickness of 15nm,
the thickness of the second protection layer was changed, and the reflection
layer was formed to a thickness of 40nm. Values of PRSNR in the vicinity
of 20nm show the highest values. Furthermore, FIG. 11 shows the values
of PRSNR before the storage test and after 200 hour-storage test. There
was a difference depending on the thickness of the first protection layer. In
the case where the first protection layer was Onm, the reduction in the
PRSNR value was large. However, in the protection layer with a thickness
of 10nm or 30nm, the reduction in the PRSNR value was suppressed; this
means such thickness values were effective. FIG. 12 shows a relationship
between the thickness of the reflection layer and the PRSNR. The
ZnS-SiO2 layer serving as the first protection layer was formed to a
thickness of 60nm, the recording layer was formed to a thickness of 17nm,
and the second protection layer was formed to a thickness of 20nm. Values
of PRSNR in the vicinity of 40nm show favorable characteristics.
(Example 28)
On a polycarbonate substrate (product name: ST3000 manufactured
by Teijin Beyer Polytec Co., LTd.) having a guide groove (with a groove
depth of 21nm and a track pitch of 0.32nm), by using the sputtering method,
a thickness of 1.1mm and a diameter of 120nm, an AlTi alloy (Ti:1.0
weight%) layer serving as the reflection layer, a silicon nitride layer serving

as the second protection layer, a layer (Bi-B-O layer) comprising Bi, B and
oxygen and serving as the recording layer, a ZnS-SiO2 (80:20 mol%) layer
serving as the first protection layer were sequentially provided followed by
laminating thereon a polycarbonate sheet (manufactured by Teijin Kasei;
Pure Ace) to a thickness of 75µm by using a UV curable resin
((manufactured by Nippon Kayaku; DVD0O3) to provide a light transmitting
layer to prepare a recordable optical recording medium of the present
invention having a thickness of 1.2mm (a recordable optical recording
medium corresponding to the standard of a so-called blue-ray disc).
Recording was conducted in a condition in conformity with the standard of
the recordable Blu-ray disc (BD-R version 1.1) by using an optical disc
evaluation device ODU-1000 (wavelength: 405nm, NA: 0.85) manufactured
by Pulstec Industrial Co., Ltd. with respect to this recordable optical
recording medium to evaluate the recording characteristics. Example 28 is
an example corresponding to claim 24. FIG. 13 shows a result obtained by
forming the reflection layer to a thickness of 35nm, the recording layer to a
thickness of 16nm and the first protection layer to a thickness of 10nm and
changing the thickness of the second protection layer. Values of jitter in the
vicinity of 10nm to 12nm show the most favorable characteristics. FIG. 14
shows the result obtained by forming the reflection layer to a thickness of
35nm, the recording layer to a thickness of 16nm, the second protection
layer to a thickness of 12nm and changing the thickness of the first

protection layer. A thickness in the vicinity of 10nm showed favorable
characteristics. FIG. 15 shows the result obtained by forming the reflection
layer to a thickness of 35nm, the second protection layer to a thickness of
12nm, the first protection layer to a thickness of 10nm and changing the
thickness of the recording layer. A thickness in the vicinity of 13nm to 16nm
showed favorable characteristics.

WE CLAIM:
1. A sputtering target for preparing a recordable optical recording medium,
comprising:
Bi and B;
oxygen; and
a complex oxide of Bi and B,
Bi4B2O9 as the complex oxide.
2. The sputtering target for preparing a recordable optical recording medium
according to claim 1, wherein the target is crystalline.
3. The sputtering target for preparing a recordable optical recording medium
according to claim 1, wherein the atomic ratio of Bi and B is set to 0.6≤Bi≤7.0□
4. The sputtering target for preparing a recordable optical recording medium
according to claim 1, wherein the packing density is 72% to 100%.
5. The sputtering target for preparing a recordable optical recording medium
according to claim 1, further comprising at least one element selected from Li, Al, Fe,
Mg, Na, and Si.
6. The sputtering target for preparing a recordable optical recording medium
according to claim 1, wherein oxygen is smaller in quantity than a stoichiometric
composition of the sputtering target.
7. The sputtering target for preparing a recordable. optical recording medium
according to claim 1, comprising at least one of Bi oxide and B oxide.
SPUTTERING TARGET AND MANUFACTURING METHOD
THEREFOR, AND RECORDABLE OPTICAL RECORDING MEDIUM
To provide a sputtering target for preparing a recordable optical
recording medium characterized by comprising Bi and B and a
manufacturing method thereof, a recordable high density optical recording
medium using the sputtering target, and a sputtering target which is capable
of improving a speed of the film formation for the improvement of
productivity, which has a high intensity at the time of the film formation and
which has a heightened packing density.

Documents:

00294-kol-2007-assignment-1.1.pdf

00294-kol-2007-correspondence-1.1.pdf

00294-kol-2007-correspondene-1.2.pdf

00294-kol-2007-form-18.pdf

00294-kol-2007-form-3-1.1.pdf

0294-kol-2007-abstract.pdf

0294-kol-2007-assignment.pdf

0294-kol-2007-claims.pdf

0294-kol-2007-correspondence others.pdf

0294-kol-2007-description (complete).pdf

0294-kol-2007-drawings.pdf

0294-kol-2007-form1.pdf

0294-kol-2007-form2.pdf

0294-kol-2007-form3.pdf

0294-kol-2007-form5.pdf

0294-kol-2007-priority document.pdf

294-KOL-2007-ABSTRACT 1.1.pdf

294-KOL-2007-AMANDED CLAIMS.pdf

294-KOL-2007-ASSIGNMENT 1.2.pdf

294-KOL-2007-ASSIGNMENT 1.1.pdf

294-KOL-2007-CORRESPONDENCE 1.1.pdf

294-KOL-2007-CORRESPONDENCE 1.2.pdf

294-KOL-2007-CORRESPONDENCE 1.3.pdf

294-KOL-2007-CORRESPONDENCE 1.4.pdf

294-KOL-2007-CORRESPONDENCE.pdf

294-KOL-2007-DESCRIPTION (COMPLETE) 1.1.pdf

294-KOL-2007-DRAWINGS 1.1.pdf

294-KOL-2007-ENGLISH TRANSLATION.pdf

294-KOL-2007-EXAMINATION REPORT REPLY RECIEVED.pdf

294-KOL-2007-EXAMINATION REPORT.pdf

294-KOL-2007-FORM 1-1.1.pdf

294-KOL-2007-FORM 18.pdf

294-KOL-2007-FORM 2-1.1.pdf

294-KOL-2007-FORM 3 1.2.pdf

294-KOL-2007-FORM 3-1.1.pdf

294-KOL-2007-FORM 5 1.3.pdf

294-KOL-2007-FORM 5-1.1.pdf

294-KOL-2007-GPA.pdf

294-KOL-2007-GRANTED-ABSTRACT.pdf

294-KOL-2007-GRANTED-CLAIMS.pdf

294-KOL-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

294-KOL-2007-GRANTED-DRAWINGS.pdf

294-KOL-2007-GRANTED-FORM 1.pdf

294-KOL-2007-GRANTED-FORM 2.pdf

294-KOL-2007-GRANTED-SPECIFICATION.pdf

294-KOL-2007-OTHERS 1.1.pdf

294-KOL-2007-OTHERS.pdf

294-KOL-2007-PETITION UNDER RULE 137-1.1.pdf

294-KOL-2007-PETITON UNDER RULE 137.pdf

294-KOL-2007-REPLY TO EXAMINATION REPORT 1.1.pdf

Abstract.jpg


Patent Number 252339
Indian Patent Application Number 294/KOL/2007
PG Journal Number 19/2012
Publication Date 11-May-2012
Grant Date 09-May-2012
Date of Filing 27-Feb-2007
Name of Patentee RICOH COMPANY LIMITED
Applicant Address 3-6 NAKAMAGOME 1-CHOME, OHTA-KU,TOKYO, JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 FUJIWARA, MASAYUKI 2-17-27,EDAMINAMI, TSUZUKI-KU, YOKOHAMA-SHI, KANAGAWA, JAPAN
2 KIBE,TAKESHI 1320-77,TAKAMORI, ISEHARA-SHI,KANAGAWA, JAPAN
3 NARUMI,SHINYA TOTSUKA GARDEN 508, 52-1,NASE-CHO, TOTSUKA-KU, YOKOHAMA-SHI, KANAGAWA, JAPAN
4 HAYASHI,YOSHITAKA 3-6-705,OODANANISHI, TSUZUKI-KU, YOKOHAMA-SHI,KANAGAWA, JAPAN
5 FUJII, TOSHISHIGE 3-25-5-611, OKAMURA, ISOGO-KU, YOKOHAMA-SHI, KANAGAWA, JAPAN
6 MIURA,HIROSHI 1-6-15, TOMIZA WAMINAMI, TAIHAKU-KU, SANDAI-SHI, MIYAGI, JAPAN
7 KATO,MASAKI ESPOIR M 101,2-10-11, HIGASHIRINKAN,SAGAMIHARA-SHI, KANAGAWA, JAPAN
8 SASA,NOBORU OBER MOTOSUMIYOSHI PLECKSEED 706, 34-20, IDANAKANO-CHO, NAKAHARA-KU, KAWASAKI-SHI, KANAGAWA, JAPAN
PCT International Classification Number G11B7/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2006-055120 2006-03-01 Japan
2 2006-213972 2006-08-04 Japan