Title of Invention

A PHASE CHANGE RECORDING MATERIAL AND INFORMATION RECORDING MEDIUM

Abstract There is disclosed a phase-change recording material characterized by containing a composition represented by the following formula (1) as the main component: wherein x, y, z and w are numbers satisfying 0.001<x<0.3, 0<y<0.4, 0<z<0.2 and 0<w<0.1, and M is at least one element selected from lanthanoids. An information recording medium having a recording layer containing a composition as defined above, is also disclosed.
Full Text DESCRIPTION
A PHASE-CHANGE RECORDING MATERIAL AND INFORMATION RECORDING
MEDIUM
TECHNICAL FIELD
The present invention relates to a phase-change
recording material and an information recording medium
employing it.
BACKGROUND ART
As a recording method utilizing the phase change, a
method has been known wherein the crystal structure of a
metal or a semiconductor is reversibly changed by
affecting energy beams or an energy flow such as light or
electric current (Joule heat) (Appl. Phys. lett., Vol. 18
(1971), pp. 254-257, U.S. Patent 3,530,441).
Used practically at present as a means for recording
on an information recording medium employing a phase-
change type recording material, is a means to utilize a
reversible change between the crystalline phase and the
amorphous phase. Specifically, it is a means to let the
crystalline state in a non-recorded/erased state and to
form amorphous marks at the time of recording. Usually,
a recording layer is locally heated to a temperature
higher than the melting point and then rapidly cooled to
form amorphous marks. On the other hand, the recording
layer is heated at a temperature of approximately at most

the melting point and at least the crystallization
temperature, and slowly cooled so that the recording
layer is kept at a temperature of at most the
crystallization temperature for a certain retention time
to carry out recrystallization. Namely, in general, a
reversible change between the stable crystalline phase
and the amorphous phase is utilized, and the information
is recorded or retrieved by detecting the difference in
physical parameters such as refractive index, electric
resistance, volume and change in density, between the
crystalline state and the amorphous state.
On the optical information recording medium among
information recording mediums, recording and retrieving
is carried out by utilizing a change in the reflectivity
accompanying the reversible change between the
crystalline state and the amorphous state caused locally
by irradiation with a focused light beam. Such an
optical information recording medium having a phase-
change type recording layer is being developed and used
practically as a low cost large capacity recording medium
excellent in portability, weather resistance, impact
resistance, etc. For example, a rewritable phase-change
type optical information recording medium (hereinafter a
phase-change type optical information recording medium
may sometimes be referred to simply as "phase-change type
optical disk", "optical disk" or "disk") such as CD-RW,
DVD-RW, DVD+RW and DVD-RAM is widely used. Further, it

has been developed to achieve a high density by the use
of blue laser or by an increase in NA of an objective
lens, or to make high speed recording possible by
improvement of the recording pulse waveform.
As a material for such a phase-change type recording
layer, a chalcogenide alloy is used in many cases. As
such a chalcogenide alloy, a Ge-Sb-Te type, In-Sb-Te
type, Ge-Sn-Te type or Ag-In-Sb-Te type alloy may, for
example, be mentioned. Such an alloy is usually an
overwritable material also.
Here, overwriting is a means wherein when recording
is carried out again on a once-recorded medium, writing
is carried out without erasing before the recording, that
is, a means of recording while erasing. On a phase-
change type optical information recording medium,
recording is carried out usually by overwriting, and
accordingly recording while erasing (i.e. overwriting)
may sometimes be referred to simply as recording.
In recent years, along with increase in the amount
of information, it has been desired to develop an
information recording medium (particularly optical
information recording medium) on which recording, erasing
and retrieving at a higher speed are possible. As a
material capable of satisfying both characteristics of
excellent jitter characteristics and storage stability of
amorphous marks even in such very high speed recording, a
material containing as the main component a ternary

composition of Sb-Ge-In is mentioned (JP-A-2001-39031,
JP-A-2002-347341). This material is promising as a
material to be used for a phase-change type optical disk
on which high speed recording and erasing of information
signals are carried out at a reference clock period of at
most 15 ns.
DISCLOSURE OF THE INVENTION
However, there is such a problem that repeated
recording durability of the above material containing as
the main component a ternary composition of Sb-Ge-In has
to be further increased.
For example, CD-RW is guaranteed to have repeated
recording durability for 10 0 0 times in many cases (to
insure the repeated recording 1000 times, it is required
that repeated recording about 2000 times is possible on
CD-RW) . On the other hand, of CD-RW employing the above
ternary composition of Sb-Ge-In as the recording
material, when the number of repeated recording is
evaluated from a practical viewpoint, the upper limit of
the number of repeated recording may be about 1000 times
in some cases.
The present invention has been made to overcome the
above problems, and the object is to provide a phase-
change recording material on which high speed
recording/erasing speed is possible, which has excellent
jitter characteristics, which has a high storage

stability of the recording signals, and which is
excellent in repeated recording durability, and an
information recording medium employing the above
material. Particularly, it is to provide an optical
information recording medium which is one mode of the
applications of the information recording medium.
Under these circumstances, the present inventors
have conducted extensive studies and as a result, found
that by adding at least either lanthanoid or Te to the
above ternary composition, both characteristics of jitter
characteristics against high speed recording/erasing and
storage stability of the recording signals are satisfied,
and further the repeated durability is remarkably
improved, and achieved the present invention.
Namely, the present invention is characterized by
having the following gists.
1. A phase-change recording material characterized by
containing a composition represented by the following
formula (1) as the main component:
{ (Sb1-xGex) 1-yIny} 1-z-wMzTew (1)
wherein x, y, z and w are numbers satisfying 0.001 0≤y≤0.4, 0 element selected from lanthanoids.
2. The phase-change recording material according to the

above 1, wherein in the above formula [1), z/y is at
least Q.001 and at most 1.
3. The phase-change recording material according to any
one of the above 1 to 2, wherein of the above phase-
change recording material, the crystalline state
corresponds to a non-recorded state and the amorphous
state corresponds to a recorded state.
4.. An information recording medium having a recording
layer, characterized in that: the above recording layer
contains a composition represented by the following
formula (1) as the main component:
{ (Sb1-xGex)1-yIny}1-z-wMzTew (1)
wherein x, y, z and w are numbers satisfying 0.001≤x≤0.3,
0≤y≤0.4, 0 element selected from lanthanoids,
5. The information recording medium according to the above
4, wherein in the above formula (1), z/y is at least 0.001 and at
most 1.
6. The information recording medium according to any one of
the above 4 or 5, wherein of the the above phase-change
recording medium, the crystalline state corresponds to a non-
recorded state and the' amorphous state corresponds to a
recorded state.
7. The information recording medium according to any one

of the above 4 to 6, wherein the above information
recording medium is an optical information recording
medium.
8. The information recording medium according to the
above 7, wherein the above optical information recording
medium further has a protective layer.
9.. The information recording medium according to the
above 7 or 8, wherein the above optical information
recording medium further has a reflective layer, and the
reflective layer contains Ag as the main component.
EFFECTS OF THE INVENTION
According to the present invention, a phase-change
recording material on which high speed recording/erasing
is possible, which has excellent recording
characteristics, which has a high storage stability of
the recording signals, and which is excellent in repeated
recording durability, and an information recording medium
employing the above material, can be obtained.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. 1 is schematic views illustrating a layer
structure of an optical information recording medium.
Fig. 2 is schematic views illustrating the power
pattern of a recording laser beam in a recording method
of an optical information recording medium.
Fig. 3 is a graph illustrating the relation between

the recording cycle and the jitter when a recorded signal
is retrieved in Examples.
Fig. 4 is a schematic view illustrating the
temperature history at the time of recording or at the
time of erasing the rewritable information recording.
Fig . 5 is a schematic view illustrating the
structure of one cell of a non-volatile memory.
Fig. 6 is schematic views illustrating the layer
structure of an optical information recording medium.
Fig. 7 is schematic views illustrating the layer
structure of an optical information recording medium.
EXPLANATION OF NUMERICAL REFERENCES
1 Upper electrode
2 Lower electrode
3 Phase-change recording layer
4 Heater portion
5 Reversibly changeable region
10 Insulating film
BEST MODE FOR CARRYING OUT THE INVENTION
Now, the embodiments of the present invention will
be explained in detail. However, the present invention
is not limited to the following embodiments, and various
modifications are possible within the range of the gists.
[1] Phase-change recording material
The phase-change recording material of the present
invention contains a composition represented by the

following formula (1) as the main component:
{ (Sb1-xGex) 1-yIny} 1-Z-wMzTew (1)
wherein x, y, z and w are numbers satisfying 0 . 001oc≤X≤0 . 3 ,
0≤y≤0.4, 0≤z≤0.2 and 0≤w≤0.1, and M is at least one
element selected from lanthanoids, provided that z and w
are not 0 at the same time. Further, each of x, y, z and
w is an atomicity ratio.
The phases-change recording material of the present
invention is characterized in that at least either
lanthanoid or Te is added in a predetermined proportion
to the specific composition of Sb-Ge-In type. The phase-
change recording material of the present invention has
such effects that it is excellent in the repeated
recording durability, in addition to the jitter
characteristics and the storage stability of the
recording signals.
It has already been disclosed by one of the present
inventors that the Sb-Ge-In type alloy is such a
recording material that it is stable in either
crystalline or amorphous state, and the phase change
between these states at a relatively high speed is
possible, and that an optical information recording
medium having a recording layer employing the Sb-Ge-In
type alloy in a specific composition exhibits excellent
jitter characteristics and storage stability of the
recording signals (JP-A-2001-39031). With respect to the
above points, the present inventors have found that the

Sb-Ge-In type alloy is excellent as a phase-change
recording material as follows.
Namely, since the crystallization speed of Sb is
high, amorphous marks cannot be formed under the
recording conditions which are employed for common
optical disks, however, the crystallization speed becomes
low when Ge is mixed with Sb. Accordingly, by mixing Ge
with Sb, the crystallization speed can be adjusted to
achieve a recordable crystallization speed.
However, in an optical information recording medium
having a recording layer employing a composition having
Ge mixed with Sb, the jitters of the recorded signal tend
to be significant. Accordingly, a phase-change recording
material having Ge mixed with Sb is problematic for
practical use. In fact, a phase-change type recording
material of Sb-Ge type alloy has been discussed in
literatures such as Appl. Phys. Lett. 60(25), 22 June
1992, pp. 3123 to 3125. However, the present inventors
have conducted recording on an optical disk employing the
Sb-Ge type alloy for the recording layer under general
recording conditions and conducted evaluation and as a
result, although recording on the optical disk was
possible, the jitters of the recording signal were
significantly high, and the optical disk was not
practicable. Accordingly, as a result of further
studies, the present inventors have found that by adding
an appropriate amount of In to the above Sb-Ge type

alloy, the jitter characteristics of the recording
signals become favorable, and found that the composition
of a Sb-Ge-In type alloy is favorable as the phase-change
recording material.
However, as a result of further studies by the
present inventors, it was found that of the phase-change
recording material having a composition of a Sb-Ge-In
type alloy, the crystallization speed tends to gradually
decrease as compared with the initial one by carrying out
repeated recording. Namely, repeated recording is
carried out several thousands times on the phase-change
recording material having a composition of a Sb-Ge-In
type alloy, due to the above decrease in the
crystallization speed, previously recorded amorphous
marks are not adequately erased. Thus, the jitter
characteristics tend to deteriorate due to the
insufficient erasure of the amorphous marks. This
tendency is remarkable when the In content is high.
The present invention has been made particularly to
overcome the above tendency, and makes it possible to
increase the repeated recording durability (for example,
the jitter characteristics when repeated recording is
carried out) by adding at least either lanthanoid or Te
in a specific composition. The reason why the repeated
recording durability improves by addition of such a metal
element is not clearly understood, but is supposed as
follows.

Namely, in the phase-change recording material
having a composition of a Sb-Ge-In type alloy, in a case
where a quick change in the temperature occurs by the
repeated recording, a phenomenon similar to segregation
may occur in some cases. If the segregation occurs, the
crystallization speed tends to be low, and thus
previously recorded amorphous marks may not be erased and
remain in some cases. By the presence of a portion in
which the amorphous marks are not erased, the jitter
characteristics tend to deteriorate. It is supposed that
by adding at least either lanthanoid or Te in a specific
composition to the Sb-Ge-In type phase-change recording
material, segregation is less likely to occur even if
repeated recording is carried out, and such a phenomenon
that the crystallization speed becomes low due to the
repeated recording is less likely to occur. It is
estimated that an optical information recording medium
employing as the recording layer a phase-change recording
material having at least either lanthanoid or Te added in
a specific composition to the Sb-Ge-In type phase-change
recording material (such as CD-RW) can maintain the
initial crystallization speed even after repeated
recording about 2 000 times.
In the present invention, "containing a
predetermined composition as the main component" means
that the content of the above predetermined composition
is at least 50 atomic% based on the entire materials or

the entire layer in which the predetermined composition
is contained. In order to further obtain the effect of
the present invention, the above predetermined
composition is contained in an amount of preferably at
least 80 atomic%, more preferably at least 90 atomic%,
particularly preferably at least 95 atomic%.
Further, in the present invention, it is preferred
that of the phase-change recording material, the
crystalline state corresponds to a non-recorded state and
the amorphous state corresponds to a recorded state.
This is because it is supposed that not many crystal
nuclei are present in the phase-change recording material
of the present invention. That is, in a case where the
amorphous state corresponds to a non-recorded state and
crystalline state marks are formed in this amorphous
state, it is preferred to use a phase-change recording
material in which many crystal nuclei are present. This
is because when a large number of crystal nuclei are
present in the phase-change recording material, the shape
of the crystalline state marks is less likely to be
influenced by the position of the crystal nuclei. On the
other hand, as described above, not many crystal nuclei
are present in the phase-change recording material of the
present invention, and accordingly favorable recording is
likely to be carried out when the crystal state
corresponds to a non-recorded state and amorphous state
recording marks are formed in the crystalline state,

rather than when the amorphous state corresponds to a
non-recorded state and crystalline state recording marks
are formed in the amorphous state.
In order that the phase-change recording material of
the present invention realizes excellent repeated
recording durability in addition to the jitter
characteristics and the storage stability of the
recording signals, it is necessary that the respective
metal elements as the main component are used in a
specific composition. Detailed explanation will be made
below.
(Sb, Ge)
The Ge amount based on the total amount of Sb and
Ge, i.e. x in the above formula (1) is at least 0.0 01 and
at most 0.3. Ge has a function to reduce the
crystallization speed, to facilitate formation of an
amorphous phase and to increase the storage stability of
the amorphous phase. Accordingly, if the Ge content is
low, the crystallization speed tends to be too high,
whereby it becomes difficult to form the amorphous phase,
or the storage stability of the amorphous phase tends to
be insufficient in some cases. Accordingly, it is
required that Ge is contained in a predetermined amount
or more, and thus 0.001≤x in the above formula (1).
Preferably 0.005≤x, more preferably O.Ol≤X, furthermore
preferably 0.02≤x, particularly preferably 0.03≤x.
On the other hand, if the Ge content is too high,

the crystallization speed tends to be too low, and the
erasure of the amorphous marks (crystallization) may not
be carried out in some cases. Accordingly, in the above
formula (1), x≤0.3 . With a view to controlling the
crystallization speed favorably, it is preferred that
x≤O.25, more preferably x≤0 . 2 , furthermore preferably
x≤O.15, particularly preferably x≤O.1.
(In)
When In is contained, the signal amplitude tends to
be high, and such an effect can be obtained that the
jitter characteristics is improved. If the content is
too low, the improving effect may not be obtained in some
cases, and thus y indicating the content of In in the
above formula (1) is 0≤y. Preferably 0≤y, more
preferably 0.01≤y, furthermore preferably 0.05≤y,
particularly preferably 0.l≤y, most preferably 0.15 ≤y.
On the other hand, if the In content is too high, an In-
Sb type stable crystalline phase having a low
reflectivity (low reflectivity crystalline phase) may be
always formed other than the crystalline phase to be used
for recording in some cases, and in such a case, a phase
change does not occur at all and recording cannot be
carried out. Accordingly, y indicating the In content in
the above formula (1) is y preferably y≤0.3, furthermore preferably y particularly preferably y recording power tends to be low when the In content is

high, and thus the above range is preferred.
(Lanthanoid)
The content of the lanthanoid is at least 0 and at
most 0.2 in the above formula (1). Namely, z indicating
the content of the lanthanoid in the above formula (1) is
0≤z≤0.2.
In a case where a lanthanoid is contained, the
decrease in the crystallization speed due to the repeated
recording is suppressed. In order to obtain this effect,
in a case where Te is not contained, 0 formula (1) . Also with a view to suppressing the
decrease in the crystallization speed due to the repeated
recording, it is preferred that 0 0.005≤z, furthermore preferably O.Ol≤z, particularly
preferably 0.02≤2. The lanthanoid is supposed to have a
role to increase the crystallization speed of the phase-
change recording material when the repeated recording is
carried out. Accordingly, it is supposed that when a
lanthanoid is added to the phase-change recording
material having the composition of the Sb-Ge-In type
alloy of which the crystallization speed tends to be low
by the repeated recording, the decrease in the
crystallization speed due to the repeated recording will
be suppressed. As mentioned above, the lanthanoid has a
role to increase the crystallization speed of the phase-
change recording material at the time of repeated
recording, and thus if the amount of the lanthanoid is

large, the crystallization speed may become higher than
initial one by the repeated recording in some cases.
On the other hand, if the content of the lanthanoid
is too high, the initial crystallization tends to be
difficult, the initial crystallization speed tends to be
too low, or the signal amplitude tends to be low.
Accordingly, in the above formula (1), z≤0 .2, and it is
preferably z≤O.15, more preferably z≤O.l, furthermore
preferably z≤O.07. As compared with a case where Te is
added as mentioned hereinafter, the decrease in the
signal amplitude is small when a lanthanoid is added, and
thus addition of a lanthanoid is preferred from this
viewpoint.
A lanthanoid represents 15 elements of La, Ce, Pr,
Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Such
lanthanoids are. a series in which the 4f orbital is
sequentially filled in view of the electron configuration
and have similar properties, and are preferred. Among
these lanthanoids, preferred is at least any of Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb and Lu, and more preferred is Gd
or Tb. By using the above lanthanoid, the change in the
crystallization speed at the time of repeated recording
can be suppressed. The lanthanoid may be used alone or
in combination as a mixture of at least two.
(Te)
The Te content is at least 0 and at most 0.1 in the
above formula (1). Namely, w indicating the Te content


in the above formula (1) is 0≤w≤.0 .1.
Also in a case where Te is added, the decrease in
the crystallization speed due to the repeated recording
is suppressed. In order to obtain this effect, in a case
where no lanthanoid is contained, 0 formula (1) . Also with a view to suppressing the
decrease in the crystallization speed due to the repeated
recording, it is preferably 0≤w, more preferably 0.005≤w,
furthermore preferably 0.01≤w, particularly preferably
0.02≤w.
On the other hand, the reflectivity of the medium
and the signal amplitude tend to be low by addition of
Te, and thus in the above formula, w≤0.1, and it is
preferably w≤0.09, more preferably w≤O.08, furthermore
preferably w≤0.07, particularly preferably w≤0.06.
(Relation between In and lanthanoid)
Of the phase-change recording material of the
present invention, the decrease in the crystallization
speed due to the repeated recording tends to be
significant if the In content in the phase-change
recording material is high. On the other hand, the
crystallization speed due to the repeated recording tends
to be high if the content of the lanthanoid in the phase-
change recording material is high. Accordingly, in order
to reduce the change in the crystallization speed due to
the repeated recording, it is preferred to control the
relation of In and lanthanoid contents.

From such a viewpoint, z/y in the above formula (1)
is usually at least 0.001, preferably at least 0.01,
more preferably at least 0.0.5, furthermore preferably
at least 0.1, most preferably at least 0.15. The change in
the crystallization speed at the time of repeated recording
can be made small within this range.
Further, z/y in the above formula (1) is preferably
at most 1, more preferably at most 0.7, furthermore
preferably at most 0.5, particularly preferably at most
0.3, most preferably at most 0.25. Within this range,
not only the initial crystallization (initialization
carried out for the first time after production of an
information recording medium) can be carried out
favorably, but also the signal amplitude can be
maintained high..
(Relation of In and Te)
With respect to the phase-change recording material
of the present invention, the signal amplitude tends to
decrease when Te is contained. Accordingly, in a case
where Te is contained, favorable signal amplitude can be
obtained by incorporating In in a large amount.
Accordingly, the ratio of the In content (atomic%) to the
Te content (atomic%) is preferably (In content)>(Te
content), more preferably (In content)>1.5x(Te content),
furthermore preferably (In content)>2x(Te content),
particularly preferably (In content)>3x(Te content), most

preferably (In content)>3.5x(Te content). On the other
hand, with a view to securing the signal amplitude,
usually (In content) content) (Relation between lanthanoid and Te)
To the phase-change recording material of the
present invention, at least either lanthanoid or Te is
added. Namely, either lanthanoid or Te may be used, or
both may be used as combined. Such an effect that the
decrease in the crystallization speed due to the repeated
recording is suppressed can be obtained by addition of
such an element, and in order to more securely obtain
such an effect, z+w is preferably at least 0.01, more
preferably at least 0.02. On the other hand, if
lanthanoid or Te is contained excessively, the signal
amplitude may decrease, or the initial crystallization
may be difficult in some cases. Accordingly, z+w is
usually at most 0.3, and it is preferably at most 0.25,
more preferably at most 0.2, furthermore preferably at
most 0.15, particularly preferably at most 0.1.
The lanthanoid has such properties that it increases
the crystallization speed of the phase-change recording
material during the repeated recording. Accordingly, by
addition of the lanthanoid, the decrease in the
crystallization speed due to the repeated recording of
the composition of the Sb-Ge-In type alloy will be
suppressed. On the other hand, if the lanthanoid is

contained in an excessively large amount, the initial
crystallization tends to be difficult.
Te makes it possible to suppress the decrease in the
crystallization speed of the phase-change recording
material due to the repeated recording. On the other
hand, if Te is contained in an excessively large amount,
the reflectivity of the medium and the signal amplitude
tend to be low.
As mentioned above, the lanthanoid and Te have an
effect to suppress the decrease in the crystallization
speed of the phase-change recording material due to the
repeated recording, and on the other hand, they have
different properties to make the initial crystallization
difficult and to reduce the reflectivity of the medium
and the signal amplitude, respectively. Accordingly,
when the lanthanoid and Te are used together and their
contents are controlled within the above range, the
initial crystallization can be carried out favorably and
the reflectivity of the medium and the signal amplitude
can be made favorable, while suppressing the decrease in
the crystallization speed of the phase-change recording
material due to the repeated recording.
Accordingly, in the present invention, it is
preferred to use the lanthanoid and Te together.
(Other matters)
The recording/erasing is carried out usually by
irradiating the recording layer with a laser beam spot

radiated from the light irradiation portion while
rotating the medium at a high speed, and relatively
moving the light irradiation portion and the medium at a
high speed. The case where the relative speed of
movement is high is referred to as a state where the
recording linear velocity (recording velocity) is high,
and the case where the relative speed of movement is low
is referred to as a state where the recording linear
velocity (recording velocity) is low.
In a state where the recording linear velocity is
high, after the recording layer is once heated by the
laser beam spot, it is rapidly cooled. Namely, the
temperature history of the recording layer is in a
quenching manner, and the higher the recording linear
velocity, the more the amorphous phase is likely to be
formed, and the less the crystalline phase is likely to
be formed, on the recording layer having the same
composition.
Accordingly, it is preferred to adjust the amounts
of Ge, In and the lanthanoid within the above ranges of
the contents depending upon the recording linear
velocity, for example, to increase the crystallization
speed in a medium of which the desired recording linear
velocity is higher, and to reduce the crystallization
speed in a medium of which the desired recording linear
velocity is low.
In order to improve various characteristics, Au, Ag,

Al, Ga, Zn, Sn, Si, Cu, Mn, Pd, Pt, Rh, Pb, Cr, Co, Mo,
W, Mn, 0, N, Se, V, Nb, Ta, Ti, Bi or the like may be
added to the phase-change recording material as the case
requires. In order to obtain the effect of improving the
characteristics, the addition amount is preferably at
least 0.1 at.% (atomic%) of the entire composition of the
alloy. However, it is preferably at most 10 at.% so as .
not to impair the preferred characteristics of the
composition of the present invention.
[2] Information recording medium
Now, the information recording medium of the present
invention will be explained below.
The information recording medium of the present
invention is an information recording medium having a
recording layer and is characterized in that the
recording layer has the composition represented by the
following formula (1) as the main component:
{ (Sb1-xGex) 1-YIny} 1-z-wMzTew (1)
wherein x, y, z and w are numbers satisfying 0.001≤x≤0.3,
0≤y≤0.4, 0≤z≤0.2 and 0≤w≤0.1, and M is at least one
element selected from lanthanoids, provided that z and w
are not 0 at the same time.
In the present invention, the information recording
medium is preferably such that the crystalline state
corresponds to a non-recorded state, and the amorphous
state corresponds to a recorded state. This is because
it is estimated that not many crystal nuclei are present

in the recording layer composition of the present
invention. Namely, in a case where the amorphous state
corresponds to a non-recorded state and crystalline state
marks are formed in the amorphous state, it is preferred
to use a recording layer composition in which many
crystal nuclei are present. This is because when a large
number of crystal nuclei are present in the recording
layer, the shape of the crystalline state marks is less
likely to be influenced by the position of the crystal
nuclei. On the other hand, as described above, not many
crystal nuclei are present in the recording layer
composition of the present invention, and accordingly
favorable recording is likely to be carried out when the
crystal state corresponds to a non-recorded state and
amorphous state recording marks are formed in the
crystalline state, rather than when the amorphous state
corresponds to a non-recorded state and crystalline state
recording marks are formed in the amorphous state.
By using the composition presented by the above
formula (1) as the recording layer, an information
recording medium having excellent recording
characteristics such as the jitter characteristics, the
storage stability of the amorphous marks and the repeated
recording durability even at an ultrahigh speed recording
can be realized.
Such an information recording medium is not
particularly limited so long as recording and retrieving

of information are carried out by detecting the
difference in physical parameters as between the
crystalline state and the amorphous state, and an
information recording medium detecting the difference in
the reflectivity, the electrical resistance, the volume,
the change in density or the like may, for example, be
mentioned. Particularly, the information recording
medium employing the phase-change recording material of
the present invention is suitable for an application to
an optical information recording medium utilizing a
change in the reflectivity due to a reversible change
between the crystalline state and the amorphous state
caused by irradiation with a laser beam.
Further, the information recording medium of the
present invention may be applied to an information
recording medium utilizing a change in the electrical
resistivity due to a reversible change between the
crystalline state and the amorphous state utilizing Joule
heat generated by the electric current flow.
Now, as one example of the information recording
medium of the present invention, the specific structure
of the optical information recording medium and the
recording/retrieving method will be explained. Further,
as another example of the information recording medium of
the present invention, a case where the information
recording medium of the present invention is used for an
application other than the optical information recording

medium will also be explained below.
[2-1] Optical information recording medium
(Layer structure)
As the optical information recording medium, usually
one having a multilayer structure as shown in Fig. l(a)
or Fig. 1(b) is employed. Namely, it is preferred that
on a substrate, a recording layer having a composition,
represented by the above formula (1) as the main
component is formed, and a protective layer is further
formed, as evident from Fig. 1(a) and Fig. 1(b).
The more preferred layer structure of the optical
information recording medium is such a structure that a
first protective layer, a recording layer, a second
protective layer and a reflective layer are formed in
this order along the incident direction of the retrieving
laser beam. Namely, in a case where the retrieving laser
beam enters from the substrate side, preferred is a layer
structure of a substrate, a first protective layer (lower
protective layer), a recording layer, a second protective
layer (upper protective layer) and a reflective layer
(Fig. l(a)), and in a case where the retrieving laser
beam enters from the recording layer side, preferred is a
layer structure of a substrate, a reflective layer, a
second protective layer (lower protective layer), a
recording layer and a first protective layer (upper
protective layer) (Fig. 1(b)).
Needless to say, each layer may consists of at least

two layers, and an interlayer may be formed between the
respective layers. For example, between the substrate
and the protective layer when the retrieving laser beam
enters from the substrate side, or on the protective
layer when the retrieving laser beam enters from the side
opposite to the substrate, a translucent and extremely
thin metal, semiconductor or dielectric layer having
absorption, etc. may be formed so as to control the
amount of the laser energy which enters the recording
layer.
Further, a reflective layer is formed on the side
opposite to the incident side of the recording/retrieving
laser beam in many cases as mentioned above, but this
reflective layer is not essential. Further, the
protective layer which is preferably formed on at least
one side of the recording layer may be made to have a
multilayer structure with materials having different
characteristics.
Now, the respective layers will be explained in
detail.
(A) Recording layer
(A-l) Materials contained in recording layer and their
amount
The materials contained in the recording layer
comprise a composition represented by the above formula
(1) as the main component. This composition was already
explained in detail, and the explanation is omitted here.

In order to effectively obtain the effect of the present
invention, the composition represented by the above
formula (1) is contained usually in an amount of at least
50 atomic%, preferably at least 80 atomic%, more
preferably at least 90 atomic%, particularly preferably
at least 95 atomic%, based on the entire recording layer.
The higher the content is, the more remarkably the effect
of the present invention can be obtained. However, even
if another component such as 0 or N is contained at the
time of film formation of the recording layer, the
effects of the present invention such as high speed
recording/erasing can be obtained when the content is
within a range of from several atomic% to 20 atomic!.
(A-2) Film thickness of recording layer
The thickness of the recording layer is usually at
least 1 nm, preferably at least 3 nm, more preferably at
least 5 nm, particularly preferably at least 10 nm. With
such a thickness, the contrast of the reflectivity
between the crystalline state and the amorphous state
will be adequate, and the crystallization speed will be
adequate, whereby it will be possible to erase the record
in a short time. Further, the reflectivity itself will
be adequate. On the other hand, the thickness of the
recording layer is usually at most 3 0 nm, preferably at
most 2 5 nm, more preferably at most 2 0 nm, furthermore
preferably at most 15 nm, still furthermore preferably at
most 12 nm, particularly preferably at most 11 nm. With

such a thickness, an adequate optical contrast will be
obtained, and cracks are less likely to form on the
recording layer. Further, no deterioration of the
recording sensitivity due to increase in the thermal
capacity will occur. Further, within the above film
thickness range, the volume change due to the phase
change can be moderately suppressed, and microscopic and
irreversible deformation of the recording layer itself or
the protective layer to be formed on or below the
recording layer, which may cause noises when recording is
repeatedly carried out, is less likely to be accumulated.
Such accumulation of the deformation tends to decrease
the repeated recording durability, and by bringing the
film thickness of the recording layer to be within the
above range, this tendency can be suppressed.
In a case where recording/retrieving is carried out
by means of a focused laser beam of an object lens having
a numerical aperture of from about 0.6 to about 0.65 from
a LD (laser diode) having a wavelength of about 6 50 nm,
such as rewritable DVD, or for a high density medium on
which recording/retrieving is carried out by means of a
focused laser beam of an object lens having a numerical
aperture of from about 0.7 to about 0.85 from a blue LD
having a wavelength of about 400 nm, the requirement
against noises is more strict, and accordingly in such a
case, the more preferred thickness of the recording layer
is at most 25 nm.

(A-l) More preferred embodiment regarding recording layer
film thickness
In the present invention, it is considered that with
respect to an optical information recording medium having
a recording layer containing the composition represented
by the above formula (1) as the main component, on which
high speed recording/erasing is possible, by making the
film thickness of the recording layer extremely thin, the
recording characteristics at the second recording after
the optical information recording medium is stored for a
long time can be made favorable and the decrease in the
reflectivity after the long term storage can be reduced.
Specifically, it seems that by making the film thickness
of the recording layer preferably at most 11 run, of the
optical information recording medium employing the
recording layer having a composition represented by the
above formula (1), the recording characteristics at the
second recording after long term storage tend to be
improved, and the decrease in the reflectivity after long
term storage tend to be reduced.
Regarding the optical information recording medium
employing the recording layer having a composition
represented by the above formula (1), the jitter at the
second recording after long term storage is somewhat poor
in some cases. The reason is not necessarily clear, but
is considered to relate to the tendency for the signal
intensity at the first recording after the long term

storage to be low. Namely, when recording is carried out
after the optical information recording medium is stored
for a long time, a signal amplitude at the first
recording tends to be low. The signal amplitude recovers
by further carrying out recording several times, and
accordingly, the decrease in the signal amplitude at the
first recording is considered to be caused by that the
recording mark is less likely to be large when the
crystalline portion after the long term storage is
changed into an amorphous state for the first time.
Further, the reason why the jitter is likely to
deteriorate at the second recording after the long term
storage is considered to be because a portion which is
changed into an amorphous state for the first time after
the long term storage (a portion which is not irradiated
with a recording laser beam at the first recording) and a
portion which is changed into an amorphous state again
(for a second time) are both present. Namely, it is
considered that there is a dispersion of the size of the
amorphous marks due to the above presence of two phases
in the second recording.
Further, the cause of the tendency for the amorphous
marks to be less likely to be large at the time of the
first recording after the long term storage is not clear,
but is considered that a certain change occurs at the
crystalline portion of the recording layer by the long
term storage, since the characteristics recover after

several recordings. By making the recording layer
extremely thin (preferably at most 11 run) , the
characteristics at the second recording after the long
term storage are improved, and this is considered to be
because the above change at the recording layer
crystalline portion tends to be suppressed.
Further, by making the recording layer extremely
thin (preferably at most 11 nm), the decrease in the
reflectivity by the long term storage tends to be
suppressed. The reason is not clear also, however, it is
considered that the change of the recording layer after
the long term storage is suppressed, similar to the
improvement of the recording characteristics at the
second recording after the long term storage.
However, if the recording layer is made extremely
thin, the recording characteristics such as the signal
amplitude may be impaired in some cases. However,
regarding this point, the recording characteristics such
as the signal amplitude can be brought to an adequately
satisfactory level by adjusting the layer structure of
the optical information recording medium and the film
thickness.
Namely, in a case of the optical information
recording medium wherein a protective layer, a recording
layer having a composition represented by the above
formula (1), a protective layer and a reflective layer
are formed on a substrate in this order or in the

opposite order, the signal intensity tends to be low when
the film thickness of the recording layer is made
extremely thin (thinner than about 12 nm for example).
Accordingly, in a case where the recording layer is made
extremely thin (at most 11 nm for example), a device is
required to obtain a high signal intensity.
For example, one method is to change the film
thickness of the protective layer located on the side
from which the laser beam enters the recording layer.
Namely, the film thickness of the protective layer is
made thinner than the film thickness of the protective
layer with which the reflectivity of the optical
information recording medium reaches the minimum value.
The film thickness at which the reflectivity reaches the
minimum value varies depending upon the laser wavelength
to be used, however, it is in the vicinity of 50 nm at
the film thickness in the vicinity of 650 nm in DVD. By
employing such a film thickness, the signal intensity
becomes optically high.
However, it is known that when the film thickness of
the protective layer on the laser beam incident side
becomes thin, the thermal influence over e.g. the
substrate tends to be significant, and the repeated
recording durability tends to deteriorate in general.
Accordingly, the above method of making the film
thickness of the protective layer thin (in the vicinity
of 50 nm for example) can be hardly employed. It is

considered that an adequate repeated recording durability
of an optical information recording medium can be
obtained by employing a protective layer A (a protective
layer containing a metal oxysulfide or a metal nitride)
as described hereinafter for the entire protective layer
or by employing the protective layer A as described
hereinafter for the protective layer region of the
protective layer which is in contact with the recording
layer, even if the film thickness of the protective layer
on the side from which the laser beam enters relative to
the recording layer is made thin (at most 50 nm for
example), against the above tendency. The details about
the protective layer A will be explained below.
Under the above situation, the film thickness of the
recording layer of the present embodiment is preferably
at most 15 nm, more preferably at most 14 nm, furthermore
preferably at most 13 nm, particularly preferably at most
12 nm, most preferably at most 11 nm.
On the other hand, as mentioned above, also in a
case where the film thickness of the recording layer is
made extremely thin in order to improve the recording
characteristics after the long term storage, no adequate
signal intensity can be obtained even by adjusting the
layers other than the recording layer if the film
thickness of the recording layer is excessively thin.
The lower limit of the signal intensity depends on the
performance of the retrieving apparatus, and in a case of

rewritable DVD, the signal intensity tends to be low and
the use tends to be difficult if the recording layer film
thickness is less than 3 nm.
(A-4) Method for producing recording layer
The above recording layer can be obtained by DC or
RF sputtering of a predetermined alloy target in an inert
gas, particularly in an Ar gas.
Further, the density of the recording layer is
usually at least 80%, preferably at least 90% of the bulk
density. As the bulk density p, an approximate value
from the following mathematical formula (2) is usually
employed, but it may be actually measured by preparing a
mass having an alloy composition constituting the
recording layer:
p=∑mipi (2)
wherein mi is the molar concentration of each element i,
and pi is the atomic weight of the element i.
In the sputtering deposition method, the high energy
Ar amount to be irradiated on the recording layer is
increased by lowering the pressure of the sputtering gas
(usually rare gas such as Ar, hereinafter explanation
will be made with reference to the case of Ar) at the
time of deposition, or by disposing the substrate in the
vicinity of the front of the target, thereby to increase
the density of the recording layer. The high energy Ar
is usually either part of Ar ions to be irradiated on the
target for sputtering which are bounced off and reach the

substrate side, or the Ar ions in the plasma which are
accelerated by the sheath voltage of the entire substrate
face and reach the substrate.
Such an irradiation effect of the high energy rare
gas is referred to as an atomic peening effect, and in
the sputtering by an Ar gas which is commonly employed,
Ar is incorporated into the sputtering film by the atomic
peening effect. Accordingly, the atomic peening effect
can be appraised by the Ar amount in the film. Namely,
the small Ar amount indicates a small high energy Ar
irradiation effect, and a film with a low density is
likely to form.
On the other hand, if the Ar amount is large,
irradiation of the high energy Ar tends to be intense,
and the density of the film tends to be high. However,
Ar incorporated in the film is likely to precipitate as a
void at the time of repeated recording, and is likely to
deteriorate the repeated recording durability.
Accordingly, the discharge is carried out under an
appropriate pressure, usually between the order of from
10-2 to 10-1 Pa.
Now, other constituting elements in the structure of
the optical information recording medium which is the
preferred embodiment of the present invention will be
explained below.
(B) Substrate
As the substrate to be used in the present

invention, a resin such as a polycarbonate, an acrylic
resin or a polyolefin, or glass, or a metal such as
aluminum may be employed. Usually guide grooves with a
depth of a level of from 20 to 80 run are formed on the
substrate, and thus preferred is a substrate made of a
resin on which the guide grooves can be formed by
molding. Further, in the case of a so-called substrate
face incidence (Fig. l(a)) wherein the focused laser beam
for erasing/retrieving the record enters from the
substrate side, the substrate is preferably transparent.
The thickness of the substrate is usually at least
0.05 mm and at most 1.5 mm, however, one of about 1.2 mm
for CD or one of about 0.6 mm for DVD is employed.
Further, in a case where the optical head of the
laser has a high NA (at least about 0.7) and a short
wavelength is employed to achieve a high density, in Fig.
1(b), a covering layer comprising a transparent resin is
further formed on the protective layer on the laser beam
incident side. As its thickness, usually a thin layer of
from about 0.01 mm to about 0.1 mm may also be used.
(C) Protective layer
(C-1) General explanation regarding protective layer used
in the present invention
In the present invention, in order to prevent
evaporation and deformation due to the phase change of
the recording layer, thereby to control the thermal
diffusion at that time, it is preferred that the optical

information recording medium further has a protective
layer. The protective layer is usually formed on one or
both sides of the recording layer, preferably on both
sides. The material of the protective layer is
determined taking into consideration the refractive
index, the thermal conductivity, the chemical stability,
the mechanical strength, the adhesive properties, etc.
Usually, a dielectric such as an oxide, sulfide, nitride
or carbide of a metal or semiconductor, having high
transparency and high melting point, or a fluoride of Ca,
Mg, Li or the like may be employed.
In this case, such an oxide, sulfide, nitride,
carbide or fluoride may not necessarily take a
stoichiometrical composition, and the composition may be
controlled to adjust the refractive index, etc., and it
is effective to use them as mixed. When repeated
recording characteristics are taken into consideration, a
mixture of dielectrics is preferred. More specifically,
a mixture of ZnS or a chalcogen compound such as a rare
earth sulfide with a heat resistant compound such as an
oxide, nitride, carbide or fluoride may be mentioned.
For example, a mixture of heat resistant compounds
containing ZnS as the main component, or a mixture of
heat resistant compounds containing an oxysulfide of the
rare earth, particularly Y2O2S as the main component is
an example of the preferred protective layer composition.
As the material to form the protective layer,

usually a dielectric material may be mentioned. The
dielectric material may, for example, be an oxide of e.g.
Sc, Y, Ce, La, Ti, Zr, Hf, V, Nb, Ta, Zn, Al, Cr, In, Si
or Ge, a nitride of e.g. Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Zn, B, Al, Si, Ge or Sn, a carbide of e.g. Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W or Si, or a mixture thereof.
Further, as the dielectric material, a sulfide, selenide
or telluride of e.g. Zn, Y, Cd, Ga, In, Si, Ge, Sn, Pb,
Sb or Bi, an oxysulfide of e.g. Y or Ce, a fluoride of
e.g. Mg or Ca, or a mixture thereof, may be mentioned.
Further, as a specific example of the dielectric
material, ZnS-SiO2, SiN, SiO2, TiO2, CrN, TaS2 or Y2O2S
may, for example, be mentioned. Among these materials,
ZnS-SiO2 is widely used in view of the high film
deposition rate, the small film stress, the low rate of
change of the volume due to the change in the temperature
and the excellent weather resistance. In a case where
ZnS-SiO2 is used, the compositional ratio of ZnS to SiO2
i.e. ZnS:SiO2 is usually from 0:1 to 1:0, preferably from
0.5:0.5 to 0.95:0.05, more preferably from 0.7:0.3 to
0.9:0.1. Most preferably ZnS:SiO2 is 0.8:0.2.
Taking the repeated recording characteristics into
consideration, the film density of the protective layer
is preferably at least 80% of the bulk state in view of
the mechanical strength. In a case where a mixture of
dielectrics is used, the theoretical density of the
above-described mathematical formula (2) is employed as

the bulk density.
The thickness of the protective layer is usually at
least 1 nm and at most 500 nm in general. When it is at
least 1 nm, the effect of preventing the deformation of
the substrate or the recording layer can be secured, and
a role as the protective layer can be fulfilled.
Further, when it is at most 500 nm, while the role as the
protective layer can be fulfilled, such a phenomenon can
be prevented that the internal stress of the protective
layer itself, the difference in the elastic
characteristics with the substrate or the like will be
remarkable, and thus cracks are formed.
Particularly when a first protective layer is
formed, the first protective layer is required to
suppress e.g. deformation of the substrate due to heat,
and thus its thickness is usually at least 1 nm,
preferably at least 5 nm, particularly preferably at
least 10 nm. With such a thickness, accumulation of the
microscopic deformation of the substrate during the
repeated recording can be suppressed, and remarkable
noise increase by scattering of the retrieving laser beam
is less likely to occur.
On the other hand, the thickness of the first
protective layer is preferably at most 2 00 nm, more
preferably at most 150 nm, furthermore preferably at most
100 nm, with relation to the time required for film
formation. With such a thickness, the change of the

groove shape of the substrate as viewed on the recording
layer plane is less likely to occur. Namely, such a
phenomenon that the depth or width of the grooves is
smaller than the intended shape on the substrate surface
is less likely to take place.
On the other hand, in a case where a second
protective layer is formed, the thickness of the second
protective layer is usually at least 1 run, preferably at
least 5 run, particularly preferably at least 10 nm so as
to suppress the deformation of the recording layer.
Further, it is preferably at most 2 00 nm, more preferably
at most 150 nm, furthermore preferably at most 100 nm,
particularly preferably at most 50 nm, so as to prevent
accumulation of the microscopic plastic deformation in
the interior of the second protective layer which occurs
due to the repeated recording and to suppress the noise
increase due to the scattering of the retrieving laser
beam.
The thicknesses of the recording layer and the
protective layers are selected taking into consideration
the interference effects attributable to the multilayer
structure in addition to the restrictions from the
viewpoint of the mechanical strength and reliability, so
that the efficiency for absorption of the laser beam will
be good, and the amplitude of recording signals, i.e. the
contrast between the recorded state and the non-recorded
state, will be large.

The protective layer may be constituted by a
plurality of layers made of different materials as
described above. Particularly, it is preferred to form
an interfacial layer containing no sulfur or having a low
sulfur content at the interface on the side which is in
contact with the recording layer and/or at the interface
on the side which is in contact with the reflective layer
containing Ag as the main component.
The protective layer is produced usually by a known
sputtering method.
(C-2) Preferred embodiment of protective layer
It is preferred that the information recording
medium used in the present invention has a protective
layer A in contact with the recording layer employing the
composition represented by the above formula (1)
(hereinafter "the composition represented by the above
formula (1)" may sometimes be referred to as "the
predetermined composition"), and the protective layer A
contains a metal oxysulfide or a metal nitride.
In a case where the information recording medium of
the present invention is used as a phase-change type
optical information recording medium, as the material of
the protective layer, usually (ZnS) 80 (SiO2) 20 is used.
This is because this material is excellent in
transparency, the adhesive properties to a conventional
recording layer, the sputtering rate, the cost, etc.
However, when the protective layer of the above

(ZnS) 80 (Si02)20 is used for the recording layer having the
predetermined composition on which high speed
recording/erasing is possible, it seems that an object to
further improve the repeated recording durability arises
in some cases. It is considered that one cause is that a
quick change in temperature is brought about in erasing
the record of a medium for high speed recording, as
compared with a medium for low speed recording. For
example, in a case where the recording linear velocity
doubles, the time to increase the temperature of the
recording layer by irradiation with the laser beam will
be 1/2, and further, the cooling rate tends to be high
also. This is because the temperature distribution of
the melted region of the recording layer is gentle when
the recording is carried out at a low linear velocity,
whereas it tends to be sharp when the recording is
carried out at a high linear velocity. Further, the
distance between the melted region and the laser beam
tends to be relatively long in the recording at a high
linear velocity as compared with the recording at a low
linear velocity. Of course, as the cause of the above
repeated recording durability not being adequate, a cause
resulting from the recording layer material itself, such
as a difference in properties regarding the substance
movement due to the melting and solidification, or such a
cause that the atomic diffusion of e.g. sulfur which is
reported in the case of the combination with a

conventional recording material is more likely to occur,
may also be considered.
In the present invention, by forming a protective
layer A containing GeN for example as the metal nitride
or Y2O2S for example as the metal oxysulfide in contact
with the recording layer containing a recording layer
material of the predetermined composition, further
improvement of the repeated recording durability of the
information recording medium can be expected. The reason
why the improvement of the repeated recording durability
can be expected by forming a protective layer A
containing a metal nitride such as GeN or a metal
oxysulfide such as Y2O2S is not necessarily clear, but is
considered to be because effects to suppress the
deformation of the recording layer due to the quick
change in the temperature by carrying out the high speed
recording as compared with a conventional one, the
substance movement in the recording layer, the atomic
diffusion between the layers, can be obtained.
(1) Protective layer A
In the present invention, it is preferred to
incorporate a metal oxidesulfide or a metal nitride into
the protective layer A in contact with the recording
layer. Of course, a metal oxysulfide and a metal nitride
may be used together. Now, explanation will be made in
further detail.
(1-1) Protective layer A containing metal oxysulfide

In the present invention, it is preferred to use the
protective layer A containing a metal oxysulfide.
Containing a metal oxysulfide means that the constituting
element in the protective layer is present while
maintaining the form of the metal oxysulfide.
In the present invention, it is expected that the
durability when recording is carried out repeatedly on
the information recording medium further improves by
forming the protective layer A containing a metal
oxysulfide in contact with the recording layer having the
predetermined composition. The reason is not clearly
understood yet, but is considered to be related with high
thermal conductivity and hardness of the protective layer
A containing a metal oxysulfide and high uniformity of
the distribution of the constituting element. Namely,
the protective layer A in the present invention has high
thermal conductivity and hardness as compared with a
protective layer employing a composite dielectric
containing ZnS as the main component, as represented by a
ZnS-SiO2 film which has conventionally been commonly
used. On the other hand, the refractive index of the
protective layer A is usually from about 1.7 to about
2.4 although it depends on the compositional ratio, and
is substantially the same as that of a protective layer
employing a composite dielectric containing ZnS as the
main component.
Further, it is considered that deformation of the

recording layer due to thermal expansion tends to be
small since the thermal conductivity of the protective
layer A containing a metal oxysulfide is high. Namely,
since the thermal conductivity of the protective layer A
is high, the heat of the recording layer which is heated
when the recording marks are formed by the laser can be
let loose quickly. Accordingly, the difference in
temperature between the interfacial region which is in
contact with the recording layer of the protective layer
A and the region of the protective layer A which is apart
from the recording layer, or the difference in
temperature between the mark-formed region and the
peripheral region can be instantaneously dissolved. As a
result, peeling of the film or occurrence of the cracks
resulting from the difference in temperature can be
suppressed. In other words, it is considered that the
overwriting deterioration can be delayed. The thermal
conductivity can be indirectly known from the value of
the laser power when amorphous marks are formed on the
prepared disk. Namely, the higher the thermal
conductivity, the higher the laser power required to heat
the recording layer tends to be. For example, in a case
where a protective layer A containing a metal oxysulfide
is used, the laser power required for mark formation
tends to be high as compared with a case where a
protective layer of ZnS=SiO2=80:20 (mol%) is used. This
is because the function of the protective layer A as a

heat dissipation layer is increased due to a high thermal
conductivity.
Further, the JIS Knoop hardness of the protective
layer using ZnS:SiO2=80:20 (mol%) is about 280, whereas
the JIS Knoop hardness of the protective layer A using
Y2O2S for example as the metal oxysulfide is about 520.
The protective layer A having a high hardness is
important with a view to preventing the deformation of
the recording layer. If the hardness is low, it is
difficult to appropriately suppress the change in the
volume of the recording layer due to recording/erasing,
i.e. the deformation resulting from the difference in the
volume between the amorphous state and the crystalline
state, and the deformation is accumulated along with the
increase in the number of the repeated overwriting, thus
causing decrease in the signal intensity.
Further, in the protective layer A containing a
metal oxysulfide, the metal atom is bonded to both sulfur
and oxygen, and accordingly the mixing properties of
sulfur with oxygen are so high and incomparable with a
protective layer employing a mixture of a sulfide and an
oxide such as ZnS-SiO2 or ZnS-Y2O3. Accordingly, it is
considered that the protective layer A has stably high
characteristics since the dispersibility of sulfur,
oxygen and metal atoms such as selenium atoms is high as
compared with conventional ZnS-SiO2. Accordingly, it is
estimated that such a phenomenon that sulfur disperses

from the protective layer to the recording layer during
the repeated overwriting to cause a decrease in the
reflectivity or a change in the crystallization speed is
suppressed.
Further, in a case where the protective layer A
containing a metal oxysulfide such as Y2O2S is formed in
contact with the recording layer having the predetermined
composition to be used in the present invention, the
signal amplitude of the information recording medium
tends to be high as compared with a case where the
protective layer A contains a metal nitride such as GeN.
The reason is not clear, but such a reason that the
properties of the crystal growth of the recording layer
are slightly changed by the protective layer A in contact
with the recording layer, and the size of the amorphous
marks to be formed varies, may be considered. Such
properties are considered to be determined by the
combination of the recording layer material and the
material of the protective layer A, and with respect to
the conventional recording layer material, the change of
the signal intensity by the material of the protective
layer A has not attracted an attention.
As the metal element used for the metal oxysulfide,
a rare earth metal element such as Sc, yttrium or a
lanthanoid element such as La or Ce; or a transition
metal element such as Ti may, for example, be mentioned.
Among them, a rare earth metal element is preferred, and

a rare earth metal element selected from the group
consisting of yttrium and La, Ce, Nd, Sm, Eu, Gd, Tb and
Dy is particularly preferred. The oxysulfide of yttrium
(Y2O2S) is thermochemically more stable than Y2O3 or Y2S3
up to about 1000°C, and accordingly the most preferred
element is yttrium.
The content of the metal oxysulfide in the
protective layer A is preferably at least 5 mol%, more
preferably at least 10 mol%, most preferably at least 15
mol%. If the content of the metal oxysulfide is too low,
the overwriting characteristics may decrease in some
cases. On the other hand, in view of the repeated
overwriting characteristics etc., the content of the
metal oxysulfide in the protective layer A is preferably
as high as possible, and the content of the metal
oxysulfide in the protective layer A may be at most 100
mol%.
Further, the content of the metal element
constituting the metal oxysulfide in the protective layer
A is usually at least 10 atomic%, preferably at least 20
atomic%, more preferably at least 2 5 atomic%. The
content of the metal element constituting the metal
oxysulfide is an index indicating the content of the
metal oxysulfide in the protective layer A, and if the
metal element is too small, the effect for further
improving the overwriting characteristics may not be
adequate in some cases. On the other hand, in view of

the repeated overwriting characteristics, the content of
the metal oxysulfide in the protective layer A is
preferably as high as possible, and thus the upper limit
of the content of the metal element constituting the
metal oxysulfide is the content of the metal element when
the protective layer A consists entirely of the metal
oxysulfide.
Further, for the protective layer A, a metal
oxysulfide and another material may be used together.
Said another material is not particularly limited so long
as it is a material which is commonly used for the
protective layer. For example, a dielectric such as an
oxide, sulfide, nitride or carbide of a metal or
semiconductor, having high transparency and high melting
point, or a fluoride of Ca, Mg, Li or the like, may be
employed in general.
In this case, such an oxide, sulfide, nitride,
carbide or fluoride may not necessarily take a
stoichiometrical composition, and the composition may be
controlled to adjust the refractive index, etc., and it
is effective to use them as mixed. When repeated
recording characteristics are taken into consideration, a
mixture of dielectrics is preferred.
Further, as the material to be contained in the
protective layer A, usually a dielectric material may be
mentioned. As the dielectric material, an oxide of e.g.
Sc, Y, Ce, La, Ti, Zr, Hf, V, Nb, Ta, Zn, Al, Cr, In, Si

or Ge, a nitride of e.g. Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Zn, B, Al, Si, Ge or Sn, a carbide of e.g. Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W or Si, or a mixture thereof may, for
example, be mentioned. Further, as the dielectric
material, a sulfide, selenide or telluride of e.g. Zn, Y,
Cd, Ga, In, Si, Ge, Sn, Pb, Sb or Bi, an oxysulfide of
e.g. Y or Ce, a fluoride of e.g. Mg or Ca, or a mixture
thereof may be mentioned.
More specifically, an oxide, sulfide, nitride,
carbide or fluoride of a metal or semiconductor, as
represented by zinc sulfide, zinc oxide, silicon oxide,
silicon nitride, aluminum nitride, aluminum oxide, a rare
earth oxide, a rare earth sulfide, a rare earth fluoride,
magnesium fluoride, etc. may, for example, be mentioned.
Among them, particularly preferred is a zinc compound
such as zinc sulfide or zinc oxide, which is excellent in
the adhesive properties with the recording layer. As a
result, a more stable and higher durability can be
obtained.
In a case where another material is contained in the
protective layer A other than the metal oxysulfide, the
content of the material is usually at most 99 mol%,
preferably at most 90 mol%. On the other hand, it is
usually at least 1 mol%, preferably at least 5 mol%.
However, the appropriate content varies depending
upon the type of the material to be mixed. For example,
in a case where zinc sulfide is used as the above

material, its amount may be high, and it is usually at
least 20 mol%, preferably at least 3 0 mol%, furthermore
preferably at'least 50 mol%, most preferably at least 60
mol%.
On the other hand, in a case where zinc oxide is
used as the above material, a too high content tends to
be unfavorable, and the content is usually at most 3 0
mol%, preferably at most 2 0 mol%, furthermore preferably
at most 10 mol%. Further, the molar content of zinc
oxide is preferably at most half the molar content of the
metal oxysulfide.
As the particularly preferred composition of the
protective layer A, a mixed composition containing Y2O2S
and ZnS may be mentioned. In this case, particularly
excellent overwriting characteristics can be obtained.
In this case, the molar ratio of ZnS to Y2O2S is usually
at least 1%, preferably at least 5%, more preferably at
least 10%, and usually at most 1000%, preferably at most
700%, furthermore preferably at most 500%.
Further, it is possible to let zinc in the metal
form be present in the protective layer A. However, it
is contained preferably in the form of a zinc compound
such as zinc oxide or zinc sulfide as described above.
In the present invention, the purity of the
protective layer A (the content of the metal oxysulfide
or the content of a mixture of the metal oxysulfide with
another material in the protective layer A) is preferably

at least 90 mol%. The purity is preferably as high as
possible, however, the influence of impurities in an
amount less than 10 mol% over the characteristics of the
protective layer A is negligible. Particularly when the
impurities are stable compounds, the bad influence tends
to be small, however, if the amount of the impurities
exceeds 10 mol%, there is high possibility that the
physical property values such as the hardness or the
stress of the film change, and the characteristics of the
protective layer A may deteriorate.
The protective layer A containing a metal oxysulfide
can be formed by deposition by means of a sputtering
method using a target containing a metal oxysulfide.
Usually, a target having a composition within a range
substantially the same as the preferred composition of
the protective layer A is used.
Namely, it is preferred to use one containing a
metal oxysulfide as the target for sputtering. The type
of the metal element of the metal oxysulfide to be used
for the target is optionally selected according to the
composition of the protective layer A.
Further, in a case where the protective layer A
contains a metal oxysulfide and another protective layer
material, a target of a mixture of the metal oxysulfide
and the another material may be used in accordance with
the composition of the another material to be used.
Further, a target of the metal oxysulfide and a target of

the above another material may be separately prepared,
and they are subjected to sputtering at the same time.
The content of the metal oxysulfide in the target is
usually at least 10 mol%, preferably at least 30 mol%,
more preferably at least 50 mol%. If the content of the
metal oxysulfide in the target is excessively low, the
metal oxysulfide may be decomposed in the target, whereby
the metal oxysulfide cannot be incorporated in the
protective layer A in some cases. On the other hand, the
content of the metal oxysulfide in the target varies
depending upon the content of the above another
protective layer material. However, in a case where a
target comprising a metal oxysulfide simple substance is
used, the content of the metal oxysulfide in the target
is usually 100 mol%.
Whether or not the metal oxysulfide is contained in
the target can be confirmed by measuring the X-ray
diffraction of the target.
Further, the target containing a metal oxysulfide is
produced usually by using a powder of the metal
oxysulfide or a mixed powder of an oxide and a sulfide of
the same metal, by using a known method such as hot
pressing method. Preferred as the metal to be used is a
rare earth or a metal element.
As the conditions for sputtering, known conditions
may be employed.
For the analysis of the composition of the

protective layer A, usually the composition may be
identified by combination of e.g. Auger electron
spectroscopy (AES), Rutherford back scattering (RBS),
inductively-coupled plasma spectrometry (ICP) etc.
(1-2) Protective layer A containing metal nitride
In the present invention, it is also preferred to
use a protective layer containing a metal nitride as the
protective layer A.
A metal nitride tends to have a high thermal
conductivity similar to the metal oxysulfide, and
accordingly it is considered that the high thermal
conductivity of the protective layer A suppresses peeling
of the film or occurrence of the cracks resulting from
the difference in temperature, and can delay
deterioration of the overwriting, similar to the above
case of one containing a metal oxysulfide as mentioned
above.
As the metal to be used for the metal nitride, at
least one element selected from the group consisting of
Si, Ge, Al, Ti, Ta, Cr, Mo, Nb, Zr and Hf may, for
example, be mentioned. The nitride of such an element is
stable, and thus the storage stability of the information
recording medium tends to improve. A plurality of the
above elements may be used. Preferred as the above
element is Si, Ge, Al or Cr which provides higher
transparency and excellent adhesion properties.
In a case where one type of the above element is

used, as the material formed by the above element and
nitrogen, a nitride of the above element simple substance
may be mentioned. More specifically, a composition in
the vicinity of e.g. Si-N, Ge-N, Cr-N or Al-N may be
mentioned. Among them, in view of higher effect for
preventing diffusion into the recording layer, it is
preferred to use Si-N (nitride of silicon), Ge-N (nitride
of germanium) or Al-N (nitride of aluminum), and it is
more preferred to use Ge-N (nitride of germanium).
In a case where at least two of the above elements
are used, as the material formed by the above elements
and nitrogen, a composite nitride of the above elements
may be mentioned. As such a compound, as representative
examples using Ge-N, one containing, together with Ge,
e.g. Al, B, Ba, Bi, C, Ca, Ce, Cr, Dy, Eu, Ga, In, K, La,
Mo, Nb, Ni, Pb, Pd, Si, Sb, Sn, Ta, Te, Ti, V, W, Yb, Zn
or Zr, such as Ge-Si-N, Ge-Sb-N, Ge-Cr-N, Ge-Al-N, Ge-Mo-
N or Ge-Ti-N may be mentioned.
The content of the metal nitride in the protective
layer A is preferably at least 5 mol%, more preferably at
least 10 mol%; most preferably at least 15 mol%. If the
content of the metal nitride is too low, the overwriting
characteristics may decrease in some cases. On the other
hand, in view of the repeated overwriting characteristics
etc., the content of the metal nitride in the protective
layer A is preferably as high as possible, and the
content of the metal nitride in the protective layer A

may be at most 100 mol%.
Further, the content of the metal element
constituting the metal nitride in the protective layer A
is usually at least 10 atomic%. Preferably at least 20
atomic%, more preferably at least 2 5 atomic%. If the
content of the metal nitride is too low, the effect for
further improving the overwriting characteristics may not
be adequate in some cases. On the other hand, in view of
the repeated overwriting characteristics etc., the
content of the metal nitride in the protective layer A is
preferably as high as possible, and thus the upper limit
of the content of the metal element constituting the
metal nitride is the content of the metal element when
the protective layer A consists entirely of the metal
nitride.
Further, for the protective layer A, a metal nitride
and another material may be used together. As the
another material and its content, the same material as
one explained for the protective layer A containing a
metal oxysulfide may be employed.
In the present invention, the purity of the
protective layer A (the content of the metal nitride or
the content of a mixture of the metal nitride and another
material in the protective layer A) is preferably at
least 90 mol%. The purity is preferably as high as
possible, however, the influence of impurities in an
amount less than 10 mol% over the characteristics of the

protective layer A is negligible. Particularly when the
impurities are stable compounds, the bad influence tends
to be small, however, if the amount of the impurities
exceeds 10 mol%, there is high possibility that the
physical property values such as the hardness or the
stress of the film change, and the characteristics of the
protective layer A may deteriorate.
The protective layer A containing a metal nitride
can be formed by deposition by means of a sputtering
method using a target containing a metal nitride.
Further, the protective layer A may be formed also by a
reactive sputtering method in which a slight amount of a
mixed gas of Ar and N2 is flown in a vacuum chamber, and
under a predetermined vacuum pressure, a voltage is
applied to a target comprising a predetermined metal (a
metal element simple substance or a metal element
composite in the metal nitride contained in the
protective layer A) for discharge, and the ejected metal
element simple substance or metal element composite is
reacted with N2 to convert it into a nitride for
deposition. Here, it has to be noted that the
transparency of the protective layer A is hardly secured
if the nitrogen content in the protective layer A is
excessively low, and the improvement of the repeated
recording durability of the optical information recording
medium tends to be insufficient if the nitrogen content
is excessively high. Accordingly, in a case where the

above reactive sputtering method is employed, it is
important to adjust the nitrogen flow amount. Further,
the pressure at the time of sputtering also has an
influence over the film properties. Usually, by
decreasing the pressure, the protective layer A can be
formed densely.
For the analysis of the composition of the
protective layer A, the composition can be identified
usually by combination of Auger electron spectroscopy
(AES), Rutherford back scattering (RBS), inductively-
coupled plasma spectroscopy (ICP) etc.
(1-3) Film thickness of protective layer A
The preferred range of the film thickness of the
protective layer A varies depending upon the position at
which the protective layer A is used.
Namely, in a case where the protective layer A is
formed as the first protective layer, the first
protective layer is required to suppress e.g. the
deformation of the substrate due to heat, and its
thickness is usually at least 1 nm, preferably at least 5
nm, particularly preferably at least 10 nm. With such a
thickness, accumulation of the microscopic deformation of
the substrate during the repeated recording can be
suppressed, and a remarkable noise increase by scattering
of the retrieving laser beam is less likely to occur.
On the other hand, the thickness of the first
protective layer is preferably at most 2 00 nm, more

preferably at most 150 nm, furthermore preferably at most
100 nm, with relation to the time required for film
formation. With such a thickness, a change in the groove
shape of the substrate as viewed on the recording layer
plane is less likely to occur. Namely, such a phenomenon
that the depth or width of the grooves is smaller than
the intended shape on the substrate surface is less
likely to take place.
In a case where the protective layer A is formed as
the second protective layer, the thickness of the second
protective layer is usually at least 1 nm, preferably at
least 5 nm, particularly preferably at least 10 nm so as
to suppress deformation of the recording layer. Further,
in order to prevent accumulation of microscopic plastic
deformation in the interior of the second protective
layer which occurs along with the repeated recording,
thereby to suppress the noise increase by scattering of
the retrieving laser beam, it is preferably at most 2 00
nm, more preferably at most 150 nm, furthermore
preferably at most 100 nm, particularly preferably at
most 50 nm.
However, in the present invention, usually the
protective layer A having a high thermal conductivity and
having a high hardness is formed in contact with the
recording layer, and accordingly the film thickness of
the protective layer A located on the side from which the
laser beam enters relative to the recording layer can be

made thin, as explained in the above explanation for the
recording layer. Namely, in a case where the protective
layer A is formed in contact with the recording layer
face on the side from which the laser beam enters, the
film thickness of the protective layer A is preferably at
most 50 run.
The sputtering rate of the material containing e.g.
a metal oxysulfide such as Y2O2S as the main component,
tends to be low as compared with the sputtering rate of a
material such as (ZnS)80(SiO2) 20 which has conventionally
been employed. Accordingly, with a view to increasing
the productivity of the information recording medium, the
protective layer A containing e.g. a metal oxysulfide may
be formed relatively thinly in contact with the recording
layer and a protective layer B may be formed in contact
with the protective layer A. Further, a material which
has conventionally been employed (e.g. (ZnS) so (SiO2) 20)
may be used for the protective layer B. The details of
the specific embodiment of such an information recording
medium will be described hereinafter.
As mentioned above, in a case where the protective
layer has a multilayer structure by using the protective
layer A and the protective layer B, the film thickness of
the protective layer A in the present invention is
usually at least 0.1 nm, preferably at least 1 nm, more
preferably at least 2 nm, furthermore preferably at least
3 nm, particularly preferably at least 5 nm. On the

other hand, the film thickness of the protective layer A
is usually at most 100 run, preferably at most 50 nm, more
preferably at most 2 5 nm, furthermore preferably at most
10 nm.
(1-4) Position of protective layer A and recording layer
In the present invention, it is preferred that the
protective layer A containing a metal oxysulfide or a
metal nitride is formed in contact with the recording
layer. More preferably, the above predetermined
protective layer A is formed on both sides of the
recording layer. It is because the repeated overwriting
characteristics can be further improved by forming the
above predetermined protective layer A on both sides of
the recording layer. In general, by forming the above
predetermined protective layer A on both sides of the
recording layer, the recording layer and the protective
layer A tend to peel off, however, it is considered that
the above problem of peeling is less likely to occur in
the recording layer employing the predetermined
composition of the present invention.
For example, if the protective layer A containing a
metal oxysulfide such as Y2O2S is formed in contact with
a conventional recording layer of SbTe eutectic (Sb70Te30)
composition, film peeling in an environment resistance
test tends to occur. This tendency becomes more
remarkable if the above protective layer A is formed on
both sides of the recording layer. For example, with

respect to a conventional recording layer employing a
SbTe eutectic composition, if the protective layer A
containing a metal oxysulfide such as Y2O2S is formed in
contact with both sides of the recording layer, film
peeling occurs in an environment resistance test with
high humidity, and the adhesive properties and the
weather resistance of the film tend to be not necessarily
sufficient.
(2) Protective layer B
Another example of the preferred layer structure of
the optical information recording medium is to make one
or both of the first and second protective layers have a
two-layer structure comprising the protective layer A and
the protective layer B. In view of e.g. the repeated
overwriting, it is preferred to make the first protective
layer located on the laser beam incident side have a two-
layer structure (Figs. 6(a), 6(b)), and it is more
preferred to make both the first and the second
protective layers have a two-layer structure comprising
the protective layer A and the protective layer B (Figs.
7(a) , 7(b) ) .
In the above preferred layer structure, the first
protective layer or the second protective layer has a
two-layer structure comprising the protective layer A and
the protective layer B, however, the layer structure is
not limited to such an embodiment so long as the
protective layer A is formed in contact with the

recording layer. For example, it may be optionally
carried out to make the first protective layer or the
second protective layer have a multilayer structure of at
least three layers, by further forming a protective layer
formed by another material in contact with the protective
layer B.
(2-1) Material, production method etc. of protective
layer B
As the material of the protective layer B, a
material commonly used for the protective layer may
optionally be used. Such a material has already been
explained, and the explanation is omitted here. The
protective layers A and B may be two layers comprising
different materials, or they may have a gradient
composition in which the respective components gradually
change.
Further, as the method for producing the protective
layer B, a production method commonly used for the
protective layer may be used.
(2-2) Film thickness of protective layer B
The protective layer B is in contact with the
protective layer A, and plays a role as the protective
layer in a two-layer structure of the protective layer A
and the protective layer B. Accordingly, the film
thickness of the protective layer B is a film thickness
obtained by subtracting the film thickness of the
protective layer A from the film thickness which is


usually required for a protective layer.
However, in the present invention, the protective
layer A usually having a high thermal conductivity and a
high hardness is formed in contact with the recording
layer, and accordingly the film thickness of the
protective layer located on the side from which the laser
beam enters relative to the recording layer (for example,
the film thickness of the protective layer A in a case
where the protective layer is formed only by the
protective layer A, or the total film thickness of the
protective layer A and the protective layer B in a case
where the protective layer A and the protective layer B
are laminated to form the protective layer) can be made
thin, as explained in the above explanation for the
recording layer.
Namely, the total of the film thickness of the
protective layer A and the film thickness of the
protective layer B is preferably at most 50 nm, in a case
where the protective layer A is formed in contact with
the recording layer face on the side from which the laser
beam enters, and the protective layer B is further formed
in contact with the protective layer A.
As mentioned above, in a case where the protective
layer has a multilayer structure by using the protective
layer A and the protective layer B, the film thickness of
the protective layer A in the present invention is
usually at least 0.1 nm, preferably at least 1 nm, more

preferably at least 2 nm, furthermore preferably at least
3 ran, particularly preferably at least 5 nm. On the
other hand, the film thickness of the protective layer A
is usually at most 100 nm, preferably at most 50 nm, more
preferably at most 25 nm, furthermore preferably at most
10 nm. Accordingly, the film thickness of the protective
layer B is the rest obtained by subtracting the film
thickness of the protective layer A from the total film
thickness of the protective layer.
The thicknesses of the recording layer and the
protective layers are selected taking into consideration
the interference effects attributable to the multilayer
structure in addition to restrictions from the viewpoint
of the mechanical strength and reliability, so that the
efficiency for absorption of the laser beam will be good,
and the amplitude of recording signals, i.e. the contrast
between the recorded state and the non-recorded state,
will be large.
(D) Reflective layer
In the optical information recording medium, a
reflective layer may further be formed. In the present
invention, it is preferred that the optical information
recording medium further has a reflective layer with a
view to increasing the heat dissipation properties of the
recoding layer.
The position at which the reflective layer is formed
usually depends at the incident direction of the

retrieving laser beam, and it is formed on the opposite
side of the recording layer from the incident side.
Namely, in a case where the retrieving laser beam enters
from the substrate side, the reflective layer is formed
usually on the opposite side of the recording layer from
the substrate, and in a case where the retrieving laser
beam enters from the recording layer side, the reflective
layer is formed usually between the recording layer and
the substrate (Figs. l(a), 1(b)).
As the material to be used for the reflective layer,
a substance having a high reflectivity is preferred, and
particularly preferred is a metal such as Au, Ag or Al
which can be expected to have a heat dissipation effect
also. The heat dissipation properties are determined by
the film thickness and the thermal conductivity, and
since the thermal conductivity is substantially in
proportion to the volume resistivity in the case of such
a metal, the heat dissipation performance may be
represented by the sheet resistivity. The sheet
resistivity is usually at least 0.05 Ω/□, preferably at
least 0.1 Ω/□, and on the other hand, it is usually at
most 0.6 Ω/□, preferably at most 0.5 Ω/□, more preferably
at most 0.4 Ω/□, furthermore preferably at most 0.2 Ω/□.
This is to guarantee particularly high heat
dissipation properties, and is necessary to suppress
recrystallization to a certain extent in a case where
competition between the formation of an amorphous phase

and the recrystallization is remarkable in the formation
of amorphous marks, as in the recording layer to be used
for the optical information recording medium. In order
to control the thermal conductivity of the reflective
layer itself or to improve the corrosion resistance, e.g.
Ta, Ti, Cr, Mo, Mg, V, Nb, Zr or Si may be added in a
small amount to the above metal. The addition amount is
usually at least 0.01 atomic% and at most 20 atomic%. An
aluminum alloy containing at least one of Ta and Ti in an
amount of at most 15 atomic%, particularly an alloy of
AlTa1- (0 and is a particularly preferred reflective layer material
with a view to improving the reliability of the optical
information recording medium.
Particularly in a case where the film thickness of
the second protective layer is at least 40 nm and at most
50 nm, the amount of the added element contained is
preferably at most 2 atomic% so as to make the reflective
layer have a high thermal conductivity.
Particularly preferred as the material of the
reflective layer is one containing Ag as the main
component. "Containing Ag as the main component" means
that Ag is contained in an amount of at least 50 atomic%
based on the entire reflective layer. The content of Ag
based on the entire reflective layer is preferably at
least 70 atomic%, more preferably at least 80 atomic%,
furthermore preferably at least 9 0 atomic%, particularly

preferably at least 95 atomic%. Most preferred with a
view to increasing the heat dissipation properties is to
employ pure Ag as the material of the reflective layer.
The reason why Ag is contained as the main component
is as follows. Namely, recording is carried out again on
recording marks which are stored for a long time, such a
phenomenon may take place in some cases that the
recrystallization speed of the phase-change recording
layer is high only at the first recording immediately
after the storage. The reason why such a phenomenon
takes place is not clear, but is supposed to be because
the size of the amorphous marks formed by the first
recording immediately after the storage is smaller than
the desired size of the marks due to increase in the
recrystallization speed of the recording layer
immediately after the storage. Accordingly, in a case
where such a phenomenon takes place, Ag having extremely
high heat dissipation properties may be used for the
reflective layer to increase the cooling rate of the
recording layer, whereby recrystallization of the
recording layer at the first recording immediately after
the storage can be suppressed and the size of the
amorphous marks can be maintained to the desired size.
A Ag alloy containing one member of Mg, Ti, Au, Cu,
Pd, Pt, Zn, Cr, Si, Ge, Bi and a rare earth element in an
amount of at least 0.01 atomic% and at most 10 atomic% in
Ag has also a high reflectivity and a high thermal

conductivity, is excellent in heat resistance and is
preferred.
The film thickness of the reflective layer is
usually at least 10 nm so that the incident laser beam is
completely reflected so that there is no transmitted
light, and it is preferably at least 2 0 nm, more
preferably at least 40 nm. Further, when it is too
thick, there is no change in the heat dissipation effect,
the productivity is unnecessarily deteriorated, and the
cracks are likely to occur, and accordingly it is usually
at most 500 nm. However, it is preferably at most 400
nm, more preferably at most 3 00 nm.
The recording layer, the protective layer and the
reflective layer are formed usually by e.g. a sputtering
method.
It is preferred to carry out deposition in an in-
line apparatus having a recording layer target, a
protective layer target and, if necessary, a reflective
layer material target provided in the same vacuum
chamber, with a view to preventing oxidation or
contamination among the respective layers. Further, it
is excellent in view of the productivity also.
(E) Protective coating layer
It is preferred to form a protective coating layer
comprising a ultraviolet-curing resin or a thermosetting
resin on the outermost surface side of the optical
information recording medium, so as to prevent direct

contact with the air or to prevent scars by the contact
with foreign materials. The protective coating layer has
a thickness of usually from 1 urn to several hundred m.
Further, a dielectric protective layer having high
hardness may further be formed, or a resin layer may
further be formed thereon.
(Initial crystallization method of optical information
recording medium)
The recording layer is formed usually by a physical
vapor deposition method in vacuum such as a sputtering
method. However, in a state immediately after the
deposition (as-deposited state), the recording layer is
usually amorphous, and therefore, it is preferred to
crystallize the recording layer to form a non-recorded or
erased state. This operation is referred to as
initialization (or initial crystallization). As the
initial crystallization operation, a method such as oven
annealing in a solid phase at a temperature of at least
the crystallization temperature (usually from 150 to
3 00°C) and at most the melting point, annealing under
irradiation with a light energy of e.g. a laser beam or a
flash lamp beam or melt initialization may, for example,
be mentioned. In the present invention, among the above
initial crystallization operations, it is preferred to
employ melt initialization, since a phase-change
recording material with a small formation of crystal
nuclei is employed.

In the melt initialization, if the recrystallization
speed is too slow, there will be a time until the thermal
equilibrium is reached, whereby other crystalline phases
are likely to be formed. Accordingly, it is preferred to
increase the cooling rate to some extent. Further, if
the recording layer is held in a melted state for a long
time, the recording layer may cause flow, a think film
such as the protective layer may peel off by the stress,
or e.g. the resin substrate may deform, thus leading to
destruction of the medium, such being unfavorable.
For example, the time for maintaining the
temperature at a level of at least the melting point is
preferably usually at most 10 s, preferably at most 1
s.
Further, for the melt initialization, it is
preferred to employ a laser beam. It is particularly
preferred to carry out initial crystallization by using
an oval laser beam having its minor axis substantially in
parallel with the scanning direction (hereinafter, this
initialization method may sometimes be referred to as
"bulk erasing"). In such a case, the length of the major
axis is usually from 10 to 1000 urn, and the length of the
minor axis is usually from 0.1 to 5 urn.
Here, the lengths of the major axis and the minor
axis of the beam are defined from the half value width in
a case where the light energy intensity distribution
within the beam is measured. With respect to the beam

shape also, the minor axis length is preferably at most 5
m, more preferably at most 2 m so as to easily realize
local heating and rapid cooling in the minor axis
direction.
As the laser beam source, various types may be used
including, for example, a semiconductor laser and a gas
laser. The power of the laser beam is usually from about
100 mW to about 10 W. Further, another light source may
be used so long as a power density and a beam shape at
the same level can be obtained. Specifically, a Xe lamp
laser beam may, for example, be mentioned.
In the initialization by bulk erasing, when a disk-
form recording medium is used for example, the minor axis
direction of an oval beam is brought substantially into
line with the circumferential direction, and by rotating
the disk, scanning is carried out in the minor axis
direction, while moving the beam in the major axis
(radial) direction every one revolution (one rotation),
whereby initialization can be carried out over the entire
surface. By doing this, a polycrystal structure aligned
in a specific direction relative to the focused laser
beam for recording/retrieving scanned along the track in
the circumferential direction can be realized.
The moving distance in the radial direction per one
rotation is preferably set to be shorter than the major
axis of the beam, so that the irradiated regions overlap,
and the same radial region will be irradiated a plurality

of times with the laser beam. As a result,
initialization can certainly be carried out, and at the
same time, it is possible to avoid non-uniformity of the
initial crystallization state attributable to the energy
distribution (usually from 10 to 20%) in the radial
direction of the beam. On the other hand, if the moving
distance is too short, undesirable crystalline phases
tend to be formed. Accordingly, the moving distance in
the radial direction is usually set to be at least 1/2 of
the major axis of the beam. Further, the scanning
velocity of the initialization energy beam is usually
within a range of from 3 to 2 0 m/s.
Whether or not at least the optical information
recording medium of the present invention can be obtained
by melt initialization can be judged by determining
whether or not the reflectivity R1 in the non-recorded
state after initialization is substantially equal to the
reflectivity R2 in the erased state by recrystallization
after recording of amorphous marks is carried out by a
practical focused laser beam for recording (for example,
a focused laser beam having a diameter of about 1 n).
Here, R2 is the reflectivity at the erased portion after
recording 10 times.
Accordingly, the optical information recording
medium of the present invention preferably satisfies the
following relational expression (3) where the
reflectivity at the non-recorded portion after initial

crystallization is Rl and the reflectivity at the erased
portion after recording 10 times is R2:
∆R=2│R1-R2│/(R1+R2)xl00(%) The reason why the reflectivity R2 at the erased
portion after recording 10 times is taken as the judgment
index is that when recording is carried out 10 times, the
influence of the reflectivity in a crystalline state
which may remain in a non-recorded state if recording is
carried out only once, can be removed, and the entire
surface of the optical information recording medium can
be made to be in a state where it is recrystallized by
recording and erasing at least once. On the other hand,
if the number of recording is excessively higher than 10
times, factors other than the change in the crystal
structure of the recording layer, such as microscopic
deformation of the recording layer due to the repeated
recording or diffusion of a foreign element from the
protective layer to the recording layer may cause a
change in the reflectivity, and accordingly it tends to
be difficult to judge whether or not the desired
crystalline state can be obtained.
In the above relational expression (3), AR is at
most 10%, and it is preferably at most 5%. When it is at
most 5%, an optical information recording medium having
lower signal noises can be obtained.
For example, of an optical information recording
medium with Rl of about 17%, R2 may be substantially

within a range of from 16 to 18%.
The above erased state may also be obtained by
irradiation with the writing power in a direct current
fashion to melt the recording layer, followed by
resolidification, without necessarily modulating the
focused recording laser beam in accordance with a
practical recording pulse-generating method.
In order to obtain the desired initial crystalline
state of the phase-change recording material to be used
for the recording layer in the present invention, it is
particularly important to set the scanning velocity of
the initialization energy beam relative to the recording
layer plane. Basically, it is important that the
crystalline state after initial crystallization is
similar to the crystalline state at the erased portion
after recording, and accordingly, the scanning velocity
is in the vicinity of the relative scanning linear
velocity of the focused laser beam to the recording layer
face when practical recording is carried out by using a
focused laser.beam. Specifically, the initialization
energy beam is scanned at a linear velocity of from about
2 0 to about 80% of the maximum linear velocity when
recording is carried out on the optical information
recording medium.
The maximum linear velocity for recording is, for
example, a linear velocity when the erase ratio becomes
at least 2 0 dB at the time of irradiation with an erasing

power Pe in a direct current fashion at that linear
velocity.
The erase ratio is defined as the difference between
the carrier level of signals of the amorphous marks
recorded substantially at a single frequency and the
carrier level after erasing by direct current irradiation
of Pe. Measurement of the erase ratio is carried out as
follows for example. Firstly, under recording conditions
under which adequate signal characteristics (i.e. such
characteristics that e.g. the reflectivity and the signal
amplitude or the jitter satisfy specified values) are
obtained, a condition with a high frequency is selected
among modified signals to be recorded, recording is
carried out 10 times at a single frequency to form
amorphous marks, and the carrier level (C.L. at
recording) is measured. Then, the direct current
irradiation is carried out once on the amorphous marks
while changing the erasing power Pe, and the carrier
level at this-time (C.L. after erasing) is measured, to
calculate the difference between C.L. at recording and
C.L. after erasing, i.e. the erase ratio. When the power
Pe of the direct current irradiation is changed, the
erase ratio tends to increase once, decrease and then
increase again in general. Here, the first peak value of
the erase ratio observed when the power Pe starts being
increased is taken as the erase ratio of the sample in
this case.

With respect to the scanning rate of the
initialization energy beam, if the initialization energy
beam is scanned at a velocity lower by about 2 0% than the
above defined maximum linear velocity, phase isolation
may occur and a single phase is less likely to be
obtained, or even if a single phase is obtained,
crystallites may extend particularly in the
initialization beam scanning direction and become giant,
or aligned in an unfavorable direction. Preferably, the
initialization energy beam is scanned at a velocity of at
least 30% of the recordable maximum linear velocity.
On the other hand, if the initialization energy beam
is scanned in a velocity equal to the recordable maximum
linear velocity i.e. at a rate higher than about 80% of
that, a region once melted by the initial scanning tends
to be formed into an amorphous state again, such being
unfavorable. This is because when the scanning linear
velocity is high, the cooling rate of the melted portion
tends to be high, and the time for resolidification tends
to be short. With a focused recording laser beam having
a diameter of about 1 micron, recrystallization by
crystal growth from the crystalline region at the
periphery of the melted region can be completed in a
short time. However, in a case where scanning is carried
out with an initialization oval laser beam, the melted
region area in the major axis direction tends to be
large, and accordingly it is necessary that

recrystallization during resolidification is carried out
over the entire melted region by lowering the scanning
linear velocity than that at the time of practical
recording. From such a viewpoint, the scanning linear
velocity of the initial energy beam is preferably at most
70% of the recording maximum linear velocity, more
preferably at most 60%, most preferably lower than 50%.
The optical information recording medium of the
present invention has such characteristics that when
initial crystallization is carried out by irradiation
with a laser beam, it is possible to increase the moving
speed of the medium relative to the laser beam. This
makes it possible to carry out initial crystallization in
a short time, and is preferred in view of improvement of
the productivity and the cost reduction.
(Recording and retrieving method of optical information
recording medium)
The recording/retrieving laser beam to be used for
the optical information recording medium of the present
invention is usually a laser beam such as a semiconductor
laser or a gas laser, and its wavelength is usually from
300 to 800 nm, preferably from about 350 to about 800 nm.
Particularly, in order to achieve a high areal density of
at least 1 Gbit/inch2, the focused laser beam diameter is
required to be small, and it is desirable to obtain a
focused laser beam by using a blue to red laser beam
having a wavelength of from 3 50 to 68 0 nm and an object

lens having a numerical aperture NA of at least 0.5.
In the present invention, as mentioned above, it is
usually preferred that the amorphous state corresponds to
recording marks. Further, in the present invention, it
is effective to record information by the mark length
modulation system. This is particularly remarkable at
the time of the mark length recording with a shortest
mark length of at most 4 urn, particularly at most 1 pi.
In a case where the recording mark is formed,
recording by a conventional binary modulation system of
the recording laser power may be carried out, however, in
the present invention, it is particularly preferred to
employ a recording method by a multi-level modulation
system of at least ternary modulation wherein off-pulse
periods are provided when a recording mark is formed as
follows.
Fig. 2 is schematic views illustrating the power
pattern of the recording laser beam in the recording
method of an optical information recording medium. When
an amorphous mark which is mark length-modulated into a
length nT (wherein T is the reference clock period, and n
is the mark length possible in the mark length modulation
recording and is an integer), the amorphous mark is
divided into m=n-k (provided that k is an integer of at
least 0) recording pulses, each recording pulse width is
iT (l (l
to the divided recording pulse in Fig. 2, description of
the reference clock period T is omitted in view of
understandability of the figure. Namely, in Fig. 2, a
part which should be described as iT is described simply
as i for example. Here, it is preferred that i i be ∑i+∑i=n+j (j is a constant which satisfies -2 so as to obtain an accurate nT mark.
At the time of recording, irradiation with a
recording laser beam with an erasing power Pe which may
crystallize the amorphous state is carried out between
marks. Further, at iT (i = l to m) , irradiation with a
recording laser beam with a writing power Pw sufficient
to melt the recording layer is carried out, and at a time
iT (l with a bias power Pb which satisfies Pb Pb The power Pb of the recording laser beam irradiated
in a time with a period mT is usually Pb Pb (l By employing the above recording method, the power
margin or the recording linear velocity margin can be
widened. This effect is particularly remarkable when the
bias power Pb is set to be adequately low so that
Pb The above recording system is a system particularly

suitable for an optical information recording medium
wherein the phase-change recording material of the
present invention is used for the recording layer. This
is because if the Ge amount is decreased to secure
erasing (recrystallization) in a short time, the critical
cooling rate required for amorphous mark recording tends
to be extremely high, and formation of favorable
amorphous marks tends to be difficult.
Namely, decrease in the Ge amount promotes
recrystallization of the amorphous marks from the
peripheral crystalline portion and at the same time,
increases the crystal growth rate at the time of melting
and resolidification. If the recrystallization speed
from the periphery of the amorphous mark is increased
above a certain level, recrystallization from the
peripheral portion of the melted region proceeds at the
time of resolidification of the melted region formed for
amorphous mark recording, and accordingly the region
which is originally to be formed into an amorphous state
tends to be recrystallized without being formed into an
amorphous state. Accordingly, it is important to set the
bias power Pb to be adequately low, or to adequately
secure the cooling section by making i (2 Further, if the linear velocity at the time of
recording increases, the clock period is shortened,
whereby the off-pulse section is shortened, and the

cooling effect tends to be impaired. In such a case, it
is effective to divide the recording pulse at the time of
nT mark recording, to set the cooling section by the off-
pulse to be at least 1 nsec, more preferably at least 5
nsec by the real time.
[2-2] Application of information recording medium other
than optical information recording medium
The information recording medium of the present
invention can be used as an optical information recording
medium, since reversible phase-change recording at least
by irradiation with laser beam is possible, as described
above. However, the rewritable information recording
medium used in the present invention can be applied to
phase-change recording by passing an electric current to
a microscopic region. Explanation will be made below
with respect to this point.
Fig. 4 is a schematic view illustrating the
temperature history (curve a) at the time of amorphous
mark recording, and the temperature history (curve b) at
the time of erasing by recrystallization. At the time of
recording, the temperature of the recording layer is
increased to at least the melting point Tm in a short
time by heating with an electric current at a high
voltage and with a short pulse or a high power level
laser beam, and after the electric current pulse or laser
beam irradiation is turned off, the recording layer is
rapidly cooled by heat dissipation to the periphery, and

formed into an amorphous phase. When the cooling rate of
the temperature at the time to from the melting point Tm
to the crystallization temperature Tg is higher than the
critical cooling rate for formation of an amorphous
phase, the recording layer is formed into an amorphous
phase. On the other hand, at the time of erasing, the
recording layer is heated to at least the crystallization
temperature Tg and at most about the melting point Tm, by
application of a relatively low voltage or irradiation
with a laser energy at a low power level, and maintained
for at least a certain time, whereby recrystallization of
the amorphous marks proceeds in a substantially solid
phase state. Namely, if the holding time t1 is adequate,
the crystallization will be completed.
Here, regardless of the state of the recording layer
before application of the energy for recording or
erasing, the recording layer is formed into an amorphous
phase when the temperature history of the curve a is
imparted to the recording layer, and the recording layer
is crystallized when the temperature history of the curve
b is imparted to the recording layer.
The reason why the rewritable information recording
medium of the present invention may be used for phase-
change recording by passing an electric current to the
microscopic region, not only as an optical information
recording medium, is as follows. Namely, it is the
temperature history as shown in Fig. 4 that causes a

reversible phase change, and the energy source which
causes such a temperature history may be either a focused
laser beam or an electric current heating (Joule heat by
conducting).
The change in the resistivity accompanying the phase
change between the crystalline phase and the amorphous
phase of the phase-change recording material used in the
present invention, is adequately equal to the change in
the resistivity by at least two orders of magnitude, as
obtained by a.GeTe-Sb2Te3 pseudo binary alloy which is
being developed as a non-volatile memory at present,
particularly a Ge2Sb2Te5 stoichiometrical composition
alloy (J. Appl. Phys., vol. 87, pages 4130 to 4133,
2000) . Namely, when the resistivity in an amorphous
state in an as-deposited state, and the resistivity after
crystallization by annealing, of a rewritable information
recording medium using a phase-change recording material
containing a composition represented by the above formula
(1) as the main component, are respectively measured,
whereupon changes by at least three figures are
confirmed. It is considered that the amorphous and
crystalline states obtained by formation into an
amorphous phase and the crystallization by current pulses
are slightly different from the above amorphous state in
an as-deposited state and the above crystalline state by
annealing, respectively. However, it is expected that
also in a case where the phase-change recording material

used in the present invention is subjected to phase
change by current pulses, a large change in the
resistivity by a level of two orders of magnitude can
adequately occur, since the above change in the
resistivity by at least three orders of magnitude can be
obtained.
Fig. 5 is a cross-sectional view illustrating the
structure of one cell of such a non-volatile memory. In
Fig. 5, a voltage is applied between an upper electrode 1
and a lower electrode 2, and an electric current is
applied to a phase-change recording layer 3 containing a
phase-change recording material (hereinafter sometimes
referred to simply as a phase-change recording layer 3)
and a heater portion 4. The phase-change recording layer
3 is covered with an insulant 10 such as SiO2. Further,
the phase-change recording layer 3 is crystallized in the
initial state. In this case, initial crystallization is
carried out by heating the entire system of Fig. 5 to the
crystallization temperature (usually from about 100 to
about 3 0 0°C) of the recording layer. In formation of an
integrated circuit, the temperature increase to such an
extent is commonly carried out.
In Fig. 5, a particularly narrow portion 4 (heater
portion) functions as a local heater, since heat is
likely to generate by the Joule heat by application of an
electric current between the upper electrode 1 and the
lower electrode 2. A reversibly changeable portion 5

adjacent thereto is locally heated and formed into an
amorphous phase via the temperature history as shown by
the curve a in Fig. 4, and recrystallized via the
temperature history as shown by the curve b in Fig. 4.
As the reading, a low electric current is passed to
such an extent that the heat generation at the heater
portion 4 can be ignored, and the potential difference
between the upper and lower electrodes is read. Here,
there is also a difference in the electric capacity
between the crystalline and amorphous states, and
accordingly the difference in the electric capacity may
be detected.
Practically, a further integrated memory has been
proposed by employing a semiconductor integrated circuit
formation technology (U.S. Patent 6,314,014), however,
its basic structure is as shown in Fig. 5, and when the
phase-change recording material used in the present
invention is incorporated in the phase-change recording
layer 3, the same function can be realized.
Here, as the energy source which causes the
temperature change as shown in Fig. 4, an electron beam
may also be mentioned. As an example of a recording
device employing an electron beam, a method wherein a
phase-change recording material is locally irradiated
with an electron beam radiated by a field emitter to
cause a phase change, as disclosed in U.S. Patent
5,557,59 6 may be mentioned.

The present invention is not limited to the above
embodiments. The above embodiments are examples, and any
one having substantially the same structure as the
technical idea as disclosed in the scope of the present
invention and having the same effects is included in the
present invention.
EXAMPLES
Now, the present invention will be explained with
reference to Examples wherein the phase-change recording
material of the present invention is applied to an
optical information recording medium. However, the
present invention is by no means restricted to the
application to an optical information recording medium
within a range not to exceed the object of the present
invention.
In the following Examples, an optical information
recording medium may be referred to simply as "a disk",
"an optical disk", "a phase-change type optical disk"
etc. in some cases.
EXAMPLES 1 to 3 and COMPARATIVE EXAMPLES 1 and 2
For measurement of the composition of the phase-
change recording material used for the recording layer of
an optical information recording medium, an acid
dissolution ICP-AES (Inductively Coupled Plasma-Atomic
Emission Spectrometry) and a fluorescent X-ray analyzer
were used. With respect to the acid dissolution ICP-AES,
JY 38 S manufactured by JOBIN YVON was used as an

analyzer, and the recording layer was dissolved in dil-
HNO3 and quantitative determination was carried out by a
matrix matching calibration method. As the fluorescent
X-ray analyzer, RIX3 0 01 manufactured by Rigaku Denki
Kogyo K.K. was used.
[Preparation of phase-change type optical disk]
On a disk-shape polycarbonate substrate having a
diameter of 120 mm and a thickness of 0.6 mm, having
guide grooves with a groove width of 0.31 m, a groove
depth of 29 nm and a groove pitch of 0.74 m, a
(ZnS)80 (Si02)2o layer (80 nm) , a Sb-Ge-In-M-Te layer (13
nm) , a (ZnS) so (SiO2) 20 layer (20 nm) , a Ta layer (2 run)
and a Ag layer (2 00 nm) were formed by a sputtering
method, and a protective coating layer comprising an
ultraviolet-curing resin was further formed to prepare a
phase-change type optical disk.
The values of x, y, z and w when the composition of
the Sb-Ge-In-M-Te recording layer is represented by
{ (Sb1-xGex) 1-yIny}1-z-wMzTew are shown in Table 1.


Except for Comparative Example 2, the above
compositions were substantially in accordance with the
crystallization speed suitable for the following
evaluation conditions. In the following initial
crystallization and measurement of the disk
characteristics, a glass substrate of 0.6 mm was overlaid
on the opposite side to the laser beam incident side.
[Initial crystallization]
Initial crystallization was tried on each of these
disks as follows. Namely, a disk rotated at 10 m/s was
irradiated with a laser beam having a wavelength of 810
nm and a power of 800 mW and having a shape with a width
of about 1 urn and a length of about 7 5 n so that the
major axis of the laser beam would be perpendicular to
the above guide grooves, and the laser beam was
continuously moved in a radius direction with a feed
amount of 50 m per rotation to try initial
crystallization. Initial crystallization could be
carried out on disks of Examples 1, 2, 3 and Comparative
Example 1 without any problem. However, no
crystallization occurred (the reflectivity was not
changed) on the disk of Comparative Example 2. Initial
crystallization was tried similarly at a linear velocity
of 2 m/s at a laser power of from 400 to 1000 mW,
however, no crystallization occurred. Accordingly, it is
considered that use of the disk of the Comparative
Example 2 as a phase-change type optical disk is

substantially difficult. It is considered to be because
the Tb content in the recording layer of Comparative
Example 2 is too high. Here, if the Ge amount is
increased, the crystallization tends to be slower, and
accordingly initial crystallization will be further
difficult.
[Disk characteristics]
With respect to the disks of Examples 1, 2 and 3 and
Comparative Example 1, recording/erasing was carried out
on the guide grooves and the disk characteristics were
evaluated as follows, by means of an optical disk tester
DDU 1000 manufactured by Pulstec Industrial Co., Ltd.
having a pickup with NA of 0.65 and a laser wavelength of
65 0 ran.
Overwriting of EFM+ modulation signal was carried
out at a linear velocity of 14 m/s up to 2000 times, and
the relation between the recording cycle and the jitter
when the recorded signal was retrieved was measured. The
reference clock frequency at the time of recording was
104.9 MHz (reference clock period was 9.53 ns), and the
recording laser division method was as follows.
Namely, when an amorphous mark with a length of nT
(T is the reference clock period, and n is a natural
number of from 3 to 14) was to be formed, the mark
formation laser irradiation time was divided as shown in
Fig. 2(b), and a recording pulse having a writing power
Pw and an off-pulse having a bias power Pb were

alternately irradiated. During the period for formation
of the space between marks (crystalline portion), an
erasing laser beam having an erasing power Pe was
irradiated. In Fig. 2 (b) , for all n, m=n-l, i=0.5
(l Pb=0.8 mW and Pe=4.5 mW.
At the time of retrieving, jitter measurement was
carried out at a linear velocity of 3.49 m/s. The jitter
was normalized by a reference clock period of 38.2 ns at
the retrieving linear velocity. Here, the jitter in the
present invention is one obtained by normalizing by the
reference clock period a standard deviation (jitter) of
the difference in time against PLL clock of the leading
edge and the trailing edge of binary signals obtained by
passing the retrieving signals through an equalizer and
LPF, followed by conversion to binary signals by a
slicer. A detailed measurement method is prescribed in
DVD-ROM standard or DVD-RW standard.
The result of the measurement of the relation
between the recording cycle and the jitter when the
recorded signal was retrieved is shown in Fig. 3. Of the
disk of Comparative Example 1 using the Sb-Ge-In type
phase-change recording material, the jitter value
exceeded 11% by the repeated recording 2000 times, and
use of the disk became difficult, whereas of the disks of
Examples 1, 2 and 3 having Tb, Gd and Te added, the
jitter value was at most 10% even after the repeated

recording 2000 times. The disk of Comparative Example 1
after the repeated recording 2000 times, was irradiated
with a DC laser beam of 4.5 mW once to try to erase the
recording marks (crystallization), whereupon unerased
marks were clearly shown by the observation on an
oscilloscope. On the other hand, on the disks of
Examples 1, 2 and 3, no such clear unerased marks were
shown by the similar observation.
EXAMPLE 4
The following experiment was carried out to indicate
possibility of recording by a change in the electric
resistivity on the phase-change recording material used
in the present invention.
Namely, on a polycarbonate substrate having a
diameter of 12 0 mm, a Ge-In-Sb-Tb amorphous film having a
film thickness of 50 nm and having the same composition
as in Example 1 was prepared by sputtering.
The resistivity of the above amorphous film was
measured, and then the amorphous film was crystallized
and the resistivity of the film after crystallization was
measured.
For initial crystallization, a laser beam having a
wavelength of"810 nm and a power of 800 mW, and having a
shape with a width of about 1 urn and a length of about 75
m was used. While rotating the Ge-In-Sb-Tb amorphous
film formed on the substrate at a linear velocity of 12
m/s, the amorphous film was irradiated with the laser

beam so that the major axis of the laser beam would be
perpendicular to the guide grooves formed on the
substrate. Further, the laser beam was continuously
moved in the radius direction with a feed amount of 5 0 m
per rotation to carry out initial crystallization.
For measurement of the resistivity, a resistivity
measurement device Loresta MP (MCP-T3 50) manufactured by
Dia Instruments Co., Ltd. was used.
No accurate resistivity of the amorphous film could
be obtained since the resistivity was too high. However,
in the measurement of another material having the same
film thickness, a resistivity at a level of about 1x10-1
Qcm can be measured, and thus the resistivity of the
composition of Example 1 in an amorphous state is
considered to be higher than 1x10-1 cm. On the other
hand, the resistivity of the Ge-In-Sb-Tb film after
crystallization was 0.52xl0-4 cm.
From the above results, it was found that there is a
change in the resistivity by at least three figures
between the amorphous state and the crystalline state of
the phase-change recording material used in the present
invention. Accordingly, it is found that the phase-
change recording material used in the present invention
provides a large difference in the resistivity by the
phase change between the amorphous state and the
crystalline state, and can be applied to a rewritable
information recording medium on which recording is

carried out by the change in the electric resistance.
INDUSTRIAL APPLICABILITY
According to the present invention, a phase-change
recording material on which high speed recording/erasing
is possible, which has excellent recording
characteristics, which has high storage stability of the
recording signals and which is excellent in repeated
recording durability, and an information recording medium
using the above material can be obtained.
The present invention has been described in detail
with reference to specific embodiments, but it should be
apparent to those skilled in the art that various changes
and modifications can be made without departing from the
intention and the scope of the present invention.
The present application is based on a Japanese
Patent Application No. 2003-079834 (filed on March 24,
2003), and the entirety is referred by a citation.

WE CLAIM :
1. A phase-change recording material characterized by
containing a composition represented by the following formula
(1) as the main component:

wherein x, y, z and w are numbers satisfying 0.001 0 selected from lanthanoids.
2. The phase-change recording material as claimed in Claim 1
wherein, in formula (1), z/y is at least 0.001 and at most 1.
3. The phase-change recording material as claimed in Claim 1 or
2, the crystalline state whereof corresponds to a non-recorded
state and the amorphous state whereof corresponds to a recorded
state.
4. An information recording medium having a recording layer,
characterized in that the said recording layer contains a
composition represented by the following formula (1) as the main
component:

wherein x, y, z and w are numbers satisfying 0.001 0 selected from lanthanoids.
5. The information recording medium as claimed in Claim 4,

wherein, in formula (1), z/y is at least 0.001 and at most 1.
6. The information recording medium as claimed in Claim 4 or 5,
the crystalline state whereof corresponds to a non-recorded
state and the amorphous state whereof corresponds to a recorded
state.
7. The information recording medium as claimed in any one of
Claims 4 to 6, which is an optical information recording medium.
8. The information recording medium as claimed in Claim 7,
which has a protective layer.
9. The information recording medium as claimed in Claim 7 or
8, being an optical information recording medium has a
reflective layer, and the reflective layer contains Ag as the
main component.

There is disclosed a phase-change recording material
characterized by containing a composition represented by the
following formula (1) as the main component:
wherein x, y, z and w are numbers satisfying 0.001 0 selected from lanthanoids. An information recording medium
having a recording layer containing a composition as defined
above, is also disclosed.

Documents:

761-KOLNP-2005-CORRESPONDENCE.pdf

761-KOLNP-2005-FORM 27.pdf

761-KOLNP-2005-FORM-27.pdf

761-kolnp-2005-granted-abstract.pdf

761-kolnp-2005-granted-assignment.pdf

761-kolnp-2005-granted-claims.pdf

761-kolnp-2005-granted-correspondence.pdf

761-kolnp-2005-granted-description (complete).pdf

761-kolnp-2005-granted-drawings.pdf

761-kolnp-2005-granted-examination report.pdf

761-kolnp-2005-granted-form 1.pdf

761-kolnp-2005-granted-form 18.pdf

761-kolnp-2005-granted-form 3.pdf

761-kolnp-2005-granted-form 5.pdf

761-kolnp-2005-granted-form 6.pdf

761-kolnp-2005-granted-gpa.pdf

761-kolnp-2005-granted-reply to examination report.pdf

761-kolnp-2005-granted-specification.pdf


Patent Number 229487
Indian Patent Application Number 761/KOLNP/2005
PG Journal Number 08/2009
Publication Date 20-Feb-2009
Grant Date 18-Feb-2009
Date of Filing 29-Apr-2005
Name of Patentee MITSUBISHI KAGAKU MEDIA CO. LTD.
Applicant Address 31-19 SHIBA 5-CHOME, MINATO-KU TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 OHNO, TAKASHI C/O MITSUBISHI KAGAKU MEDIA CO. LTD.31-19 SHIBA 5-CHOME, MINATO-KU TOKYO 1080014
2 HORIE, MICHIKAZU C/O MITSUBISHI KAGAKU MEDIA CO. LTD.31-19 SHIBA 5-CHOME, MINATO-KU TOKYO 1080014
PCT International Classification Number B41M 5/26
PCT International Application Number PCT/JP2004/004002
PCT International Filing date 2004-03-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-079834 2003-03-24 Japan