Title of Invention

AN OPTICAL INFORMATION RECORDING MEDIUM .

Abstract An optical information recording medium utilizing a crystalline state as a non-recorded state and an amorphous state as a recorded state, which employs a phase-change recording layer comprising an alloy having the composition of the following formula (1) as the main component: (Sb1-xSnx)1-y-w-zGeyTewM1z formula (1) wherein each of x, y, z and w represents atomicity, x, z and w are numbers which satisfy 0.01&#8804;x&#8804;0.5, 0&#8804;z&#8804;0.3 and 0&#8804;w&#8804;0.1, respectively, and the element Ml is at least one element selected from the group consisting of In, Ga, Pt, Pd, Ag, rare earth elements, Se, N, O, C, Zn, Si, Al, Bi, Ta, W, Nb and V, and (I) when z=0 and w=0, y is a number which satisfies 0.1&#8804; y&#8804;0.3, (II) when 0<z&#8804;0.3 and w=0, y is a number which satisfies 0.05&#8804;y&#8804;0.3, and (III) when 0&#8804;z&#8804;0.3 and 0<w&#8804;0.1, y is a number which satisfies 0.01&#8804;y&#8804;0.3. and on atleast one side of the recording layer, a heat resistant protective layer is formed, on a substrate.
Full Text The present invention relates to an optical
information recording medium utilizing a crystalline state
as a non-recorded state and an amorphous state as a
recorded state, which employs a phase-change recording
layer comprising an alloy. Particularly, it
relates to a phase-change recording material used for an
information recording medium on which a high speed
recording/erasing is possible, and an information
recording medium employing the phase-change recording
material. Further, it relates to an information
recording medium of which initial crystallization is
easily carried out, which has a high signal amplitude,
which is excellent in repetitive overwriting properties,
which is excellent in storage stability and which has
excellent jitter properties at a high transfer rate
recording.
As a rewritable information recording medium, 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 heating) (J. Feinleib et a1.
"RAPID REVERSIBLE LIGHT-INDUCED CRYSTALLIZATION OF
AMORPHOUS SEMICONDUCTORS", 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 rewritable
phase-change recording material, is to utilize a
reversible change between the crystalline phase and the
amorphous phase to let the crystalline state in a non-
recorded/erased state and to form amorphous marks at the
time of recording. Usually, the recording layer is
locally heated to a temperature higher than the melting
point and then rapidly cooled to form amorphous marks,
and the recording layer is heated at a temperature of
approximately at most melting point and at least
crystallization temperature, and slc-wly 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. The information is
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.
Particularly as the application of the information
recording medium as an optical recording medium,
recording/retrieving/erasing of the information 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 of a focused light beam. Such an optical
information recording medium having a phase-change type
and rewritable type 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,
rewritable CD such as CD-RW has already been used widely
and rewritable DVD such as DVD-RW, DVD+RW and DVD-RAM is
being on sale.
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 GeSbTe type, InSbTe type,
GeSnTe type or AglnSbTe type alloy may, for example, be
mentioned. Particularly, a GeTe-Sb2Te3 pseudo-binary
alloy type material is widely used as a recording layer
material for an optical recording medium, and in recent
years, its application at a non-volatile memory utilizing
a change in the electric resistance has been actively
studied.
However, in proportion to increase in the volume of

information in recent years, an optical recording medium
on which recording/retrieving of information at a higher
speed is possible, has been desired. Further, high
storage stability of recorded information i.e. that
information recorded on an optical recording medium does
not deteriorate and is stable even after long-term
storage, is also one of important performances required
for an information recording medium. Among the above
information recording media, with respect to the
rewritable information recording medium, in order to
merely achieve rewriting at a high speed, in a case of
utilizing the phase change between the amorphous state
and the crystalline state for example, a material having
a high crystallization speed is sufficient. However,
with a material with which a high speed crystallization
is possible, the tendency for the amorphous state to be
crystallized in a short time during storage will be
remarkable. Accordingly, in order to obtain a rewritable
information recording medium with which
recording/retrieving at a high speed is possible, and
which has a high storage stability of recorded
information, transition from the amorphous state to the
crystalline state at a high speed by high-speed
crystallization is required at the time of erasing, on
the contrary, stabilization of the amorphous state by an
extremely slow crystallization is required in a storage
state in the vicinity of room temperature. That is,

seemingly conflicting properties are required for the
phase-change recording material.
Further, signal properties being stable after
rewriting of information is carried out many times, i.e.
high repetitive overwriting properties are also one of
important performances required for a rewritable
information recording medium.
Further, in a case where the rewritable information
recording medium is used as an optical recording medium
on which recording/retrieving of information is carried
out optically, it tends to be difficult to carry out
initial crystallization of the recording layer after
production in a short time. However, in view of
increasing the production efficiency, carrying out the
initial crystallization in a short time is also one of
important performances required for an optical recording
medium and therefore for a rewritable information
recording medium.
Under these circumstances, the present invention has
been made to meet such demands, and it is an object of
the present invention to provide a phase-change recording
material capable of being used for an information
recording medium on which recording/erasing at a higher
speed is possible, which has a high storage stability of
the recording signals, which is excellent in overwriting
properties and which has a high productivity, and an
information recording medium employing the above

material. Further, it is an object of the present
invention to provide an optical recording medium which is
one form of the application of the information recording
medium.
Accordingly the present invention provides an
optical information recording medium utilizing a
crystalline state as a non-recorded state and an amorphous
state as a recorded state, which employs a phase-change
recording layer comprising an alloy having the composition
of the following formula (1) as the main component:

wherein each of x, y, z and w represents atomicity, x, z
and w are numbers which satisfy
and respectively, and the element Ml is at
least one element selected from the group consisting of
In, Ga, Pt, Pd, Ag, rare earth elements, Se, N, 0, C, Zn,
Si, Al, Bi, Ta, W, Nb and V, and
(I) when z=0 and w=0, y is a number which satisfies

(II) when and w=0, y is a number which satisfies
and
(III) when and y is a number which
satisfies and on atleast one side of the
recording layer, a heat resistant protective layer is
formed, on a substrate.

Brief Description of the Accompanying Drawings:
Figs. 1(a) and 1(b) are schematic views illustrating
the layer structure of an optical recording medium.
Fig. 2 is a schematic view illustrating the power
pattern of recording light in a method of recording on an
optical recording medium.
Fig. 3 is a conceptual diagram illustrating the
temperature history at the time of amorphous mark
recording and the temperature history at the time of
erasing by recrystallization.
Fig. 4 is a sectional view illustrating the
structure of one cell of a non-volatile memory.

Figs. 5(a), 5(b), 5(c) and 5(d) are diagrams
illustrating the recording properties of an optical
recording medium in Example of the present invention.
Figs. 6(a), 6(b), 6(c) and 6(d) are diagrams
illustrating the recording properties of an optical
recording medium in another Example of the present
invention.
Fig. 7 is a diagram illustrating the recording
properties of an optical recording medium in still
another Example of the present invention.
Now, the present invention will be described in
detail with reference to the preferred embodiments.
By use of a reconrding layer comprising an alloy
having the above composition comprising Ge added to a Sb-
Sn type alloy, as the main component, an information
recording medium having a higher phase-change speed than
that of a conventionally known information recording
medium can be obtained, and accordingly recording/erasing
at a higher speed can be carried out. For example, for
an optical recording medium among information recording
media, a phase-change recording material having a
composition such as GeSbTe has conventionally been
employed, however, with a composition which provides an
adequately high crystallization speed to such an extent
that erasing at a high, speed is possible, crystallization
may not take place uniformly and the noise tends to be
significant, such being problematic. On the other hand,

with the phase-change recording material of SbSnGe type
used in the present invention, the crystallization speed
is high and uniform crystallization becomes possible, and
accordingly it can be preferably used for high-speed
recording. Further, with a conventional optical
recording medium, it tends to be difficult to achieve
both high crystallization speed and storage stability of
recorded signals, however, with the information recording
medium employing the phase-change recording material of
the present invention, it becomes possible to achieve
both the above performances.
1. Phase-change recording material
The phase-change recording material used in the
present invention is a phase-change recording material
used for an information recording medium utilizing a
crystalline state as a non-recorded state and an
amorphous state as a recorded state, and has the
composition of the following formula (1) as the main
component:
(Sb1-xSnx)1-y-w-zGeyTewM1z formula (1)
wherein each of x, y, z and w represents atomicity, x, z
and w are numbers which satisfy 0.01≤x≤0.5, 0≤z≤0.3
and 0≤w≤0.1, and the element Ml is at least one element
selected from the group consisting of In, Ga, Pt, Pd, Ag,
rare earth elements, Se, N, 0, C, Zn, Si, Al, Bi, Ta, W,
Nb and V, and
when (I) z=0 and w=0, y is a number which satisfies 0.1≤


when (II) and w=0, y is a number which satisfies
and
when (III) and y is a number which
satisfies
In the present specification, "having a
predetermined composition as the main component" means
that the content of the predetermined composition is at
least 50 atomic% in the entire material or in the entire
layer containing the predetermined composition.
Further, when the information recording medium used
in the present invention is an optical recording medium,
"utilizing a crystalline state as a non-recorded state
and an amorphous state as a recorded state" means that an
amorphous mark is formed in the crystalline phase.
In the present invention, Ge is incorporated into
the Sb-Sn type alloy. Ge has a role to control the
crystallization speed of the phase-change recording
material, and accordingly by controlling the content of
Ge in a predetermined range (10 atomic% to 30 atomic%), a
phase-change recording material having a crystallization
speed suitable for high speed recording can be obtained.
Further, in the present invention, by incorporating
Te into the Sb-Sn-Ge alloy as the case requires, a phase-
change recording material more excellent in recording
properties can be obtained. Specifically, by
incorporating Ge, favorable recording properties can be

obtained even in a case where repetitive recording is
carried out on a phase-change material after long-term
storage. Te also has a role to control the
crystallization speed in the same manner as Ge, and
accordingly when Ge and Te are incorporated into the Sb-
Sn type alloy, the range of Ge content can be extended.
Specifically, the lower limit of the Ge content can be
decreased to 1 atomic%. Further, by decreasing the Ge
content, recording properties after long-term storage of
the phase-change recording material can be improved.
In the present invention, by incorporating a
predetermined element such as In into the Sb-Sn-Ge alloy
or Sb-Sn-Ge-Te alloy, further effects such that the
signal amplitude is increased, can be obtained. Further,
by using the predetermined element such as In, it may be
possible to further control the crystallization speed
together with Ge and Te in some cases.
Namely, in the present invention, by incorporating
Ge into the Sb-Sn type alloy, a phase-change recording
material excellent in high speed recording and storage
stability of recording signals can be obtained, by
favorably controlling the crystallization speed.
Further, by incorporating another element such as Te
and/or In into the Sb-Sn-Ge alloy, further effects such
that favorable recording properties can be obtained even
in the case where a repetitive recording is carried out
on the phase-change recording material after long-term

storage, and that the signal amplitude can be increased,
can be obtained. Further, depending upon the element to
be incorporated into the Sb-Sn-Ge alloy, the
crystallization speed may be controlled more precisely,
and further, recording performance such as recording
properties after long-term storage will be favorable.
Thus, according to the present invention, a phase-change
recording material having desired performances required
for the application of use can be obtained.
Further, in the present invention, by employing the
phase-change recording material having the composition of
the above formula (1) as the main component, for an
information recording medium utilizing a crystalline
state as a non-recorded state and an amorphous state as a
recorded state, quality of recording signals remarkably
improves. Particularly by the use of the above phase-
change recording material for a rewritable information
recording medium, high speed recording/erasing,
improvement in storage stability of recording signals,
improvement in overwriting properties, and improvement in
overwriting properties in a case where overwriting is
further carried out on the rewritable information
recording medium after long-term storage, will be
achieved. Further, a rewritable information recording
medium of which the initial crystallization is easy and
which has a high productivity can be obtained. As the
rewritable information recording medium, an optical

recording medium (such as CD-RW) may, for example, be
mentioned, on which recording/retrieving/erasing of
information is carried out by utilizing a change in the
reflectivity due to a reversible change between the
crystalline state and the amorphous state by irradiation
of a focused light beam.
Now, the phase-change recording material will be
explained with reference to the items (A) when z=0 and
w=0, (B) when and w=0, (C) when and
in the above formula (1), and (D) other items.
(A) When z=0 and w=0
When z=0 and w=0 in the above formula (1), the
phase-change recording material of the present invention
is a SbSnGe ternary composition, and the above formula
(1) has the following formula (1a):

wherein x and y are numbers which satisfy
and respectively.
In the formula (la), when x is at least 0.01, the
crystalline state tends to be uniform, and the noise at
the time of retrieving can be decreased, such being
advantageous. Here, the uniform crystalline state means
a poly-crystalline structure substantially comprising
single crystalline phase and comprising fine
crystallites. Fine crystallites mean that the average
crystalline grain size is the same or lower order as the
size of the recording marks, and the dispersion of the

grain size is small.
In the formula (1a), x is preferably more
preferably furthermore preferably and
particularly preferably . When x is within this
range, more uniform crystalline state can be obtained,
and the noise at the time of retrieving can be further
decreased.
On the contrary, in the above formula (la), when x
is smaller than 0.01 (Sn is smaller than 1 atomic%), no
uniform crystalline state in the entire phase-change
recording material can be obtained. This means that a
uniform initial crystalline state (non-recorded state) as
a presupposition to form high quality amorphous recording
marks, can not be obtained. That is, that no uniform
crystalline state in the entire phase-change recording
material can be obtained, means the it tends to be
difficult to let the crystalline state in a non-recorded
state and the amorphous state in a recorded state.
Further, when x is large, the difference in optical
properties between the crystalline state and the
amorphous state tends to be significant, and accordingly
a high signal amplitude can be obtained when the
information recording medium of the present invention is
used as an optical recording medium. However, when x is
larger than 0.5, it tends to be difficult to stably carry
out formation of amorphous marks (recording) and
crystallization of the amorphous marks (erased/non-

recorded state), and accordingly x is at most 0.5.
Further, in a case where a reversible phase change
between the crystalline state and the amorphous state is
repeatedly carried out, in order to carry out the
reversible phase change (rewriting of information) at
least 100 times more securely, preferably
particularly preferably It is considered that
the value of x is more preferably within the above range
because when Sn is excessively incorporated, no phase
change of the phase-change recording material by the
change of crystallization/amorphous mechanism considered
to be due to phase separation of Sn will not take place.
Particularly, when x is small within a range of x of
at least 0.2 and at most 0.35, although the signal
amplitude tends to be low, the durability of the phase-
change recording material tends to improve when
repetitive recordings is carried out, such being
preferred.
Accordingly, of the phase-change recording material
used in the present invention, by controlling the value
of x, the above properties can flexibly be realized, and
accordingly an appropriate composition depending upon the
purpose of use of an information recording medium for
which the phase-change recording material is used can be
used.
On the other hand, by changing the Ge Content in the
above formula (la), the crystallization speed can be

controlled. Namely, when y is small, in the recording
layer composition (Sb1-xSnx) 1-yGey, the crystallization
speed tends to be high. With respect to the rewritable
information recording medium, takings recording/erasing in
a short time into consideration, the crystallization
speed is preferably high. Accordingly, in order to
obtain an appropriate crystallization speed depending
upon the recording conditions of the rewritable
information recording medium, the Ge content to be
incorporated should be optionally controlled.
Specifically, taking e.g. a case of using the rewritable
information recording medium as an optical recording
medium into consideration, the range of y is at least
0.1, preferably at least 0.12, more preferably at least
0.15, and on the other hand, at most 0.3, preferably at
most 0.25, more preferably at most 0.2, as the scanning
linear velocity adjustment mechanism of the focused light
beam, the laser power rise time, etc. are restricted.
As described above, when the Ge content is low (y is
decreased), the crystallization speed increases. For the
phase-change recording material of the present invention,
a crystallization speed to a certain extent is required.
However, if the crystallization speed is too high, the
phase-change recording material once melted in the
process of amorphous state formation may be
recrystallized, at the time of its re-solidification, and
no amorphous state tends to be obtained. Further,

storage stability of the obtained amorphous state tends
to decrease. Accordingly, in order to let the
crystalline state in a non-recorded state and the
amorphous state in a recorded state, it is necessary that
y is at least 0.1 (Ge is incorporated in an amount of at
least 10 atomic%).
Further, in the phase-change recording material used
in the present invention, Ge is considered to be relevant
to the stability of the amorphous marks. Namely, it is
considered that when the Ge content is increased,
stability of the amorphous marks tends to improve.
However, if y is larger than 0.3, the amorphous marks
tend to be too stable, and recrystallization (erasing) in
a short time and initial crystallization tend to be
difficult. In the above formula (1a), when the Ge
content is within a range of from at least 10 atomic% and
at most 30 atomic%, the amorphous marks will be extremely
stable while securing the required crystallization speed,
and not only the crystalline state and the amorphous
state can be utilized as a non-recorded state and a
recorded state, respectively, but also storage stability
of the recorded signals will be excellent.
Of the phase-change recording material used in the
present invention, the crystallization speed preferably
changes significantly depending upon the temperature at
the time of crystallization. Namely, it is preferred
that the crystallization speed is high when the

temperature at the time of crystallization is in a high
temperature region in which the temperature is adequately
higher than the crystallization temperature and is close
to the melting point, and on the other hand, the
crystallization speed is low in a low temperature region
in the vicinity of room temperature. In the present
invention, by using Ge, the above temperature dependency
of the crystallization speed can be realized.
(B) When and w=0
When and w=0 in the above formula (1), the
phase-change recording material of the present invention
has a SbSnGeMl quaternary composition, and the above
formula (1) has the following formula (lb):

wherein x and y are numbers which satisfy
and respectively. In the above formula
(lb), the element Ml is at least one member selected from
the group consisting of In, Ga, Pt, Pd, Ag, rare earth
elements, Se, N, O, C, Zn, Si, Al, Bi, Ta, W, Nb and V.
In order to improve the overwriting properties when
overwriting is carried out on the amorphous recording
marks after long-term storage, the Sn content is
preferably low, however, if the amount of Sn is small, no
uniform crystalline state tends to be obtained, the noise
tends to be significant, and the initial properties tend
to somewhat deteriorate in some cases. In such a case,
by incorporating the element Ml, the increase of the

noise can be suppressed. That is, by using the element
M1, the disc excellent in initial properties and having
favorable overwriting properties when overwriting is
carried out on the recording marks after long-term
storage can be obtained.
The reason why the value of x is within a range of
in the above formula (1b), is as explained
in the above item (A) . Further, in the above formula
(1b), when x is large, the difference in optical
properties between the crystalline state and the
amorphous state tends to be significant, and accordingly
a high signal amplitude can be obtained when the
information recording medium of the present invention is
used particularly as an optical recording medium.
However, in view of further improvement of the repetitive
overwriting durability and the signal properties in the
case where overwriting is further carried out on the
amorphous recording marks after long-term storage, x is
preferably at most 0.2. In the SbSnGe ternary
composition as in the above formula (1a), in a case where
x≤0.2, the noise of the medium tends to be significant
when x is small, however, by addition of the element Ml,
the noise can be decreased. Accordingly, a phase-change
recording material which is more excellent in signal
properties when overwriting is further carried out on the
recording marks after long-term storage can be obtained.
In the above formula (1b), as the element M1 is

required to be incorporated, the value of z is higher
than 0, but is preferably at least 0.005, more preferably
at least 0.01. Within this range, the crystalline state
will be more uniform in the entire phase-change recording
material, and the noise will be reduced. Further, when z
is within the above range, even when x≤0.2 in the above
formula (1b), the noise can securely be reduced. On the
other hand, the value of z is at most 0.3, preferably at
most 0.25, more preferably at most 0.2. Within this
range, the change in the reflectivity at the time of
phase change between the crystallines state and the
amorphous state will be adequately large, and further,
the phase change speed can be increased.
In the above formula (1b), the element M1 is at
least an member selected from the group consisting of In,
Ga, Pt, Pd, Ag, rare earth elements, Se, N, O, C, Zn, Si,
Al, Bi, Ta, W, Nb and V. By using a small amount of such
an element M1, recording properties after a lapse of long
time can be improved, or other effects may further be
obtained, substantially without changing the
crystallization speed. Now, the effects of the element
Ml will be explained with regard to (B-1) element
selected from In, Ga, Pd, Pt and Ag, (B-2) rare earth
elements and (B-3) element selected from Se, N, O, C, Zn,
Si, Al, Bi, Ta, W, Nb and V.
By use of the element Ml, control of the
crystallization speed may be possible in some cases.

Accordingly, by using the element M1, the lower limit of
the Ge content can be decreased (the amount of Ge can be
smaller than 10 atomic%) in the SbSnGeM1 quaternary
composition of the above formula (lb) . This will be
explained in the following item (B-4) . However, the
adjustment of the crystallization speed by use of the
element Ml is the secondary effect, and the adjustment of
the crystallization speed of the phase-change recording
material is carried out by control of the Ge content
first.
(B-1) Element selected from In, Ga, Pd, Pt and Ag
When the element M1 is an element selected from In,
Ga, Pd, Pt and Ag in the above formula (1b), although the
initial crystallization tends to be somewhat difficult,
an effect of increasing the stability of the amorphous
marks may be obtained by increasing the crystallization
temperature. Further, when the phase-change recording
material of the present invention is used for a recording
layer of an optical recording medium, the signal
amplitude can be increased, such being advantageous.
Here, the increase of the signal amplitude means an
increase of the change in the refractive index between
the crystalline states and the amorphous state.
When the Sn content in the phases-change recording
material is decreased, the signal amplitude tends to be
low in some cases, and in such a case also, by use of the
above element as the element Ml, the decrease of the

signal amplitude can be compensated. When the Sn content
is decreased, repetitive overwriting properties, etc. may
be improved, and accordingly when at least one element
selected from In, Ga, Pd, Pt and Ag is used as the
element Ml, x is preferably at most 0.2, particularly
preferably at most 0.15 in the above formula (1b).
Particularly when the element M1 to be added is In
or Ga, the overwriting properties when overwriting is
carried out on the recording marks after long-term
storage may be improved. When In is compared with Ga, In
provides a higher effect of decreasing the noise. When
the element Ml to be added is Pt or Pd, although the
improvement of the signal amplitude tends to be small,
initial crystallization can be carried out easily, such
being advantageous.
Among these elements, it is most preferred to use In
when the phase-change recording material of the present
invention is used for the optical recording medium. When
In is used, it is preferred to control the In and Sn
contents. Specifically, x+z in the above formula (1b) is
preferably at least 0.05, particularly preferably at
least 0.1. Further, the above x+z is preferably at most
0.3, particularly preferably at most 0.25.
(B-2) Rare earth elements
The element M1 may be a rare earth element in the
above formula (1b). The rare earth elements are Group 3B
element of the Periodic Table, and specifically, they

include Sc, Y, lanthanoids and actinoids. Such Group 3B
elements of the Periodic Table have similar properties,
and accordingly any of the above elements may be used as
the element Ml. Preferred is a series in which the 4f
orbital is sequentially filled in view of the electron
configuration, and it is preferred to use one or more
lanthanoids (15 elements of La, Ce, Pr, Nd, Pm, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tin, Yb and Lu) which tend to have
similar properties. Among the above lanthanoid,
particularly preferred are Tb and Gd. By use of Tb or
Gd, the initial crystallization of the information
recording medium will be carried out easily.
Further, when a lanthanoid is used as the element
Ml, the following effect is also obtained. Of the phase-
change recording material of SbSnGe type of the present
invention, the crystallization speed tends to gradually
decrease and the recording properties tend to deteriorate
in some cases if repetitive overwriting recording is
carried out, depending upon e.g. the recording
conditions. For example, when the above phase-change
recording material is used for a recording layer of a
rewritable optical recording medium as one of information
recording media, when the number of repetitive recording
exceeds 1,000 times, the jitter properties tend to
deteriorate in some cases. This tends to be remarkable
when x is high within a range of Sn of 0.2≤x≤0.35.
However, when x is increased (when the amount of Sn is

increased), the signal amplitude tends to be high, and
recording with a low power may be possible, such being
advantageous. Accordingly, if the deterioration of the
jitter properties due to repetitive recording can be
reduced, it is effective to increase the value of x as
far as possible (to increase the amount of Sn as far as
possible) so as to increase the signal amplitude.
Addition of a lanthanoid provides an effect of
suppressing deterioration of the jitter properties
accompanying the decrease of the crystallization speed
when the above repetitive recording is carried out.
Namely, by incorporating a lanthanoid into the SbSnGe
type phase-change recording material of the present
invention, an information recording medium which has a
high signal amplitude, on which recording is possible
with a low power, and which is very excellent in
repetitive recording durability will be obtained.
The effect by incorporating a lanthanoid is
remarkable particularly when the phase-change recording
material of the present invention is used for an optical
recording medium.
(B-3) Element selected from Se, N, O, C, Zn, Si, Al, Bi,
Ta, W, Nb and V
When the element M1 is an element selected from Se,
C, Si and Al in the above formula (1b), although the
initial crystallization tends to be somewhat difficult,
the signal amplitude can be increased, such being

advantageous, and an effect of increasing the stability
of the amorphous marks may also be obtained by increasing
the crystallization temperature.
Further, when the element M1 is an element selected
from Bi, Ta, W, Nb and V, although improvement of the
signal amplitude is small, the initial crystallization
can easily be carried out, such being advantageous.
Further, when the element Ml is an element selected
from N, 0 and Zn, fine adjustment between the optical
properties and the crystallization speed can be carried
out.
When the element Ml is at least one member selected
from the group consisting of Se, N, O, C, Zn, Si, Al, Bi,
Ta, W, Nb and V, the upper limit of the content of the
element Ml is most preferably 10 atomic%. Namely, z in
the above formula (lb) is preferably z≤0.1, more
preferably z≤0.05. This is because if the above element
is incorporated in an amount larger than 10 atomic%, the
noise tends to be significant, or the initial
crystallization tends to be difficult in some cases.
(B-4) Secondary effect by use of the element M1
By using the element Ml in the above formula (lb), y
representing the amount of Ge can be decreased to be
smaller than 0.1. As explained in the above item (A), in
the ternary composition of SbSnGe, the Ge content can not
be lower than 10 atomic% (y cannot be smaller than 0.1)
in order that the crystallization speed is not too high,

and in order to maintain formation stability and storage
stability of the amorphous state recording marks.
However, by addition of the element M1, the
crystallization speed can be decreased so as to achieve
favorable formation of the amorphous state and
improvement of the storage stability in some cases. The
effect is remarkable particularly when In, Ga, Ag or a
lanthanoid (particularly Tb or Gd) is used. Accordingly,
the lower limit of the Ge content can be decreased as
compared with a case of the SbSnGe ternary composition.
Decrease of the Ge content also provides the following
effect.
When Ge is incorporated in a large amount, the
crystallization speed of the phase-change recording
material tends to be low, and the storage stability of
the amorphous phase tends to improve. Namely, by using
Ge, recrystallization of the amorphous state in a storage
state in the vicinity of room temperature can mainly be
suppressed, thus improving the storage stability of the
amorphous state. Accordingly, by using Ge, the recording
stability of the phase-change recording material
improves.
However, such an improvement of the archival
stability of the amorphous phase may cause such a problem
in some cases that the phase change can not favorably be
carried out when the amorphous phase after a lapse of
long time is crystallized again (erasing of the recording

marks). The reason why the above recrystallization of
the amorphous phase can not favorably be carried out is
not necessarily understood clearly, however, it is
considered that the amorphous state once formed by rapid
cooling transit to another more stable amorphous state
with a lapse of time, and accordingly crystallization
after long-term storage can not favorably be carried out.
As the amorphous state once formed by rapid cooling is in
a locally stable state, it is very likely that the state
of atomic bond slightly changes in a long time, and the
amorphous state transits to a state which is more stable
in view of energy.
Further, from such a viewpoint that emphasis is put
on the recording properties when the amorphous marks are
recrystallized (erased) after a lapse of long time and
then the overwriting of amorphous marks is carried out
again, it is preferred to achieve the effect of improving
the erasing properties after a lapse of long time, even
by making the storage stability of the amorphous phase in
the vicinity of room temperature be somewhat unstable, by
decreasing the Ge content as far as possible.
However, as described above, in the SbSnGe type
ternary composition, if the Ge content is lower than 10
atomic%, the crystallization speed tends to be too high,
whereby it tends to be difficult to let the crystalline
state in a non-recorded state and the amorphous state in
a recorded state. Further, even though the amorphous

state is formed, the amorphous state tends to be
recrystallized in storage at room temperature, and
accordingly it is difficult to make the Ge content less
than 10 atomic% in the SbSnGe type ternary composition.
Accordingly, in the present invention, the effect of
decreasing the crystallization speed or the effect of
improving the storage stability of the amorphous state by
the element Ml, and the effect of increasing the
crystallization speed or the effect of decreasing the
storage stability of the amorphous state by decreasing
the Ge content, are counterbalanced with each other, and
accordingly the recording properties after a lapse of
long time will be improved substantially without changing
the crystallization speed.
However, the effect of decreasing the
crystallization speed by the element Ml is not so high as
the effect of decreasing the crystallization speed by Te,
as mentioned hereinafter. Accordingly, when the element
Ml is incorporated into the SbSnGe type ternary
composition, the crystallization speed of the phase-
change recording material tends to be too high, if the
lower limit of the Ge content is lower than 5 atomic%
(y=0.05). Accordingly, as described hereinafter,
although the lower limit of the Ge content can be
decreased to 1 atomic% (y=0.01) in a case where Te is
incorporated into the SbSnGe type ternary composition,
the lower limit of the Ge content can be decreased only

to 5 atomic% (y=0.05) in a case where the element M1
alone is incorporated into the SbSnGe type ternary
composition.
Namely, in the above formula (lb), the value of y is
at least 0.05, preferably at least 0.08, more preferably
at least 0.1, furthermore preferably at least 0.12,
particularly preferably at least 0.15. Within this
range, favorable recording properties will be obtained
even after a lapse of long time. On the other hand, the
value of y is at most 0.3, preferably at most 0.25, more
preferably at most 0.2. Within this range,
crystallization speed required at the time of high
transfer rate recording/erasing can be obtained.

In the above formula (1), when and
the phase-change recording material of the present
invention has a composition containing Te. The formula
(1) has the following formula (1c):

wherein x and y are numbers which satisfy
and respectively. Further, in the above
formula (1c), the element M1 is at least one member
selected from the group consisting of In, Ga, Pt, Pd, Ag,
rare earth elements, Se, N, O, C, Zn, Si, Al, Bi, Ta, W,
Nb and V.
The reason why the value of x is within a range of
in the above formula (lc) is as explained in

the above item (A) . In the SbSnGe ternary composition as
in the above formula (la), when x is increased (such as x
the difference in optical properties between the
crystalline state and the amorphous state tends to be
significant, and accordingly a high signal amplitude can
be obtained particularly when the information recording
medium of the present invention is used as an optical
recording medium. However, from a viewpoint to further
improve repetitive overwriting durability and signal
properties in a case where overwriting is further carried
out on recording marks after long-term storage, it is
preferred to decrease x to a certain extent. If Te is
added, even in a case where x is at least 0.2 and is
relatively high, the repetitive recording durability and
signal properties when overwriting is further carried out
on recording marks after long-term storage will improve.
Accordingly, a phase-change recording material excellent
in all of the initial properties, repetitive recording
durability and signal properties in a case where
overwriting is further carried out on recording marks
after long-term storage, will be obtained.
The Te content is higher than 0 atomic% (0 preferably at least 0.1 atomic% , more
preferably at least 1 atomic% , particularly
preferably at least 3 atomic% . Within this
range, overwriting properties will be favorable when
overwriting is carried out on recording marks after long-

term storage. On the other hand, if the Te content is
high, a crystalline phase of GeTe or a crystalline phase
of GeSbTe tends to appear, the uniformity of the
crystalline structure in the phase-change recording
material of the present invention containing SbSn as the
main component tends to decrease, and the reflectivity of
the crystalline state and the signal amplitude tend to be
low. Accordingly, the Te content is at most 10 atomic%
preferably at most 9 atomic% more
preferably at most 7 atomic% . When the Te
content is at most 7 atomic%, the reflectivity of the
crystalline state and the signal amplitude can adequately
be secured.
Now, the meaning of use of Te in the phase-change
recording material of the present invention will be
explained in further detail. That is, by using Te, the
Ge content in the above formula (1c) can be decreased to
be less than 10 atomic% (y atomic% (y a SbSnGe ternary composition, from such a viewpoint that
the crystallization speed is adjusted to let the
crystalline state in a non-recorded state and the
amorphous state in a recorded state, y representing the
Ge content can not be less than 0.1. Further, as
explained in the above item (B), in the case of the a
quaternary composition comprising Ml (such as In) having
a role to adjust e.g. the crystallization speed added to

SbSnGe, the lower limit of the Ge content can be
decreased to 5 atomic% (y=0.05). However, in such a case
also, when the Ge content is lower than 5 atomic%, the
crystallization speed of the phase-change recording
material tends to be too high.
When Te is incorporated in the phase-change
recording material having such a composition, the
crystallization speed can further be decreased. As
mentioned above, Ge is an element which has a powerful
role to decrease the crystallization speed. Accordingly,
the lower limit of the Ge content can be decreased as
compared with the composition of SbSnGe or SbSnGeM1.
Decreasing the Ge content also has the following effects.
When Ge is incorporated in a large amount, the
crystallization speed of the phase-change recording
material tends to be low, whereby the storage stability
of the amorphous state tends to improve. Namely, by use
of Ge, recrystallization of the amorphous state stored
mainly in the vicinity of room temperature can be
suppressed, and the storage stability of the amorphous
state will improve. Accordingly, by using Ge, the
recording stability of the phase-change recording
material will improve.
However, this improvement of the storage stability
of the amorphous state may cause such a problem that the
phase change can not. favorably be carried out when the
amorphous state after a lapse of long time after

recording, is crystallized again (erasing of recording
marks) in some cases. The reason why the amorphous state
can not favorably be crystallized again is not
necessarily understood clearly, however, it is considered
that the amorphous state once formed by rapid cooling
transfers to another more stable amorphous state as time
goes by.
Accordingly, from such a viewpoint that emphasis is
put on recording properties in such a case that the
amorphous marks are once recrystallized (erased) after
the lapse of long time and then the amorphous marks are
recorded again, it is preferred to achieve the effect of
improving the erasing properties after a lapse of long
time, even by making the storage stability of the
amorphous state in the vicinity of room temperature be
somewhat unstable, by decreasing the Ge content as far as
possible. However, as described above, when the Ge
content is low, the crystallization speed tends to be too
high, whereby it becomes difficult to let the crystalline
state in a non-recorded state and the amorphous state in
a recorded state. Further, even if the amorphous state
is formed, the amorphous state is likely to be
recrystallized in storage at room temperature.
Accordingly, in the present invention, by use of Te, the
effect of decreasing the crystallization speed or the
effect of improving the storage stability of the
amorphous state by Te, and the effect of increasing the

crystallization speed or the effect of decreasing the
storage stability of the amorphous state by decreasing
the Ge content, are counterbalanced with each other, and
accordingly the recording properties after a lapse of
long time will be improved substantially without changing
the crystallization speed.
Further, it is estimated that by use of Te, such an
effect that transfer of the amorphous state to another
more stable amorphous state by the above-described change
with time is suppressed, is also obtained.
Taking the above into consideration, y representing
the Ge content in the above formula (1c) is at least
0.01, preferably at least 0.05, more preferably at least
0.08, further more preferably at least 0.1. Within this
range, favorable recording properties even after a lapse
of long time will be obtained. On the other hand, the
value of y is at most 0.3, preferably at most 0.25, more
preferably at most 0.2. Within this range,
crystallization speed required for recording/erasing at a
high transfer rate will be obtained.
One purpose of use of Te in combination with Ge for
the phase-change recording material is further to
increase long-term storage stability as compared with the
case of Ge alone as described above. Accordingly, it is
preferred that Te is used subsidiary to Ge. Further, the
total content of Ge and Te is preferably y+w≤0.3, more
preferably y+w≤0.2. On the other hand, in order to

secure stability of the amorphous marks, y+w is usually
at least 0.05, preferably at least 0.07, more preferably
at least 0.1.
Further, the meaning of use of the element Ml in the
above formula (1c) is as explained in the above item (B)
(by use of the element Ml, the increase of the noise will
be suppressed, another effect may further be obtained
depending upon the type of the element Ml used, etc.).
Further, the range of z representing the content of the
element M1 in the above formula (1c) and the reason why z
is within such a range, etc. are also explained in the
above item (B).
The reflectivity in the crystalline state and the
signal amplitude of the phase-change recording material
tend to decrease by addition of Te, and accordingly when
an element which has a role to increase the signal
amplitude such as In, Pd, Ag or Au is added as the
element M1 simultaneously with addition of Te, a more
favorable phase-change recording material will be
obtained. Most preferred as the element M1 to be used in
combination with Te is In. In this case, the formula (1)
has the following formula (Id):
(Sb1-xSnx)1-y-w-zGeyTewIn2 (1d)
Particularly, in order to suppress the decrease in the
optical contrast due to addition of Te, the amount of In
or Sn should be large, and the ratio of the total content
of In and Sn {xx(1-y-w-z)+z} to the Te content w, i.e.

{xx(1-y-w-z)+z}/w is at least 2, more preferably at least
3.
(D) Other items
The phase-change recording material of the present
invention preferably contains Sb as the main component.
As the element most effective for high-speed
crystallization is Sb, favorable recrystallization can be
carried out even in a case where recrystallization of
amorphous marks (erasing) is carried out by irradiation
of an energy beam in a time shorter than 100 nsec, for
example, when a phase-change recording material
containing Sb as the main component is used.
Accordingly, in the above formula (1), the Sb content is
preferably at least 50 atomic%. Namely, it is preferred
that (1-x) x (1-y-w-z) ≤ 0 . 5 . By using Sb as the main
component, a single crystalline phcise comprising a Sb
hexagonal structure as the base will easily be obtained.
Further, in the above formula (1), in order to
precisely control the crystallization speed, it is
important to control the total content of Ge, Te and the
element M1. Accordingly, y+z+w is preferably at least
0.1, more preferably at least 0.15. Within such a range,
amorphous marks will favorably be formed. On the other
hand, y+z+w is preferably at most 0.4, more preferably at
most 0.3. Within such a range, the phase-change speed
will be adequately high, and the change in the
reflectivity at the time of phase change will be

significant. Further, within the above range, appearance
of another stable crystalline phase by combination of Ge,
Te and the element Ml will be suppressed.
The meaning of controlling the sum of y, z and w in
the above formula (1) will be explained in detail below.
In the above formula (1), by changing the Ge
content, the crystallization speed can be controlled.
Namely, in the recording composition (Sb1-xSnx)1-y-w-
zGeyTewM1z, the crystallization speed tends to be high
when y is small. It is necessary that the
crystallization speed is high for recording/erasing in a
short time on a rewritable information recording medium
in general. Accordingly, in order to obtain
crystallization speed depending upon the recording
conditions of a rewritable information recording medium,
the Ge content to be incorporated should be optionally
controlled. However, the crystallization speed also
relates to the values of z and w, and when z or w is
high, the crystallization speed tends to be low.
Accordingly, in order to control the crystallization
speed, it is effective to control y+z+w to be within the
above predetermined range by decreasing y when z or w is
high.
JP-A-63-201927 discloses recording elements of a
write once type, comprising a SbSnGe type alloy.
However, the principle of forming the recording marks is
different from that of the present invention. Namely, in

the write once type medium as disclosed in JP-A-63-
201927, an amorphous film obtained at the time of
preparation of the medium is utilized as a non-recorded
state, and crystalline recording marks are formed therein
by light irradiation. On the other hand, in the phase-
change recording material of the present invention, the
crystalline state of the phase-change recording material
is in a non-recorded state, and the amorphous state is in
a recorded state. Particularly when the phase-change
recording material of the present invention is used for
an optical recording medium, it is important that the
entire recording layer containing the phase-change
recording material is in a uniform crystalline state. In
the optical recording medium, amorphous recording marks
are formed in the above recording layer in the uniform
crystalline state.
Here, the performances required for the phase-change
recording material are significantly different between
the case where crystalline recording marks are formed on
a write once type medium and the case where the amorphous
recording marks are formed as in the medium of the
present invention.
First, the range of the crystallization speed
required for the phase-change recording material is
different as between the case where crystalline recording
marks are formed on a write once type medium and the case
where amorphous recording marks are formed as in the

medium of the present invention. Namely, in a case where
crystalline recording marks are formed on a write once
type medium, it is required to use a phase-change
recording material having a very high crystallization
speed, because not only once formed crystalline recording
marks are not required to be recovered to the amorphous
state, but also it is unfavorable that the recording
marks recover to the amorphous state from the viewpoint
of securing the stability of the crystalline marks.
Further, in a phase-change recording material having a
low crystallization speed, before the entire area which
is melted by e.g. light irradiation becomes in a
crystalline state, part of the area becomes in an
amorphous state, and thus the recording marks may deform,
such being problematic.
On the other hand, in a case where the amorphous
recording marks are formed as in the medium of the
present invention, if the crystallization speed of the
phase-change recording material is too high, the area
which is melted by e.g. light irradiation is
recrystallized, and the amorphous recording marks can not
be formed. Accordingly, in order to stably form the
amorphous recording marks, it is required to achieve the
crystallization speed with the crystallization speed and
the stability of the amorphous recording marks are well
balanced. Accordingly, in order to keep a favorable
balance of the crystallization speed with the stability

of the amorphous recording marks, the temperature
dependency of the crystallization speed is preferably
high. Namely, in a case where the amorphous recording
marks are recrystallized, the temperature at the time of
crystallization is in a high temperature region which is
adequately higher than the crystallization temperature
and is close to the melting point, and the
crystallization speed is preferably high in this
temperature region. On the other hand, from the
viewpoint to increase the storage stability of the
amorphous recording marks, in a low temperature region
which is adequately lower than the crystallization
temperature and is in the vicinity of the room
temperature, the crystallization speed is preferably low
in order to prevent recrystallization of amorphous marks.
In the phase-change recording material of the present
invention, by using Ge and further by controlling the Ge
content, the above temperature dependency of the
crystallization speed can be realized.
Second, the required properties regarding
crystalline nucleation in the phase-change recording
material are also totally different as between the case
of forming crystalline recording marks on a write once
type medium and the case where amorphous recording marks
are formed as in the medium of the present invention.
Namely, in a case where crystalline recording marks are
formed in the amorphous state, it is required that a

large number of crystalline nuclei are present in the
amorphous state. This is because the crystalline
recording marks can not be formed in a region where no
crystalline nuclei are present, and it is required that a
large number of crystalline nuclei are present in the
region on which recording marks are to be formed, in
order to accurately control the shape and the position of
the crystalline recording marks. If the number of the
crystalline nuclei is insufficient, as the position of
the crystalline recording mark formation depends on the
position of the crystalline nuclei, recording properties
such as jitters tend to deteriorate.
On the other hand, in a case where amorphous
recording marks are formed in a uniform crystalline state
as in the medium of the present invention, it is
preferred that no crystalline nuclei are present in the
phase-change recording material, or even if they are
present, the number of the crystalline nuclei is small to
such an extent that the crystalline nuclei do not
substantially function in the process of forming
amorphous recording marks. This is because if the
crystalline nuclei effectively function in the process of
mark formation, a part of or the entire melted region on
which the amorphous marks are to be formed, is
recrystallized without being formed into an amorphous
state. Namely, in a case where amorphous marks are
formed, it is preferred that the shape of the marks is

determined only by the heat history of the phase-change
recording material without being affected by the number
or the position of the crystalline nuclei as far as
possible.
Further, in the present invention, even if no
crystalline nuclei are present in the recording marks
when the amorphous recording marks are erased by
recrystallization, crystalline growth takes place with
crystals at the periphery of the recording marks as the
starting point, and accordingly it is not required that
the crystalline nuclei are present in the amorphous
state. In the present invention, by using Ge and further
by controlling the Ge content, formation of the
crystalline nuclei in the phase-change recording material
can effectively be suppressed. Formation of the
crystalline nuclei proceeds in a temperature region lower
than a temperature region in which the crystalline growth
takes place in general. Accordingly, suppression of the
crystalline nucleation is preferred also in view of
storage stability of the amorphous marks in the vicinity
of room temperature.
As mentioned above, the properties required for the
phase-change recording material (such as the optimum
region of the crystallization speed) and the crystalline
state of the phase-change recording material (such as
whether it is in a crystalline state in which a large
number of crystalline nuclei are present, or it is a

uniform crystalline state with a small number of
crystalline nuclei), are different as between the case
where crystalline recording marks are formed in a write
once type medium and the case where amorphous recording
marks are formed as in the medium of the present
invention. As a result, the composition ranges of the
phase-change recording material on which crystal
recording marks are formed and the phase-change recording
material on which amorphous recording marks are formed,
are different of course.
JP-A-2002-11958 discloses a write once type optical
recording medium comprising InSnSb and a slight amount of
Ge incorporated thereinto. However, the optical
recording medium is to form recording marks in a
crystalline state on a recording layer in an amorphous
state (crystal recording type), and accordingly formation
of recording marks in an amorphous state and improvement
of storage stability of the recording marks in an
amorphous state are not considered at all. Further, the
recording medium is an optical recording medium of a
crystal recording type, the Ge content is less than 5
atomic% in the recording layer composition as
specifically disclosed.
2. Information recording medium
The information recording medium of the present
invention is an information recording medium utilizing
the crystalline state as a non-recorded state and the

amorphous state as a recorded state, and is characterized
by using the phase-change recording material having the
composition of the above formula (1) as the main
component. As explained in the above item "1. phase-
change recording material", when the phase-change
recording material having the composition of the above
formula (1) as the main component is used for a
rewritable information recording medium, the effect of
improving the quality of the recording signals and the
effect of improving the productivity of the information
recording medium tend to be particularly remarkable.
Accordingly, in the present invention, the information
recording medium is preferably used as a rewritable
information recording medium on which the information can
be rewritten by a reversible change of the phase-change
recording material having the composition of the above
formula (1) as the main component between the crystalline
state and the amorphous state.
More preferably, the information recording medium of
the present invention is an optical recording medium, and
is an information recording medium having a phase-change
type recording layer containing the phase-change
recording material having the composition of the above
formula (1) as the main component and at least one
protective layer. More preferably, the optical recording
medium is a rewritable information recording medium.
Now, the specific constitution of the medium and the

recording/retrieving method will be described in detail
in the following items (A) to (C), in a case of applying
the phase-change recording material to be used in the
present invention to a rewritable optical recording
medium (hereinafter "rewritable optical recording medium"
will be referred to simply as "optical recording
medium").
(A) Layer structure
As the optical recording medium, usually one having
the multilayer structure as shown in Fig. 1(a) or Fig.
1(b) is employed. Namely, as evident from Figs. 1(a) and
1(b), it is preferred that the recording layer to be used
for the optical recording medium of the present invention
and on at least one side thereof, heat resistant
protective layers are formed, on a substrate. A
reflective layer is formed on the side opposite to the
incidence of recording and retrieving light beam in many
cases, but the reflective layer is not essential.
Further, a translucent absorption film is optionally
formed on the side of the incidence of light with a
purpose of controlling the light absorption. Further,
the protective layer which is preferably formed on at
least one side of the recording layer, is made to have a
multilayer structure with materials having different
properties.
Now, the recording layer will be explained below.
As the material contained in the recording layer,

the phase-change recording material of the above formula
(1) is used as the main component. In order to
effectively obtain the effect of the present invention,
the phase-change recording material of the above formula
(1) is contained in an amount of usually at least 50
atomic%, preferably at least 80 atomic%, more preferably
at least 90 atomic%, particularly preferably at least 95
atomic%, in the entire recording layer. The higher the
content, the more remarkable the effect of the present
invention. However, the effect of the present invention
such as high speed recording/erasing will securely be
obtained even if another component such as O or N is
incorporated at the time of recording layer formation, if
its content is within a range of several atomic% to 20
atomic%.
The thickness of the recording layer is usually at
least 1 nm, preferably at least 5 nm, particularly
preferably at least 10 nm, whereby the contrast of the
reflectivity between the crystalline state and the
amorphous state will be sufficient, and the
crystallization speed will be sufficient, whereby
recording/erasing in a short time will be possible.
Further, the reflectivity itself will be sufficient. On
the other hand, the thickness of the recording layer is
usually at most 30 nm, preferably at most 25 nm,
particularly preferably at most 20 nm, whereby a
sufficient optical contrast will be obtained, and no

cracks are likely to form on the recording layer.
Further, no significant deterioration of the recording
sensitivity due to increase of the thermal capacity will
take place. Further, within the above film thickness
range, the volume change due to a phase change can
appropriately be suppressed, whereby microscopic and
irreversible deformation of the recording layer itself or
the protective layer to be formed on or below it, which
may cause noise, is less likely to be accumulated when
overwriting is repeatedly carried out. Such an
accumulation of the deformation tends to decrease the
repetitive overwriting durability, and this tendency can
be suppressed by making the thickness of the recording
layer within the above range.
The requirement against noise is more severe in a
case where recording/retrieving is carried out by means
of a focused light beam with LD (laser diode) having a
wavelength of about 650 nm with an objective lens with a
numerical aperture of from about 0.6 to about 0.65, such
as a rewritable DVD, or in a case of a high density
medium on which recording/retrieving is carried out by
means of a focused light beam with a blue LD having a
wavelength of about 400 nm with an objective lens with a
numerical aperture of from about 0.7 to about 0.85.
Accordingly, in such a case, a more preferred thickness
of the recording layer is at most 25 nm.
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. The bulk density p is usually an approximate
value by the following formula (2), but it may actually
be measured by preparing a mass of the alloy composition
constituting the recording layer:
ρ =∑mi ρ i(2)
wherein mi is the molar concentration of each element i,
and ρ i is the atomic mass of each element i.
In a film formation method by sputtering, the
density of the recording layer can be increased by
increasing the high energy Ar amount to be irradiated on
the recording layer, by e.g. decreasing the pressure of
the sputtering gas (usually an inert gas such as Ar: the
following explanation will be made with reference to the
case of Ar as an example) at the time of film formation
or by disposing a substrate in the vicinity of the front
of the target. The high energy Ar is either part of Ar
ions to be irradiated on the target for sputtering, being
reflected and arriving at the substrate side, or Ar ions
in the plasma being accelerated by the sheath voltage on
the entire substrate surface arriving at the substrate is
general.
Such an irradiation effect of a high energy inert
gas is called atomic peening effect, and in sputtering by

an Ar gas commonly used, Ar is incorporated in the
sputtering film by the atomic peening effect. The atomic
peening effect may be estimated from the Ar amount in the
film. Namely, the smaller Ar amount means a smaller
effect of high energy Ar irradiation, and a less dense
film is likely to form.
On the other hand, when the Ar amount is large,
irradiation of the high energy Ar tends to be intense,
and the density of the film will be high, however, Ar
incorporated in the film is likely to deposit as voids at
the time of repetitive overwriting, whereby repetitive
durability is likely to deteriorate. Accordingly, a
charging is carried out under an appropriate pressure,
usually in the order of from 10-2 to 10-1 Pa.
Now, other components in the structure of the
optical recording medium which is an preferred embodiment
of the present invention will be explained below.
As the substrate used in the present invention, a
resin such as polycarbonate, acryl or polyolefin, glass
or a metal such as aluminum may be employed. Guide
grooves having a depth of from about 20 to about 80 nm
are usually formed on the substrate, and preferred is a.
substrate made of a resin on which the guide grooves can
be formed by molding. Further, in a case of a so-called
incidence from the substrate side wherein the focused
light beam for recording/erasing/retrieving is incident
from the substrate side (Fig. 1(a)), the substrate is

preferably transparent.
In order to prevent evaporation/deformation of the
recording layer due to the phase change and to control
heat diffusion at that time, a protective layer is
usually formed on one side or on both sides of the
recording layer, preferably on both sides. The material
of the protective layer is determined in consideration of
refractive index, thermal conductivity, chemical
stability, mechanical strength, adhesion properties and
so on. Generally, a dielectric material such as an
oxide, a sulfide, a carbide or a nitride of a metal or a
semiconductor material having a high transparency and a
high melting point, or a fluoride of Ca, Mg, Li or the
like, may be used.
In such a case, these oxide, sulfide, carbide,
nitride and fluoride are not always necessary to have a
stoichiometric composition. It is effective to control
the composition to adjust the refractive index and so on,
or to use a mixture of these materials. A mixture of
dielectric materials is preferred taking the repetitive
recording properties into consideration. More
specifically, a mixture of a heat resistant compound such
as an oxide, a nitride, a carbide or a fluoride with ZnS
or a chalcogen compound such as a rare earth sulfide may
be mentioned. For example, a mixture of heat resistant
compounds containing ZnS as the main component, and a
mixture of heat resistant compounds containing an

oxysulfide of rare earth particularly Y2O2S as the main
component, are mentioned as examples of 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,
Ge, Sn, Sb or Te, a nitride of e.g. Ti, Zr, Hf, V, Nb,
Ta, Cr, Mo, W, Zn, B, Al, Ga, In, Si, Ge, Sn, Sb or Pb, a
carbide of e.g. Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, B,
Al, Ga, In or Si, or a mixture thereof. Further, as the
dielectric material, a sulfide, a selenide or a telluride
of e.g. Zn, Y, Cd, Ga, In, Si, Ge, Sn, Pb, Sb or Bi, a
fluoride of e.g. Mg or Ca, or a mixture thereof may be
mentioned.
Further, as specific examples 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 a high film formation
speed, a small film stress, a small volume change due to
the change in temperature and an excellent weather
resistance.
Taking the repetitive recording properties into
consideration, the film density of the protective layer
is preferably at least 80% of the bulk state, in view of
mechanical strength. When a mixture of dielectric
materials is used, the theoretical density of the above

formula (2) is employed as the bulk density.
The thickness of the protective layer is usually
from 1 nm to 500 nm in general. When the thickness is at
least 1 nm, the effect of preventing the deformation of
the substrate or the recording layer can be adequately
obtained, and its role as a protective layer can
adequately be performed. Further, when the thickness is
at most 500 nm, while the role as the protective layer is
adequately performed, e.g. the internal stress of the
protective layer itself or the difference in elastic
properties with the substrate tend to be remarkable, thus
preventing generation of cracks.
Particularly when a protective layer (hereinafter
sometimes referred to as a lower protective layer) is
formed between the optical-beam entrance substance and
the recording layer, the lower protective layer is
required to suppress deformation of the substance by
heat, and accordingly its thickness is usually at least 1
nm, preferably at least 5 nm, particularly preferably at
least 10 nm, whereby accumulation of microscopic
deformation of the substance during repetitive
overwriting will be suppressed, whereby the increase of
noise caused by scattering of the retrieving light will
not be remarkable.
On the other hand, the thickness of the lower
protective layer is preferably at most 200 nm, more
preferably at most 150 nm, furthermore preferably at most

100 nm, in relation to the time required for film
formation. When the thickness is within this range, the
groove shape of the substrate as observed on the
recording layer plane will not change. Namely, such a
phenomenon is less likely to take place that the depth or
width of the grooves are smaller than the shape attempted
on the substrate surface.
On the other hand, when a protective layer
(hereinafter sometimes referred to as an upper protective
layer) is formed on the side of the recording layer
opposite to the optical-beam entrance side, the thickness
of the upper protective layer is usually at least 1 nm,
preferably at least 5 nm, particularly preferably at
least 10 nm, in order to suppress deformation of the
recording layer. Further, in order to prevent
accumulation of microscopic plastic deformation in the
inside of the upper protective layer generated due to the
repetitive overwriting and to suppress the noise increase
due to scattering of retrieving light, 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.
The thickness of each of the recording layer and the
protective layer is selected so as to provide good laser
light absorbing efficiency and to increase the amplitude
of the recording signals, i.e. to increase the contrast
between a recorded state and a non-recorded state in

consideration of an interfering effect caused by a
multilayer structure, in addition to restrictions from
mechanical strength and reliability.
On the optical recording medium, a reflective layer
may further be formed. The position on which the
reflective layer is formed usually depends on the
direction of incidence of retrieving light, and it is
formed on the side of the recording layer opposite to the
incidence side. namely, in a case where a retrieving
light is incident from the substrate side, the reflective
layer is usually formed on the side of the recording
layer opposite to the substrate, and in a case where
retrieving light is incident from the recording layer
side, the reflective layer is formed usually between the
recording layer and the substrate (Figs. 1(a), (b)) .
The material used for the reflective layer is
preferably a substance having a high reflectivity, and
particularly preferred is a metal such as Au, Ag or Al
with which heat dissipation effect can be expected. Its
heat dissipation property is determined by the film
thickness and the thermal conductivity, and as the
thermal conductivity is substantially in proportion to
the specific volume resistance in the case of these
metals, and accordingly the heat dissipation property can
be represented by the sheet resistivity. The sheet
resistivity is usually at least 0.05 Ω/□, preferably at
least 0.1 Ω/□, and usually at most 0.6 Ω/□, preferably

at most 0.5 Ω/□ .
This is to secure a particularly high heat
dissipation property, and it is required to suppress
recrystallization to a certain extent in a case where the
competition between amorphous state forming and
recrystallization is significant in formation of the
amorphous marks as in the recording layer to be used for
the optical recording medium. A small amount of Ta, Ti,
Cr, Mo, Mg, V, Nb, Zr, Si or the like may added to the
above metal to control the thermal conductivity of the
reflective layer itself or to improve corrosion
resistance. The addition amount is usually at least 0.01
atomic% and at most 2 0 atomic%. An aluminum alloy
containing Ta and/or Ti in an amount of at most 15
atomic%, particularly an alloy of AlαTa1-α (0≤ α ≤0.15)
is excellent in corrosion resistance, and is a
particularly preferred reflective layer material in view
of improving the reliability of the optical recording
medium.
Further, a Ag alloy comprising Ag and at least one
member selected from Mg, Ti, Au, Cu, Pd, Pt, Zn, Cr, Si,
Ge and rare earth elements in an amount of at least 0.01
atomic% and at most 10 atomic% added to Ag, also has high
reflectivity and thermal conductivity and excellent heat
resistance and is thereby preferred.
Particularly when the thickness of the upper
protective layer is at least 5 nm and at most 50 nm, the

amount of the element to be added is preferably at most 2
atomic% in order that the reflective layer has a high
thermal conductivity.
Particularly preferred as a material of the
reflective layer is one containing Ag as the main
component. The reason why it is preferred to employ Ag
as the main component is as follows. Namely, when
overwriting is carried out again on the recording marks
after long-term storage, such a phenomenon may take place
in some cases that the recrystallization speed of the
phase-change recording layer is high only at the time of
the first overwriting immediately after the storage.
Although the reason of such a phenomenon is not clearly
understood, by increase of the recrystallization speed of
the recording layer immediately after the storage, the
size of the amorphous marks formed by the first
overwriting immediately after the storage is smaller than
the desired size of the marks. Accordingly, when such a
phenomenon takes place, recrystallization of the
recording layer at the time of the first overwriting
immediately after the storage can be suppressed, whereby
a desired size of the amorphous marks can be maintained,
by increasing the cooling rate of the recording layer by
using Ag having a very high release property for the
reflective layer.
The thickness of the reflective layer is preferably
at least 10 nm so that the incident light is completely

reflected without transmitted light. Further, if it is
too thick, no further heat dissipation effect will be
obtained but the productivity will be poor, and cracks
are likely to form, and accordingly it is usually at most
500 nm.
The preferred layer structure of the optical
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 direction of incidence of retrieving light.
Namely, in a case where retrieving light is incident from
the substrate side, preferred is a layer structure of a
substrate, a lower protective layer, a recording layer,
an upper protective layer and a reflective layer, and in
a case where retrieving light is incident from the
recording layer side, preferred is a layer structure of a
substrate, a reflective layer, a lower protective layer,
a recording layer and an upper protective layer.
Needless to say, each layer may consist of at least
two layers, and an interlayer may be formed therebetween.
For example, between the substrate and the protective
layer in the case where the retrieving light is incident
from the substrate side, or on the protective layer in
the case where retrieving light is incident from the side
opposite to the substrate side, an extremely thin
translucent layer of a metal, a semiconductor or a
dielectric material having absorption property or the

like may be formed so as to control the amount of light
energy incident on the recording layer.
Each of the recording layer, the protective layer
and the reflective layer if formed usually by e.g. a
sputtering method.
The film formation is carried out preferably by
placing a target for recording layer, a target for
protective layer or a target for reflective layer
material as the case requires, in an in-line device
located in the same vacuum chamber because the oxidation
and contamination by adjacent layers can be prevented.
Further, such a method is advantageous in productivity.
On the outermost side of the optical recording
medium, a protective coat comprising an ultraviolet-
curing resin or a thermosetting resin is preferably
formed so as to prevent a direct contact with air or to
prevent scars due to contact with a foreign substance.
The protective coat usually has a thickness of from 1 -urn
to several hundireds urn. Further, a dielectric material
protective layei: having a high hardness may further be
formed, or a resin layer may further be formed thereon.
(B) Method of initial crystallization of the optical
recording medium
The recording layer is formed usually by a physical
deposition method in vacuum such as a sputtering method,
and the recording layer is usually amorphous in a state
immediately after film formation (in an as-deposited

state), and accordingly this is crystallized to be in a
non-recorded/erased state in the present invention. This
operation is called initialization. As the initial
crystallization operation, oven annealing in a solid
phase at a temperature of at least the crystallization
temperature (usually from 150 to 300°C) and at most the
melting point, annealing by irradiation with light energy
such as laser light or flash lamp light, or melt
initialization may, for example, be mentioned. In the
present invention, it is preferred to employ the melt
initialization among the above initial crystallization
operations, as a phase-change recording material with
small formation of crystalline nuclei is employed.
In the melt initialization, if the recrystallization
speed is too slow, another crystalline phase may form as
there is a sufficient time to achieve thermal
equilibrium, and accordingly it is preferred to increase
the cooling rate to a certain extent. Further, when it
is kept in a melted state for a long time, the recording
layer may flow, a thin film such as the protective layer
may be peeled off by stress, or e.g. a resin substrate
may deform, thus causing destruction of the medium.
For example, the time for which the recording layer
is kept at a temperature of at least the melting point is
usually at most 10 us, preferably at most 1 us.
Further, for the melt initialization, it is
preferred to employ laser light, and it is particularly

preferred to carry out the initial crystallization by
using elliptical shape laser light having a minor axis
substantially in. parallel with the scanning direction
(hereinafter this initialization method will sometimes be
referred to as "bulk erasing") . In such a case, the
length of the major axis is usually from 10 to 1,000 µm,
and the length of the minor axis is usually from 0.1 to 5
µm.
The lengths of the major axis and the minor axis of
the beam are defined from the full width at half maximum
when the light energy intensity distribution of the beam
is measured. The beam shape also preferably has a minor
axis length of at most 5 µm, more preferably at most 2
µm, so that the local heating in a minor axis direction
and rapid cooling are easily realized.
As a laser light source, various ones such as a
semiconductor laser or a gas laser may be used. The
laser light power is usually from about 100 mW to 10 W.
Another light source may be used so long as the power
density and the beam shape at the same level are
obtained. Specifically, a Xe lamp light may, for
example, be mentioned.
At the time of initialization by bulk erasing, when
a disc recording medium is used for example,
initialization of the entire surface can be carried out
in such a manner that the minor axis direction of the
elliptical beam is substantially agreed with the

tangential direction of the disc, and scanning is carried
out in the minor axis direction while rotating the disc,
and at the same time, the beam is moved to the long axis
(radius) direction every one cycle (one rotation). By
doing this, a polycrystalline structure aligned in a
specific direction relative to the focused light beam for
recording/retrieving for scanning along the track in a
periphery direction can be realized.
It is preferred that the distance of movement in a
radius direction per one rotation is shorter than the
beam major axis for overlapping, and the same radius is
irradiated with laser light beam several times. As a
result, secure initialization is possible, and at the
same time, the non-uniformity in the initialized state
derived from the energy distribution (usually from 10 to
20%) in a beam radius direction can be avoided. On the
other hand, if the amount of movement is too small, the
above unfavorable crystalline phase is likely to form,
and accordingly the amount of movement in a radius
direction is usually at least half the beam major axis.
At least whether an optical recording medium to be
used in the present invention can be obtained by the melt
initialization, can be judged by whether the reflectivity
R1 in a non-recorded state after the initialization and
the reflectivity R2 in an erased state by
recrystallization after overwriting is carried out on the
amorphous marks by a practical focused light beam for

recording with a diameter of about 1 urn, are
substantially the same. R2 is the reflectivity at the
erased part after 10 times overwriting.
Accordingly, the optical recording medium to be used
in the present invention preferably satisfies the
following relational expression (3) where Rl is the
reflectivity at a non-recorded part after the initial
crystallization and R2 is the reflectivity at an erased
part after 10 time overwriting:

The reason why the reflectivity R2 at an erased part
after 10 time overwriting is employed as a judgment index
is that when overwriting is carried out for 10 times, the
influence of the reflectivity in a crystalline state
which may remain in a non-recorded state by only one
recording can be eliminated, and the entire surface of
the optical recording medium can be in a recrystallized
state at least once by recording/erasing. On the other
hand, if the number of overwriting considerably exceeds
10 times, factors other than the change in the
crystalline structure, such as microscopic deformation by
repetitive overwriting or diffusion of another element
from the protective layer, may cause the change in the
reflectivity, and the judgment whether a desired
crystalline state can be obtained or not tends to be
difficult.
In the above relational expression (3), ΔR is at

most 10%, preferably at most 5%. When it is at most 5%,
an optical recording medium which causes a lower signal
noise can be obtained.
For example, of the optical recording medium having
an R1 at a level of 17%, R2 should be approximately
within a range of from 16 to 18%. The scanning velocity
of the energy beam for initialization is usually within a
range of from about 3 to about 20 m/s.
The above erased state may be obtained also by
melting the recording layer by irradiating a write power
in a direct current mode and re-solidifying it, not
necessarily by modulating the focused laser light for
recording in accordance with the practical method of
generating the recording pulse.
In order to obtain a desired initial crystalline
state of the phase-change recording material to be used
in the present invention, setting of the scanning
velocity of the energy beam for initialization relative
to the recording layer plane is particularly important.
Basically, it is important that the crystalline state
after the initial crystallization is similar to the
crystalline state at the erased state after overwriting,
and accordingly it is preferred that the scanning
velocity of the energy beam for initialization is close
to the relative scanning linear velocity of the focused
light beam relative to the recording layer plane when
overwriting is practically carried out by using the

focused light beam. Specifically, scanning is carried
out by the energy beam for initialization at a linear
velocity of from about 20 to about 80% of the maximum
linear velocity where recording by overwriting is
possible on the optical recording medium.
The maximum linear velocity for overwriting is that
the erasing ratio is at least 20 dB when, for example, an
erasing power Pe is irradiated in a direct current mode
at the maximum linear velocity.
The erasing ratio is defined as the difference
between the carrier level of the signals for the
amorphous marks recorded at the substantially same
frequency and the carrier level after erasing by direct
current irradiation of Pe. Measurement of the erasing
ratio is carried out as follows for example. First,
under the recording conditions where adequate signal
properties (i.e. such properties that the reflectivity
and the signal amplitude, and jitter and the like satisfy
predetermined values) are obtained, a condition with a
high frequency is selected among modulating signals to be
recorded, and overwriting is carried out 10 times at the
single frequency to form amorphous marks, and the carrier
level (C.L. at recording) is measured. Then, direct
current irradiation is carried out on the amorphous marks
once while changing the erasing power Pe, and the carrier
level at that time (C.L. after erasing) is measured, and
the difference between C.L. at recording and C.L. after

erasing, i.e. the erasing ratio is calculated. When the
power Pe of the direct current irradiation is changed,
the erasing ratio tends to once increase, decrease and
increase again in general. Here, the first peak value of
the erasing ratio as observed when the power Pe is
started to increase, is taken as the erasing power of the
sample.
If the scanning velocity of the energy beam for
initialization is lower than the velocity of
approximately 20% of the above-defined maximum linear
velocity, phase separation may take place, whereby no
single phase is likely to be obtained, or even if a
single phase is obtained, the crystallites tend to extend
particularly in the scanning direction of the beam for
initialization and to grow to an enormous size, or tend
to align in an unfavorable direction. Preferably,
scanning of the energy beam for initialization is carried
out at a velocity of at least 30% of the maximum linear
velocity with which overwriting is possible.
On the other hand, if scanning of the energy beam
for initialization is carried out at a velocity equal to
the maximum linear velocity with which recording by
overwriting is possible, or at a velocity higher than
approximately 80% of the maximum linear velocity, the
region once melted by the scanning for initialization is
formed into amorphous again, such being unfavorable.
This is because the cooling rate of the melted portion

becomes high when the scanning linear velocity is high,
and the time required for re-solidification becomes
short. Recrystallization by the crystal growth from the
crystal region around the periphery of the melted region
will be completed in a short time with focused light beam
for recording having a diameter of about 1 µm. However,
when scanning is carried out with elliptical light beam
for initialization, the area of the melted region in a
major axis direction becomes large, and accordingly it is
required to decrease the scanning linear velocity as
compared with practical overwriting, so that the
recrystallization at the time of re-solidification is
carried out in the entire melted region. From such a
viewpoint, the scanning linear velocity of the energy
beam for initialization is preferably at most 70% of the
maximum linear velocity for overwriting, more preferably
at most 60%.
The optical recording medium to be used in the
present invention has such a characteristic that when it
is subjected to initial crystallization by irradiation
with laser light, the rate of movement of the medium
relative to the laser light can be increased. This leads
to possibility of the initial crystallization in a short
time, which improves productivity and makes cost cutting
possible.
(C) Method of recording/retrieving of the optical
recording medium

The recording and retrieving light to be used for
the optical recording medium used in the present
invention is usually laser light of e.g. 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 surface
recording density of at least 1 Gbit/inch2, the focused
light beam diameter is required to be small, and it is
preferred to obtain a focused light beam by using blue to
red laser light having a wavelength of from 350 to 680 nm
and an objective lens having a numerical aperture NA of
at least 0.5.
In the present invention, as mentioned above, the
amorphous state is utilized as the recording marks.
Further, in the present invention, it is effective to
record information by a mark length modulation method.
This is particularly remarkable for mark length recording
with a shortest mark length of at most 4 urn, particularly
at most 1 µm.
When recording marks are formed, recording by means
of a conventional two power level modulation method may
be carried out, however, in the present invention, it is
particularly preferred to employ a recording method by a
multiple power level modulation method of at least three
values wherein an off-pulse period is provided when the
recording marks are formed as shown below.
Fig. 2 is a schematic view illustrating a power

pattern of a recording light in a method of recording on
the optical recording medium. In forming amorphous mark,
the mark length of which is modulated to a length nT (T
is a reference clock period, n is a mark length which the
mark may have by mark length modulation recording and is
an integer), (n-j)T (wherein j is a real number of at
least 0 and at most 2) is divided into recording pulses
in a number of m=n-k (wherein k is an integer of at least
0) , and the recording pulse width of each pulse is αiT
and each recording pulse is accompanied by an
off-pulse section for a time of . In Fig. 2
which indicates a divided recording pulse, indication of
the reference clock period T is omitted in view of
viewability of the figure. Namely, in Fig. 2, the
portion which should be described as a iT is simply
described as αi. Here, it is preferred that or α
is usually n, but it
is possible that (j is a constant which
satisfies ) in order to obtain accurate nT marks.
At the time of recording, a recording light with an
erasing power Pe which may recrystallize the amorphous
state is irradiated between marks. Further, recording
light with a write power Pw which is sufficient to melt
the recording layer is irradiated in a time of
and a recording light with a bias power Pb of
Pb

The power Pb of the recording light to be irradiated
in a time of a period βmT is usually Pb in the same manner as the period of
, however, it is possible that
By employing the above recording method, the power
margin or the linear velocity margin at the time of
recording can be increased. This effect is particularly
remarkable when the bias power Pb is adequately low so
that
The above recording method is a method particularly
suitable for an optical recording medium employing the
phase-change recording material of the present invention
for the recording layer. When the Ge amount is decreased
to secure erasing in a short time, the critical cooling
rate required for forming of amorphous marks will be
extremely high, and formation of favorable amorphous
marks tends to be difficult.
Namely, this is because decrease of the Ge amount
accelerates recrystallization from the crystallized part
around the periphery of the amorphous marks, and at the
same time, increases the crystal growth rate at the time
of melting and re-solidification also. If the
recrystallization rate from around the periphery of the
amorphous marks is increased to a certain extent,
recrystallization from around the periphery of the melted
region tends to proceed at the time of re-solidification
of the melted region formed for recording of amorphous

marks, and the melted region tends to be recrystallized
without being formed into an amorphous state, unless the
cooling rate is extremely high.
In addition, the clock period is shortened, and the
off-pulse section becomes short, whereby the cooling
effect tends to be impaired. Accordingly, it is
effective to set the cooling section by off-pulses to at
least 1 nsec, more preferably at lest 3 nsec as the real
time by dividing the recording pulses at the time of nT
mark recording.
(D) Use of the information recording medium of the
present invention other than as an optical recording
medium
On the information recording medium of the present
invention, at least recording by a reversible phase
change by irradiation with light is possible, and
accordingly it can be used as an optical recording medium
as described above. However, a rewritable information
recording medium used in the present invention can be
applied to recording by a phase change by applying an
electric current to a microscopic region, for example.
This point will be explained below.
Fig. 3 is a conceptual diagram illustrating the
temperature history at the time of amorphous mark
recording (curve a) and the temperature history at the
time of erasing by recrystallization (curve b). 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 a high voltage and short pulse
electric current or a high power level light beam, and
after the application of the electric current pulse or
irradiation with light beam is terminated, the recording
layer, is rapidly cooled and becomes amorphous by heat
dissipation to the periphery. When the cooling rate in a
time τ0 when the temperature is decreased from the
melting point Tm to the crystallization temperature Tg is
higher than the critical cooling rate for forming an
amorphous state, the recording layer becomes amorphous.
On the other hand, at the time of erasing, by application
of a relatively low voltage or irradiation with light
energy at a low power level, the recording layer is
heated to a temperature of at least the crystallization
temperature Tg and approximately at most the melting
point Tm, and is kept for at least a certain time,
whereby recrystallization of the amorphous marks proceeds
in a substantially solid state. Namely, if the holding
time τ1 is sufficient, crystallization is completed.
The recording layer becomes amorphous when the
temperature history as illustrated by the curve a is
applied to the recording layer and the recording layer is
crystallized when the temperature history as illustrated
by the curve b is applied to the recording layer, even if
the recording layer before application of energy for
recording or erasing is in any state.

The reason why the rewritable information recording
medium to be used in the present invention can be used
not only as an optical recording medium but also for
recording by a phase change by applying an electric
current to a microscopic region, is as follows. Namely,
it is the temperature history as illustrated in Fig. 3
that causes a reversible phase change, and the energy
source which causes such a temperature history may be
either focused light beam or heating by electric current
(Joule heating by current conducting).
The change in the resistivity due to the phase
change of the phase-change recording material to be used
in the present invention between the crystalline state
and the amorphous state is adequately comparable to the
change in the resistivity of at least two digits as
observed in a GeTe-Sb2Te3 pseudo-binary alloy which is
being developed as a non-volatile memory at present,
particularly a Ge2Sb2Te5 stoichiometric composition alloy
(J. Appl. Phys., Vol. 87 (2000), pp. 4130-4133). In
fact, of a rewritable information recording medium
employing the phase-change recording material having the
SbSnGeTeMl composition of the above formula (1) as the
main component, the resistivity in an as-deposited
amorphous state and the resistivity after crystallization
by annealing were respectively measured, whereupon
changes of at least three digits were confirmed (see the
following Examples). Although it is considered that the

amorphous state and the crystalline state obtained by
amorphization and crystallization by electric current
pulses are slightly different from the above as-deposited
amorphous state and the crystalline state by annealing,
respectively, it is expected that a significant change in
the resistivity at a level of two digits will adequately
be obtained even in a case of a phase change by electric
current pulses of the phase-change recording material to
be used in the present invention.
Fig. 4 is a sectional view illustrating the
structure of one cell of such a non-volatile memory (such
a non-volatile memory is also disclosed in Collected
Papers of Phase-Change Optical Information Storage
Symposium, 2001, pp. 61-66). In Fig. 4, the electric
voltage is applied to between an upper electrode 1 and a
lower electrode 2, and electricity is applied to the
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 insulating material 10 of e.g. SiO2. Further,
the phase-change recording layer 3 is crystallized in an
initial state. The initial crystallization in such a
case is carried out by heating the entire system of Fig.
4 to a crystallization temperature of the recording layer
(usually from about 100 to about 300°C). For formation
of an integrated circuit, the rise in temperature to such

an extent is commonly carried out.
Further, on the portion 4 (heater portion) which is
particularly thin in Fig. 4, heat generation due to Joule
heating is likely to occur by conducting between the
upper electrode 1 and the lower electrode 2, and
accordingly it functions as a localized heater. A
reversibly changeable portion 5 adjacent thereto is
locally heated and becomes amorphous via the temperature
history as illustrated by the curve a in Fig. 3, and
recrystallized via the temperature history as illustrated
in the curve b in Fig. 3.
Read-out is carried out in such a manner that a low
electric current to such an extent that heat generation
at the heater portion 4 is ignorable is applied, and a
potential difference generated between the upper and
lower electrodes is read. There is also a difference in
the electric capacity between the crystalline and
amorphous states, and thus the difference in the electric
capacity may also be detected.
In fact, a more integrated memory by using the
semiconductor integrated circuit formation technology has
been proposed (U.S. Patent 6,314,014). Its basic
structure is as illustrated in Fig. 4, and by
incorporating the phase-change recording material to be
used in the present invention into the phase-change
recording layer 3, the same functions can be realized.
As an energy source which causes a temperature

change as illustrated in Fig. 3, electron beam may also
be mentioned. As an example of a recording device
employing electron beam, a method of generating a phase
change on a phase-change recording material by locally
irradiating electron beam emitted by a field emitter, as
disclosed in U.S. Patent 5,557,596, may be mentioned.
Now, Examples wherein the phase-change recording
material of the present invention is applied to an
optical recording medium (the optical recording medium
will sometimes be referred to simply as a disc in
Examples) and Examples wherein the applicability of the
phase-change recording material of the present invention
to a rewritable information recording medium on which
recording is carried out by a change in the electric
resistance, will be explained. The following Examples
are merely one embodiment of the present invention, and
the present invention is by no means restricted to an
optical recording medium and application to a rewritable
information recording medium on which recording is
carried out by a change in the electric resistance,
unless they exceed the gist of the invention.
In Examples of the optical recording medium, the
reflectivity at a portion on which amorphous recording
marks are formed, is relatively low as compared with the
reflectivity in the crystalline state after the initial
crystallization (in a non-recorded state) and after
erasing. Further, the recording mark portions being in

an amorphous state and the erased/non-recorded state
being in a polycrystalline state in the recording layer
of the optical recording medium were confirmed by
observation of the recording layer by a transmission
electron microscope. Further, the crystalline state was
in a substantially single phase, and the crystal grain
sizes were approximately at most about several urn.
For measurement of the composition of the phase-
change recording material used for a recording layer of
an optical recording medium, acid dissolution ICP-AES
(Inductively Coupled Plasma-Atomic Emission Spectrometry)
was employed. By using JY 38 S manufactured by JOBIN
YVON as an analyzer, the recording layer was dissolved in
diluted HNO3 (diluted nitric acid) and quantitative
analysis was carried out by means of matrix matching
calibration method.
Measurement of the disc properties was carried out
by using DDU1000 manufactured by Pulstec Industrial Co.,
Ltd., by applying focus servo and tracking servo to
grooves with a retrieving power of less than 1 mW.
EXAMPLES 1 and 2 and COMPARATIVE EXAMPLES 1 to 4
On a disc-shape polycarbonate substrate with a
diameter of 120 mm and a thickness of 1.2 mm, having
guide grooves with a groove width of approximately 0.5
µm, a groove depth of approximately 40 nm and a groove
pitch of 1.6 µm, a (ZnS)8o (SiO2)20 layer (80 nm) , a Ge-Sb-
Sn recording layer (15 nm) , a (ZnS)80(SiO2)20 layer (30

nm) and a Al99.5Ta0.5 alloy reflective layer (200 nm) were
formed by a sputtering method to prepare a phase-change
optical disc.
The values x and y when the recording layer
composition is represented as (Sb1-xSnx)1-yGey are shown in
Table 1.



Each of these discs was subjected to initial
crystallization as follows. Namely, a laser light having
a wavelength of 810 nm and a power of 1,600 mW and having
a shape with a width of about 1 µm and a length of about
150 una was irradiated on the disc rotating at 12 m/s so
that the major axis was perpendicular to the above guide
grooves, and the laser light was continuously moved in a
radius direction with a feed of 60 µm per rotation to
carry out initialization.
Then, EFM random signals were recorded at a linear
velocity of 28.8 m/s by using a disc evaluation apparatus
(DDU1000) having a laser wavelength of 780 nm and a
pickup of NA0.5 as follows. Marks with lengths of from
3T to 11T (T is a reference clock period and is 9.6 nsec)
contained in the EFM signals were formed by irradiating a
series of pulses of the following laser pulses connected
in sequence.
3T: Pulse with a power Pw and a length 2T, pulse
with a power Pb and a length 0.6T.
4T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 0.95T, pulse with a power Pw
and a length 1.05T, pulse with a power Pb and a length
0.3T.
5T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1.3 5T, pulse with a power Pw
and a length 1.45T, pulse with a power Pb and a length
0.3T.

6T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 0.9T,
pulse with a power Pw and a length 1T, pulse with a power
Pb and a length 0.3T.
7T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1.35T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 1T,
pulse with a power Pw and a length 1.4T, pulse with a
power Pb and a length 0.3T.
8T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 1T,
pulse with a power Pw and a length 1T, pulse with a power
Pb and a length 0.9T, pulse with a power Pw and a length
1T, pulse with a power Pb and a length 0.3T.
9T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1.3 5T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 1T,
pulse with a power Pw and a length 1T, pulse with a power
Pb and a length 1T, pulse with a power Pw and a length
1.4T, pulse with a power Pb and a length 0.3T.
10T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 1T,
pulse with a power Pw and a length 1T, pulse with a power
Pb and a length 1T, pulse with a power Pw and a length

1T, pulse with a power Pb and a length 0.9T, pulse with a
power Pw and a length 1T, pulse with a power Pb and a
length 0.3T.
11T: Pulse with a power Pw and a length 1T, pulse
with a power Pb and a length 1.35T, pulse with a power Pw
and a length 1T, pulse with a power Pb and a length 1T,
pulse with a power Pw and a length 1T, pulse with a power
Pb and a length 1T, pulse with a power Pw and a length
1T, pulse with a power Pb and a length 1T, pulse with a
power Pw and a length 1.4T, pulse with a power Pb and a
length 0.3T.
An erasing power Pe was irradiated between pulses
When each of the above laser pulses of 3T to 11T is
represented by the notation system as shown in Fig. 2,
αi and βi are as shown in Table 2. In the section αiT,
a write power Pw is irradiated, and in the section βiT, a
bias power Pb=0.8 mW is irradiated.


for mark formation. Further, the irradiation position of
the pulses for 3T mark formation was shifted toward ahead
of the original position of the 3T mark in the EFM random
signal by 0.3 5T (the irradiation was carried out at
earlier timing than the original 3T mark in the EFM
signal), and the irradiation position of the pulses for
4T mark formation was shifted toward ahead of the
original timing of the 4T mark in the EFM random signal
by 0.1T. By doing this, the marks to be formed are
closer to the original random signals. Further, during
recording, the Pe/Pw ratio was fixed to 0.31 unless
otherwise specified.
The recorded part was retrieved at a linear velocity
of 1.2 m/s to evaluate the properties of the recording
signals.
The results of evaluation of the discs of Examples 1
and 2 are shown in Figs. 5 and 6, respectively. Items
evaluated are 3T mark jitter and 3T space jitter of
retrieving signals when EFM random signals were recorded
by overwriting ten times while changing Pw in a range of
from 22 to 28 mW (the results are shown in Fig. 5(a) and
Fig. 6(a)), the reflectivity at a crystalline part (the
results are shown in Fig. 5(b) and Fig. 6(b)), the signal
amplitude defined by "(signal level reflectivity of
crystallized part)-(signal level reflectivity of 11T mark
part)" (the results are shown in Fig. 5(c) and Fig.
6(c)), and 3T mark jitter and 3T space jitter of

retrieving signals when repetitive direct overwriting was
carried out by fixing the write power (the results are
shown in Fig. 5(d) and Fig. 6(d)). The write power at
the time of repetitive direct overwriting was 25 mW in
Example 1 and 24 mW in Example 2.
It is found from the results shown in Figs. 5(d) and
6(d) that there is a recording condition under which the
jitter value is adequately smaller than 40 nsec by 1,000
times or less overwriting for each of the discs of
Examples 1 and 2. Accordingly, it is found that each of
the discs of Examples 1 and 2 is adequately practicable
as a rewritable information recording medium from this
viewpoint. In the vicinity of the recording layer
composition of each of the discs of Examples 1 and 2,
when the recording layer composition is represented as
(Sb1-xSnx)1-yGey, the repetitive overwriting properties
tend to be excellent when the value x is smaller, as
shown by comparison of Figs. 6(d) and Fig. 5(d).
Further, as shown from the comparison between Fig. 5(c)
and Fig. 6(c),. the signal amplitude tends to be excellent
when the value x is higher.
Further, when a Sb-Sn-Ge-M1 composition was employed
as the phase-change recording material, and Bi, Ta, W,
Nb, N, O, C, Se, Al, Si, Zn or V was added in an amount
of from about 1 to about 10 atomic% as the element Ml
( (Sb1-xSnx)1-y-zGeYM1z wherein x=0.25, y=0.18 and 0.01≤z≤
0.1 or x=0.32, y=0.18 and 0.01≤z≤0.1) in each of the

discs of Examples 1 and 2, the same rewritable recording
properties as those of the discs of Examples 1 and 2 were
obtained.
Further, when each of these discs was kept at 105°C
for 3 hours and then the above recorded part was
retrieved, whereupon no deterioration of the jitter of
the recorded signals or signal amplitude was shown at
all.
As shown in Table 1, with respect to each of the
discs of Comparative Example 1, no uniform increase in
the reflectivity by the initial crystallization operation
was shown, and there were always several parts on which
the reflectivity was locally low in a track corresponding
to one rotation of the disc. Further, as shown in Table
1, no uniform initial crystallization could be carried
out on each of the discs of Comparative Example 1 even by
changing the crystallization speed by controlling the Ge
amount.
Further, of each of the discs of Comparative Example
1, the noise level was higher than that of the disc of
Example 1 by 13 dB when the noise level was measured at
500 kHz by means of a spectrum analyzer (manufactured by
ADVANTEST CORPORATION, TR4171) at a linear velocity of
1.2 m/s with a resolution band width of 30 kHz with a
video band width of 30 Hz.
With respect to each of the discs of Comparative
Example 1, initial crystallization was attempted also by

irradiating DC laser light of from 6 to 12 W at a linear
velocity of from 1.2 to 4.8 m/s by using a disc
evaluation apparatus, however, no uniform increase in the
reflectivity was shown, and the initial crystallization
could not be favorably carried out. Recording of
amorphous marks was attempted on each of the above discs
on which no uniform initial crystallization could be
carried out, the jitter was at least 40 nsec at the first
recording. This means that the crystalline state and the
amorphous state can not be utilized as a non-recorded
state and a recorded state, respectively, in each of the
discs of Comparative Example 1.
From these results, it is found that when the phase-
change recording material contains no Sn, use as an
information recording medium utilizing the crystalline
state as a non-recorded state and the amorphous state as
a recorded state tends to be difficult.
Further, of the disc of Comparative Example 3 also,
no uniform increase in the reflectivity by the
initialization operation was shown. This is considered
to be because the phase change speed from the amorphous
phase to the crystalline phase is too slow as the Ge
content is high (y=0.35). With respect to the disc of
Comparative Example 3, initial crystallization was
attempted also by irradiating DC laser light of from 6 to
12 mW at a linear velocity of from 1.2 to 4.8 m/s (at
this linear velocity range, the disc is very close to a

stationary state) by using a disc evaluation apparatus,
however, no uniform increase in the reflectivity was
shown, and the initial crystallization could not
favorably be carried out. From these results, it is
found that when the Ge content of the phase-change
recording material is higher than 0.3, use as a
rewritable information recording medium tends to be
difficult.
With respect to the disc of Comparative Example 2,
although uniform reflectivity was obtained after the
initial crystallization, no formation of amorphous marks
could be performed. Further, formation of amorphous
marks was attempted by changing the linear velocity,
formation of amorphous marks could not be carried out at
least at a linear velocity of at most 38.4 m/s. This is
considered to be because the crystallization speed was
too high as the Ge content was low (y=0.09), and
accordingly the melted portion was recrystallized. From
these results, it was found that when the Ge content of
the phase-change recording material is lower than 0.1,
use as a rewritable information recording medium is
substantially difficult. A linear velocity of at least
38.4 m/s could not be achieved due to restriction in view
of apparatus in general, and thus amorphous mark
formation is substantially impossible. Even if
amorphization is achieved under an extremely special
condition, such an amorphous mark should be easily

recrystallized soon at room temperature. And thus, it is
not suitable for storage media.
With respect to each of the discs of Comparative
Example 4, although uniform reflectivity was obtained
after the initial crystallization, no 3T space jitter of
at most 40 nsec could be obtained when
recording/retrieving was carried out under the same
conditions as in Examples 1 and 2. Further, discs of
Comparative Example 4 by changing the Ge content thereby
to change the crystallization speed were prepared as
shown in Table 1, and the recording properties of these
discs were examined. As a result, it was found that with
respect to each disc of Comparative Example 4 wherein x
is fixed to 0.59, it is difficult to satisfy both
formation of amorphous marks and crystallization of
amorphous marks even by changing the Ge content, and
further, the signal amplitude is at a level of 0.05 and
is small at least with a composition which provide a
crystallization speed required for crystallization of the
marks. Namely, if the Sn content is too high, use as a
rewritable medium is substantially difficult.
COMPARATIVE EXAMPLE 5
Each of the discs of Comparative Example 5 is a disc
of Example 1 except that a phase-change recording
material wherein Ge is replaced with In was used. Of
each of the discs of Comparative Example 5, the values of
x and y when the recording layer composition is

represented as (Sb1-xSnx) 1-yIny, whether initial
crystallization was possible or not and recording
properties are shown in Table 1.
In the phase-change recording material used for each
of the discs of Comparative Example 5, the Sn amount was
within a range of from 0.01 to 0.5 and the In amount is
within a range in the vicinity of from 0.1 to 0.3 (within
the range of Ge content in the present invention). With
respect to each of these discs, although uniform
reflectivity was obtained after the initial
crystallization, formation of amorphous marks could not
be performed at least at a linear velocity of at most
38.4 m/s. Formation of amorphous marks could not be
performed even by changing the In content.
From these results, it is found that Ge is important
for formation of amorphous marks, and use as an
information recording medium is substantially difficult
when Ge is replaced with In. With a composition
(Sb0.73Sn0.27) 0.56In0.44 wherein the In amount was further
increased, the recording material was changed to a state
which was considered to be another crystalline state with
a low reflectivity, at the time of initial
crystallization.
Accordingly, a favorable optical recording medium
can be obtained with a composition (Sb1-xSnx) 1-yGey wherein
0.01≤x≤0.5 and 0.1≤y≤0.3.
EXAMPLE 3

The following experiment was carried out so as to
examine whether the phase-change recording material of
the present invention can be used as a recording material
for an information recording medium on which recording is
carried out by the change in the electric resistance.
Namely, on a polycarbonate substrate with a diameter
of 120 mm, a Ge0.18Sb0.66Sn0.16 ((Sb1-xSnx)1-yGey wherein x=0.2
and y=0.18) amorphous film in a film thickness of 50 nm
was formed by sputtering. After the resistivity of this
amorphous film was measured, the film was crystallized
and the resistivity of the film after recrystallization
was measured again. The crystallization was chaired out
under the same conditions as for the discs of Examples,
and for measurement of the resistivity, a resistivity
meter Loresta MP (MCP-T350) manufactured by DIA
INSTRUMENTS was used. The resistivities before and after
the crystallization were 1.03x10-1 Ωcm and 0.80x10-4 Ωcm,
respectively, and it was found that there is a change in
the resistivity by almost three orders of magnitude as
between the amorphous state and the crystalline state.
In the same method as mentioned above, on a
polycarbonate substrate, a Ge0.17Sb0.75Sn0.08 ((Sb1-xSnx)1-YGey
wherein x=0.1 and y=0.17) amorphous film was formed by
sputtering, and the resistivities of the film in an
amorphous state and in a crystalline state were measured.
As a result, the resistivity in an amorphous state was
5.96x10-1 Ωcm and the resistivity in a crystalline state

was 0.8x10-4 Ωcm, and it was found that there is a change
in the resistivity of almost three orders of magnitude as
between the amorphous state and the crystalline state.
Further, in the same method as mentioned above, on a
polycarbonate substrate, a Ge0.16Sb0.84 ((Sb1-xSnx)1-yGeY
wherein x=0 and y=0.16) amorphous film was formed by
sputtering, and the resistivities of the film in an
amorphous state and in a crystalline state were measured.
As a result, the resistivity in an amorphous state was
1.51x10-0 Ωcm and the resistivity in a crystalline state
was 0.7x10-4 Qcm, and it was found that there is a change
in the resistivity of almost four orders of magnitude as
between the amorphous state and the crystalline state.
From the results of measurement of the resistivities
of the films formed from the three phase-change recording
materials, it is found that the change in the resistivity
as between the amorphous state and the crystalline state
can be controlled by changing the Sn content in the
phase-change recording material. Namely, it is found
that the change in the resistivity as between the
amorphous state and the crystalline state becomes
significant when the Sn content is decreased.
In a case where the phase-change recording material
of the present invention is used for a non-volatile
memory utilizing the change in the resistivity, a
composition containing no Sn (0≤x in the composition
(Sb1-xSnx)1-y-w-zGeyTewM1z) may be employed only to make the

change in resistivity significant. However, usually, it
is required to control the change in the resistivity to
be within a predetermined range from the viewpoint of
design of an electronic circuit into which the non-
volatile memory is incorporated. Accordingly, by using a
phase-change recording material containing Sn, a high
performance non-volatile memory wherein the change in the
resistivity is controlled to be within a predetermined
range can be obtained.
Further, a favorable change in the resistivity as
between the amorphous state and the crystalline state can
be obtained also by adding an element such as Te or the
element Ml to the above GeSbSn ternary composition. In
fact, on a polycarbonate substrate, a
Ge0.08In0.11Sb0.65Sn0.11Te0.05 ((Sb1-xSnx)1-y-w-zGeYTewInz wherein
x=0.14, y=0.08, w=0.05 and z=0.11) amorphous film was
formed by sputtering, and the resistivities of the film
in an amorphous state and in a crystalline state were
measured. As a result, the resistivity in an amorphous
state was 8.73X101 Ωcm and the resistivity in a
crystalline state was 1.12x10-4 Ωcm, and it was found
that there is a change in the resistivity of almost three
orders of magnitude as between the amorphous state and
the crystalline state.
From the above experiment, it is found that the
phase-change recording material to be used in the present
invention can be applied to a rewritable information

recording medium on which recording is carried out by the
change in the electric resistance, since the difference
in the resistivity due to a phase change as between the
amorphous state and the crystalline state can be
controlled to be within a predetermined range while the
difference is made to be significant.
EXAMPLES 4 to 11 and COMPARATIVE EXAMPLE 6
For measurement of the composition of a phase-change
recording material used for a recording layer of an
optical recording medium, acid dissolution ICP-AES
(Inductively Coupled Plasma-Atomic Emission Spectrometry)
and a X-ray fluorescent analyzer were employed.
Regarding the acid dissolution ICP-AES, using JY 38 S
manufactured by JOBIN YVON as an analyzer, the recording
layer was dissolved in diluted HNO3 and quantitative
evaluation was carried out by means of a matrix matching
calibration method. As the X-ray fluorescent analyzer,
RIX3001 manufactured by Rigaku Denki Kogyo K.K. was used.
Measurement of the disc properties was carried out
by using DDU1000 manufactured by PULSTEC INDUSTRIAL Co.,
Ltd., by applying focus servo and tracking servo to
grooves with a retrieving power of 0.8 mW.
On a disc-shape polycarbonate substrate with a
diameter of 120 mm and a thickness of 1.2 mm, having
guide grooves with a groove width of approximately 0.5
urn, a groove depth of approximately 40 nm and a groove
pitch of 1.6 µm, a (ZnS)80(SiO2)20 layer, a Ge-Sb-Sn-M1

recording layer, a (ZnS)80(SiO2)20 layer and a Al99.5Ta0.5
alloy reflective layer were formed by a sputtering
method, whereby 8 types of phase-change optical discs
were prepared (Comparative Example 6 and Examples 4 to
10) . Similarly, a phase-change optical disc comprising a
(ZnS)80(SiO2)20 layer, a Ge-Sb-Sn-M recording layer, a
(ZnS)80(SiO2)20 layer, a germanium nitride layer and a Ag
reflective layer was also prepared. (Example 11). The
germanium nitride layer is an interfacial layer to
prevent mutual diffusion of elements between the
(ZnS)80(SiO2)20 layer and the Ag layer.
Of each disc, the film thickness and the values x, y
and z when the recording layer composition is represented
as (Sb1-xSnx)1-y-zGeyM1z are shown in Table 3. As evident
from Table 3, film thicknesses of layers constituting the
discs are slightly different. This is to make the
reflectivity at the crystallized part and the signal
amplitude be at the same level. The reflectivities at
the crystallized part of all the discs except for
Comparative Example 6 were within a range of from 19 to
21%.



Each of these discs was subjected to the initial
crystallization as follows. Namely, laser light having a
wavelength of 810 nm and a power of 1,600 mW and having a
shape with a width of about 1 urn and a length of about
150 urn was irradiated on the disc rotating at 12 m/s so
that the major axis was perpendicular to the above guide
grooves, and the laser light was continuously moved in a
radius direction with a feed of 60 urn per one rotation to
carry out initialization. As this initialization
conditions were not optimum depending upon the disc, DC
laser light of 10 mW was irradiated once at a linear
velocity of 4 m/s by using a disc evaluation apparatus
having a laser wavelength of 780 nm and a pickup of
NA0.5.
The disc of Comparative Example 6 could not function
as a recording medium as the change in the reflectivity
by the above initialization operation was small.
With respect to each of the discs of Example 4 and
Examples 5 to 8, the noise at the initialized part was
measured under the following conditions. Namely, the
noise level at 50 0 kHz was measured by using a spectrum
analyzer (TR4171 manufactured by ADVANTEST CORPORATION)
at a linear velocity of 1.2 m/s with a evaluation band
width of 30 kHz with a video band width of 30 Hz. The
results are shown in Table 3 . The noise of each of the
discs of Examples 5 to 8 is small as compared with the
disc of Example 4. With the GeSbSn type material, the

noise tends to be significant when the Sn content (the
value x) is low. Accordingly, the noise of the disc of
Example 4 wherein x=0.2 is slightly strong, however, in
Examples 5 to 8 wherein the value of x is equal to or
less than that of Example 4, the noise is apparently
small, and it is found that the effect of reducing noise
by addition of In, Pd, Pt or Ag is high.
Then, EFM random signals were recorded on each of
the discs of Examples 4, 5, 9, 10 and 11 (In added or not
added system) at a linear velocity of 28.8 m/s by using a
disc evaluation apparatus (DDU1000) having a layer
wavelength of 780 nm and a pickup of NA0.5 as described
hereinafter. Marks with lengths of from 3T to 11T (T is
a reference clock period and is 9.6 nsec) contained in
the EFM signals were formed by irradiating a series of
pulses of the following laser pulses connected in
sequence.
3T: Pulse with a power Pw and a length 2T, pulse
with a power 0.8 mW and a length 0.6T.
4T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 0.95T, pulse with a
power Pw and a length 1.05T, pulse with a power 0.8 mW
and a length 0.3T.
5T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.35T, pulse with a
power Pw and a length 1.45T, pulse with a power 0.8 mW
and a length 0.3T.

6T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 0.9T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 0.3T.
7T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.35T, pulse with a
power Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1.4T, pulse
with a power 0.8 mW and a length 0.3T.
8T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 0.9T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 0.3T.
9T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.35T, pulse with a
power Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1.4T, pulse with a power 0.8 mW and a
length 0.3T.
10T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a

length 1T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 0.9T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 0.3T.
11T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.35T, pulse with a
power Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1.4T, pulse
with a power 0.8 mW and a length 0.3T.
An erasing power Pe was irradiated between the above
pulses for mark formation. Further, the irradiation
position of the pulses for 3T mark formation was shifted
toward ahead of the original position of the 3T mark in
the EFM random signals by 0.35T (the irradiation was
carried out at earlier timing than the original 3T mark
in the EFM signal), and the irradiation position of the
pulses for 4T mark formation was shifted toward ahead of
the original timing of the 4T mark in the EFM random
signals by 0.1T. By doing this, marks to be formed are
closer to the original EFM random signals. Further, the
Pe/Pw ratio was fixed at 0.31 during recording.
On each of the discs, the above EFM random signals
were recorded by overwriting ten times by using such a

write power that the jitter with a length between marks
corresponding to a length 3T (hereinafter referred to as
3T space jitter") becomes almost minimum after recording
by overwriting ten times with changing the write power Pw
(hereinafter sometimes referred to as "recording before
aging"), and the 3T space jitter was measured. The value
of 3T space jitter and the value of the write power are
shown in Table 3. In Table 3, the values of the 3T space
jitter and the write power are shown in the column
"recording before aging".
Then, each of the discs of Examples 5, 9, 10 and 11
was held in an environment of 105°C for 3 hours (aging
test) . Then, the recorded part was retrieved
(hereinafter sometimes be referred to as "after aging"),
and the 3T space jitter was measured. The values of the
3T space jitter is shown in Table 3. In Table 3, the
value of the 3T space jitter is shown in the column
"after aging".
Further, EFM random signals were recorded once on
the recorded part before aging while changing the write
power after the aging test (hereinafter sometimes be
referred to as "recording after aging"), and the 3T space
jitter was measured. The value of the smallest 3T space
jitter and the write power are shown in Table 3. In
Table 3, the values of the 3T space jitter and the write
power are shown in the column "recording after aging".
This aging test was carried out under very severe

conditions as compared with a conventional environmental
test. Thus, if the properties after this aging test
deteriorate, it can be said that the performances of the
disc in practical use are adequately secured.
Retrieving of the recording marks was carried out at
a linear velocity of 1.2 m/s.
Although the noise of the disc of Example 4 is
somewhat significant, the 3T space jitter by recording
before aging was at most 40 nsec, and the disc was
adequately practicable.
The jitter properties (the value of 3T space jitter)
of the disc of Example 9 by recording before aging are
better than those of the disc of Example 4 since the Sn
content is high (the value x is high). However, the
value of 3T space jitter by recording after aging is 48.8
nsec and is slightly high. On the other hand, with
respect to each of the discs of Example 5, 10 and 11
wherein In was added to a composition with a small Sn (a
small x), it is found that the value of 3T space jitter
by recording after aging is improved.
As shown from the comparison between Example 10 and
Example 11 using substantially same recording layer
compositions, the recording properties after aging become
better by employing Ag as the reflective layer.
Further, no deterioration of the jitter at the
recorded part before aging due to the aging test was
shown on any disc, and it is found that the amorphous

marks are adequately stable.
EXAMPLE 12 and COMPARATIVE EXAMPLE 7
Disks were prepared in the same manner as mentioned
above (Examples 4 to 11 and Comparative Example 6) except
that Te was used as the element to be added, and the Te
content was 5 atomic% (Example 12) or 11 atomic%
(Comparative Example 7), and each of the discs was
evaluated. Of each of the discs, the film thickness and
the values of x, y and w when the recording layer
composition is represented as (Sb1-xSnx)1-y-wGeyTew are
shown in Table 4.



With respect to the disc of Example 12, the
recording properties after aging at the same level as the
above Examples 5 and 10 were obtained, and it is found
that the recording properties after aging are favorable
by addition of Te. The reflectivity at the crystallized
part of the disc of Example 12 was 16.6% and showed a
value slightly lower than those of discs of other
Examples.
The disc of Comparative Example 7 was not a
practicable phase-change optical disc as the reflectivity
in a crystalline state was so low as 12.1% and the signal
amplitude was low.
Further, no deterioration of the jitter at the
recorded part before aging due to the aging test was
shown on the disc of Example 12 also, and it is found
that the amorphous marks are adequately stable.
EXAMPLES 13 to 17
For measurement of the composition of a phase-change
recording material used for a recording layer of an
optical recording medium, acid dissolution ICP-AES
(Inductively Coupled Plasma-Atomic Emission Spectrometry)
and a X-ray fluorescent analyzer were employed.
Regarding the acid dissolution ICP-AES, using JY 38 S
manufactured by JOBIN YVON as an analyzer, the recording
layer was dissolved in diluted HNO3 and quantitative
evaluation was carried out by means of a matrix matching
calibration method. As the X-ray fluorescent analyzer,

RIX3001 manufactured by Rigaku Denki Kogyo K.K. was used.
Measurement of the disc properties was carried out
by using DDU1000 manufactured by PULSTEC INDUSTRIAL Co.,
Ltd., by applying focus servo and tracking servo to
grooves with a retrieving power of 0.8 mW.
On a disc-shape polycarbonate substrate with a
diameter of 12 0 mm and a thickness of 1.2 mm, having
guide grooves with a groove width of approximately 0.5
µm, a groove depth of approximately 40 nm and a groove
pitch of 1.6 µm, a (ZnS)80(SiO2)20 layer, a Ge-Sb-Sn-M1
recording layer, a (ZnS)80(SiO2)20 layer and a Al99.5Ta0.5
alloy reflective layer were formed by a sputtering
method, whereby two types of phase-change optical discs
wherein Ml was Tb and Gd, respectively (Examples 13 and
14) were prepared. Namely, Tb was used as the element Ml
in Example 13, and Gd was used as the element Ml in
Example 14.
Then, the same phase-change optical disc of Example
4 except that the reflective layer was a Ag reflective
layer, and a germanium nitride layer was inserted between
the reflective layer and the protective layer was
prepared (Example 15). Similarly, the same phase-change
optical discs of Examples 13 and 14 except that the
reflective layer was a Ag reflective layer, and a
germanium nitride layer was inserted between the
reflective layer and the protective layer, were prepared
(Examples 16 and 17). The reason why the germanium

nitride layer was inserted between the reflective layer
and the protective layer in the case of using the Ag
reflective layer is to prevent mutual diffusion of
elements between the (ZnS)80(SiO2)20 protective layer and
the Ag reflective layer.
The element Ml, the layer structure, the film
thickness and the values of x, y and z when the recording
layer composition is represented as (Sb1-xSnx)1-y-zGeyM1z,
of each of the discs of Examples 4, 13 and 14 are shown
in Table 5.



Each of the discs was subjected to initial
crystallization as follows. Namely, laser light having a
wavelength of 810 nm and a power of 1,600 mW and having a
shape with a width of about 1 urn and a length of about
150 µm was irradiated on the disc rotating at 12 m/s so
that the major axis was perpendicular to the above guide
grooves, and the laser light was continuously moved in a
radius direction with a feed of 60 µm per one rotation.
Then, DC laser light of 10 mW was irradiated once at a
linear velocity of 4 m/s by using a disc evaluation
apparatus having a laser wavelength of 780 nm and a
pickup of NA0.5.
The reflectivity at the crystallized part of each of
the discs of Examples 13 and 14 after initial
crystallization was within a range of from 19 to 21%.
Further, the reflectivity at the crystallized part of the
disc of Example 4 after initial crystallization was also
within a range of from 19 to 21% (see Example 4).
Each of the discs of Examples 13 and 14 was
subjected to noise measurement in the same manner as the
discs of Example 4 and Examples 5 to 8. The results are
shown in Table 5. The noise of each of the discs of
Examples 13 and 14 was small as compared with the disc of
Example 4, and it is found that the effect of reducing
the noise is high by addition of a lanthanoid such as Tb
or Gd i.e. a rare earth element.
Then, repetitive overwriting durability of each of

the discs of Examples 15 to 17 was measured by using a
disc evaluation apparatus having a laser wavelength of
780 nm and a pickup of NA0.5. EFM random signals were
recorded at a linear velocity of 28.8 m/s as mentioned
hereinafter. Marks with lengths of from 3T to 11T (T is
a reference clock period and is 9.6 nsec) contained in
EFM signals were formed by irradiating a series of pulses
of the following laser pulses connected in sequence.
3T: Pulse with a power Pw and a length 2T, pulse
with a power 0.8 mW and a length 0.6T.
4T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 0.95T, pulse with a
power Pw and a length 1.15T, pulse with a power 0.8 mW
and a length 0.3T.
5T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1.4T, pulse with a power
Pw and a length 1.55T, pulse with a power 0.8 mW and a
length 0.3T.
6T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 0.9T, pulse with a power Pw and a length 1.1T,
pulse with a power 0.8 mW and a length 0.3T.
7T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1.4T, Pulse with a power
Pw and a length IT, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1.5T, pulse

with a power 0.8 mW and a length 0.3T.
8T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 0.9T, pulse with a power
Pw and a length 1.1T, pulse with a power 0.8 mW and a
length 0.3T.
9T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1.4T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1.5T, pulse with a power 0.8 mW and a
length 0.3T.
10T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 0.9T, pulse with a power Pw and a length 1.1T,
pulse with a power 0.8 mW and a length 0.3T.
11T: Pulse with a power Pw and a length 1.1T, pulse
with a power 0.8 mW and a length 1.4T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1T, pulse

with a power 0.8 mW and a length 1T, pulse with a power
Pw and a length 1T, pulse with a power 0.8 mW and a
length 1T, pulse with a power Pw and a length 1.5T, pulse
with a power 0.8 mW and a length 0.3T.
An erasing power Pe was irradiated between the above
pulses for mark formation. The irradiation position of
the pulses for 3T mark formation was shifted toward ahead
of the original position of the 3T mark in the EFM random
signal by 0.3T (the irradiation was carried out at
earlier timing than the original 3T mark in the EFM
signal), and the irradiation position of pulses for 4T
mark formation was shifted toward ahead of the original
timing of the 4T mark in the EFM random signal by 0.1T.
By doing this, the marks to be formed are closer to the
original EFM random signals. Further, Pe/Pw = 8 mW/26 mW
at the time of recording.
The relation between the number of repetitive
overwriting and the 3T space jitter of each of the discs
of Examples 15 to 17 is shown in Fig. 7. Retrieving was
carried out at 1.2 m/s. Each of the discs of Examples 15
to 17 provides favorable jitter properties until the
number of repetitive overwriting is 1,000 times, and it
is found that they are discs having no problem in view of
practical use. However, with respect to the disc of
Example 15, as the number of repetitive overwriting was
further increased, the 3T space jitter became 46.2 nsec
at the time of overwriting for 2,000 times. It is

considered that since no lanthanoid element i.e. rare
earth element was contained in the phase-change recording
material of the disc of Example 15, the crystallization
speed decreased due to the repetitive overwriting, and
erasing of the marks was incomplete, whereby the jitter
increased. On the other hand, each of the discs of
Examples 16 and 17 wherein a lanthanoid (Tb, Gd) was
incorporated into the phase-change recording material
showed a favorable jitter value even after overwriting
for 2,000 times. This is considered to be because
decrease of the crystallization speed due to increase in
the number of the repetitive overwriting is reduced by
addition of a lanthanoid.
REFERENCE EXAMPLE 1
The following experiment was carried out to examine
whether the recording layer composition used for the disc
of Example 15 is suitable for formation of crystalline
marks, i.e. whether it is possible to record crystalline
marks in the amorphous film after sputtering of the
recording layer.
The disc used for the experiment was prepared in the
same manner as in Example 15 except that the film
thickness of the (ZnS)80(SiO2)20 layer adjacent to the
substrate was 150 nm. This is because the reflectivity
of the amorphous film in a state where sputtering of the
recording layer was carried out (non-recorded state in a
case of forming crystalline marks) of the disc of Example

15 as it was, was low, and no focus servo could be
applied, and thus the film thickness of the
(ZnS)80(SiO2)20 layer was made thicker than that of
Example 15 to increase the reflectivity of the amorphous
film and thereby to apply focus servo. As a result of
making the film thickness of the (ZnS)80(SiO2)20 layer
adjacent to the substrate 150 nm, the reflectivity of the
amorphous film was 7%, whereby focus servo and tracking
servo could be applied.
DC laser light of from 5 to 20 mW was irradiated
once at a linear velocity of 28.8 m/s by using a disc
evaluation apparatus (DDU1000 manufactured by Pulstec
Industrial Co., Ltd.), however, no crystallization took
place at all. Taking that the erasing power Pe (the
erasing power is a power to erase the amorphous marks
i.e. a crystallization power) was 8 mW in Example 15 into
consideration, the above DC laser light of from 5 to 20
mW provides an adequately wide range of laser power so as
to confirm whether the crystalline marks can be formed or
not. As no crystalline phase marks could be formed even
with such a wide range of laser power, it can be said
that recording of crystalline marks on the amorphous film
of the disc is very difficult. Namely, it is considered
that substantially no crystalline nuclei are present in
the amorphous recording layer of the disc immediately
after film formation, or even if they are present, they
are not so dense as to form crystalline marks.

Further, when the above DC laser light was
irradiated several times, crystallization took place and
an increase in the reflectivity was observed. However,
the increase in the reflectivity was not uniform, and it
was observed that a part which was likely to be
crystallized and a part which was hardly crystallized
were mingled. This indicates that crystalline nuclei are
not originally present in such a number that crystalline
marks having a high signal quality can be formed, in the
recording layer composition of Example 15. Accordingly,
even by carrying out a pretreatment such as irradiation
with laser on the disc, the number of the crystalline
nuclei in the recording layer in an amorphous state is
originally small, and thus it is difficult to form
crystalline marks having recording properties which can
be used practically.
Accordingly, it is found that the density of the
crystalline nuclei is very low in the phase-change
recording material of the present invention in an
amorphous state particularly in an amorphous state
immediately after film formation by sputtering.
Accordingly, it is found that on an information recording
medium employing this phase-change recording material, it
is very difficult to apply a recording method utilizing
the crystalline state as recording marks.
EXAMPLES 18 and 19 and COMPARATIVE EXAMPLES 8 and 9
For measurement of the composition of a phase-change

recording material used for a recording layer of an
optical recording medium, acid dissolution ICP-AES
(Inductively Coupled Plasma-Atomic Emission Spectrometry)
and a X-ray fluorescent analyzer were employed.
Regarding the acid dissolution ICP-AES, using JY 38 S
manufactured by JOBIN YVON as an analyzer, the recording
layer was dissolved in diluted HNO3 and quantitative
evaluation was carried out by means of a matrix matching
calibration method. As the X-ray fluorescent analyzer,
RIX3001 manufactured by Rigaku Denki Kogyo K.K. was used.
Measurement of the disc properties was carried out
by using DDU1000 manufactured by PULSTEC INDUSTRIAL Co.,
Ltd. by applying focus servo and tracking servo to
grooves with a retrieving power of 0.8 mW.
On a disc-shape polycarbonate substrate with a
diameter of 120 mm and a thickness of 1.2 mm, having
guide grooves with a groove width, of approximately 0.5
µm, a groove depth of approximately 40 nm and a groove
pitch of 1.6 urn, a (ZnS)80(SiO2)20 layer, a Ge-Sb-Sn-M1-T
recording layer, a (ZnS)80(SiO2)20 layer, a Ta layer and a
Ag reflective layer were formed by a sputtering method,
whereby phase-change optical discs wherein M1 was In were
prepared (Examples 18 and 19 and Comparative Example 8).
The reason why the Ta layer was inserted between the
reflective layer and the protective layer in the case of
using the Ag reflective layer is to prevent mutual
diffusion of elements between the (ZnS)80(SiO2)20

protective layer and the Ag reflective layer. In
Comparative Example 9, no In was used as the element Ml,
and a Ag99.5Ta0.5 reflective layer was formed instead of
the Ta layer and the Ag reflective layer.
The element Ml, the layer structure, the film
thickness and the values of x, y, z and w when the
recording layer composition is represented as
(Sb1-xSnx)1-y-zGeyM1zTaw, of each disc are shown in Table 6.



Each of the discs was subjected to initial
crystallization as follows. Namely, laser light having a
wavelength of 810 nm and a power of 1,600 mW and having a
shape with a width of about 1 urn and a length of about
150 µm was irradiated on the disc rotating at 12 m/s so
that the major axis was perpendicular to the above guide
grooves, and the laser light was continuously moved in a
radius direction with a feed of 60 µm per one rotation.
Then, of each of the discs of Examples 18, 19 and
Comparative Examples 8 and 9, recording signal properties
after overwriting for 10 times were measured by using a
disc evaluation apparatus having a laser wavelength of
780 nm and a pickup of NA0.5.
On the disc of Example 18, recording was carried out
under the following condition. EFM random signals were
recorded at a linear velocity of 28.8 m/s as mentioned
hereinafter. Marks with lengths of from 3T to 11T (T is
a reference clock period and is 9.6 nsec) contained in
EFM signals were formed by irradiating a series of pulses
of the following laser pulses connected in sequence.
3T: Pulse with a power Pw and a length 1.4T, pulse
with a power 0.8 mW and a length 0.85T.
4T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 0.4T.
5T: Pulse with a power Pw and a length 1T, pulse

with a power 0.8 mW and a length 1.45T, pulse with a
power Pw and a length 1.4T, pulse with a power 0.8 mW and
a length 0.4T.
6T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 0.4T.
7T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.45T, pulse with a power Pw and a length 1.4T,
pulse with a power 0.8 mW and a length 0.4T.
8T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 1.1T, pulse with a
power Pw and a length 0.9T, pulse with a power 0.8 mW and
a length 0.4T.
9T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 1.45T, pulse with
a power Pw and a length 1.4T, pulse with a power 0.8 mW
and a length 0.4T.

10T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 1.1T, pulse with a
power Pw and a length 0.9T, pulse with a power 0.8 mW and
a length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 0.4T.
11T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.1T, pulse with a power
Pw and a length 0.9T, pulse with a power 0.8 mW and a
length 1.1T, pulse with a power Pw and a length 0.9T,
pulse with a power 0.8 mW and a length 1.1T, pulse with a
power Pw and a length 0.9T, pulse with a power 0.8 mW and
a length 1.45T, pulse with a power Pw and a length 1.4T,
pulse with a power 0.8 mW and a length 0.4T.
An erasing power Pe was irradiated between the above
pulses for mark formation. Pe/Pw=0.27 during recording.
The values of 3T space jitter and Pw after 10 times
overwriting are shown in Table 6. Retrieving was carried
out at 1.2 m/s. It is found from Table 6 that the disc
of Example 18 has excellent overwriting jitter
properties. The value y representing the Ge amount is
0.07, which is a considerably small value as compared
with the value y of Example 1 for example. This
indicates that the Ge amount can be decreased by
incorporation of Te or In as compared with discs having

the same level of crystallization speed.
Recording was carried out on the disc of Example 19
under the following conditions. EFM random signals were
recorded at a linear velocity of 38.4 m/s as mentioned
hereinafter. Marks with lengths of from 3T to 11T (T is
a reference clock period and is 7.2 nsec) contained in
the EFM signals were formed by irradiating a series of
pulses of the following laser pulses connected in
sequence.
3T: Pulse with a power Pw and a length 1.81T, pulse
with a power 0.8 mW and a length 0.7 5T.
4T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 0.31T.
5T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.31T, pulse with a
power Pw and a length 1.3 8T, pulse with a power 0.8 mW
and a length 0.31T.
6T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 1.06T, pulse with a power Pw and a length
0.94T, pulse with a power 0.8 mW and a length 0.31T.
7T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW

and a length 1.31T, pulse with a power Pw and a length
1.38T, pulse with a power 0.8 mW and a length 0.31T.
8T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 1.06T, Pulse with a power Pw and a length
0.94T, pulse with a power 0.8 mW and a length 1.06T,
pulse with a power Pw and a length 0.94T, pulse with a
power 0.8 mW and a length 0.31T.
9T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 1.06T, pulse with a power Pw and a length
0.94T, pulse with a power 0.8 mW and a length 1.31T,
pulse with a power Pw and a length 1.38T, pulse with a
power 0.8 mW and a length 0.31T.
10T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a
power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 1.06T, pulse with a power Pw and a length
0.94T, pulse with a power 0.8 mW and a length 1.06T,
pulse with a power Pw and a length 0.94T, pulse with a
power 0.8 mW and a length 1.06T, pulse with a power Pw
and a length 0.94T, pulse with a power 0.8 mW and a
length 0.31T.
11T: Pulse with a power Pw and a length 1T, pulse
with a power 0.8 mW and a length 1.06T, pulse with a

power Pw and a length 0.94T, pulse with a power 0.8 mW
and a length 1.06T, pulse with a power Pw and a length
0.94T, pulse with a power 0.8 mW and a length 1.06T,
pulse with a power Pw and a length 0.94T, pulse with a
power 0.8 mW and a length 1.31T, pulse with a power Pw
and a length 1.38T, pulse with a power 0.8 mW and a
length 0.31T.
An erasing power Pe was irradiated between the above
pulses for mark formation. Further, the irradiation
position of the pulses for 3T mark formation was shifted
toward ahead of the original timing of the 3T mark in the
EFM random signals by 0.06T (irradiation was carried out
at earlier time than the original 3T mark in the EFM
signal). By doing this, the marks to be formed are
closer to the original EFM random signals. Pe/Pw=0.25
during recording.
The values of 3T space jitter and Pw after 10 times
overwriting are shown in Table 6. Retrieving was carried
out at 1.2 m/s. It is found from Table 6 that the disc
of Example 19 has excellent overwriting jitter
properties. The value y representing the Ge amount is
0.04. It is found that the Ge amount can be decreased by
incorporation of Te or In. This indicates that the Ge
amount can be decreased by incorporation of Te or In as
compared with discs having the same level of
crystallization speed.
On the other hand, on each of the discs of

Comparative Examples 8 and 9 containing no Ge, amorphous
marks could not adequately be formed at least at a linear
velocity of at most 38.4 m/s. Accordingly, use as an
information recording medium is substantially difficult.
According to the present invention, a phase-change
recording material of which the phase change speed is
high, on which a high speed recording/erasing is
possible, which is excellent in storage stability, of
which the signal intensity is high, of with which high
speed initialization is possible, can be obtained, and an
information recording medium employing it can be
obtained. When the phase-change recording material of
the present invention is used for a rewritable
information recording medium, particularly favorable
recording properties can be obtained.
Further, when a phase-change recording material of
the present invention is used for an optical recording
medium particularly a rewritable optical recording
medium, an optical recording medium on which high speed
recording/erasing is possible, with which storage
stability of amorphous marks are excellent, which are
excellent in jitter properties, which has a high
reflectivity and signal amplitude, and which is excellent
in repetitive overwriting properties and further,
overwriting properties in overwriting is carried out on
recording marks after long-term storage, can be obtained.
Further, by using the phase-change recording

material of the present invention, an information
recording medium with a high productivity can be
obtained. Particularly when a phase-change recording
material of the present invention is used for an optical
recording medium, an optical recording medium of which
initial crystallization is easy and which remarkably
improves the productivity can be obtained.
The present invention has been described in detail
with reference to specific embodiments, but it is obvious
for the person skilled in the art that various changes
and modifications were possible without departing from
the intention and the scope of the present invention.
The entire disclosures of Japanese Patent
Application No. 2002-059005 filed on March 5, 2002,
Japanese Patent Application No. 2002-202744 filed on July
11, 2002 and Japanese Patent Application No. 2002-322708
filed on November 6, 2002 including specifications,
claims, drawings and summaries are incorporated herein by
reference in their entireties.

WE CLAIM:
l.An optical information recording medium utilizing a
crystalline state as a non-recorded state and an
amorphous state as a recorded state, which employs a
phase-change recording layer comprising an alloy having
the composition of the following formula (1) as the main
component:

wherein each of x, y, z and w represents atomicity, x, z
and w are numbers which satisfy 0.01≤x≤0.5, 0≤z≤0.3
and 0≤w≤0.1, respectively, and the element Ml is at
least one element selected from the group consisting of
In, Ga, Pt, Pd, Ag, rare earth elements, Se, N, O, C, Zn,
Si, Al, Bi, Ta, W, Nb and V, and
(I) when z=0 and w=0, y is a number which satisfies 0.12≤
y≤0.3,
(II) when 0 0.05≤y≤0.3, and
(III) when 0≤z≤0.3 and 0 satisfies 0.01≤y≤0.3. and on atleast one side of the
recording layer, a heat resistant protective layer is
formed, on a substrate.
2.The optical information recording medium as claimed in
claim 1, wherein in theinformation is rewritten by a
reversible change of the phase-change recording material
having the composition of the formula (1) as the main
component, between the crystalline state and the
amorphous state.

3.The optical information recording medium as claimed in
claim 1 or 2, wherein in the formula (1), (1-x) X(1-y-w-
2)≥0.5 is satisfied.
4.The optical information recording medium as claimed in
any one of claims 1 to 3, wherein in the formula (1),
0.1 ≤y+z+w≤0.4 is satisfied.
5.The optical information recording medium as claimed in
any one of claims 1 to 4, wherein in the formula (1),
the value of x is 0.1≤x≤0.35.
6.The optical information recording medium as claimed in
any one of claims 1 to 5, wherein the optical
information recording medium comprises a phase-change
type recording layer containing the phase-change
recording material having the composition of the above
formula (1) as the main component, and at least one
protective layer.
7.The optical information recording medium as claimed in
any one of claims 1 to 6, wherein the optical
information recording medium further comprises a
reflective layer, and the reflective layer contains Ag as
the main component.
8.An optical information recording medium substantially as
herein describe, particularly with reference to the
accompanying drawings.

An optical information recording medium utilizing a
crystalline state as a non-recorded state and an amorphous
state as a recorded state, which employs a phase-change
recording layer comprising an alloy having the composition
of the following formula (1) as the main component:
(Sb1-xSnx)1-y-w-zGeyTewM1z formula (1)
wherein each of x, y, z and w represents atomicity, x, z
and w are numbers which satisfy 0.01≤x≤0.5, 0≤z≤0.3
and 0≤w≤0.1, respectively, and the element Ml is at
least one element selected from the group consisting of
In, Ga, Pt, Pd, Ag, rare earth elements, Se, N, O, C, Zn,
Si, Al, Bi, Ta, W, Nb and V, and
(I) when z=0 and w=0, y is a number which satisfies 0.1≤
y≤0.3,
(II) when 0 0.05≤y≤0.3, and
(III) when 0≤z≤0.3 and 0 satisfies 0.01≤y≤0.3. and on atleast one side of the
recording layer, a heat resistant protective layer is
formed, on a substrate.

Documents:

125-KOL-2003-CORRESPONDENCE.pdf

125-kol-2003-granted-abstract.pdf

125-kol-2003-granted-claims.pdf

125-kol-2003-granted-correspondence.pdf

125-kol-2003-granted-description (complete).pdf

125-kol-2003-granted-drawings.pdf

125-kol-2003-granted-examination report.pdf

125-kol-2003-granted-form 1.pdf

125-kol-2003-granted-form 18.pdf

125-kol-2003-granted-form 2.pdf

125-kol-2003-granted-form 3.pdf

125-kol-2003-granted-form 5.pdf

125-kol-2003-granted-gpa.pdf

125-kol-2003-granted-priority document.pdf

125-kol-2003-granted-reply to examination report.pdf

125-kol-2003-granted-specification.pdf

125-kol-2003-granted-translated copy of priority document.pdf

125-KOL-2003-OTHERS.pdf


Patent Number 227292
Indian Patent Application Number 125/KOL/2003
PG Journal Number 02/2009
Publication Date 09-Jan-2009
Grant Date 06-Jan-2009
Date of Filing 27-Feb-2003
Name of Patentee MITSUBISHI CHEMICAL CORPORATION
Applicant Address 5-2, MARUNOUCHI 2-CHOME, CHIYODA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 MICHIKAZU HORIE C/O MITSUBHISHI CHEMICAL CORPORATOPN, 1000, KAMOSHIDA-CHO, AOBA-KU, YOKOHAMA-SHI KANAGAWA
2 TAKASHI OHNO C/O MITSUBHISHI CHEMICAL CORPORATOPN, 1000, KAMOSHIDA-CHO, AOBA-KU, YOKOHAMA-SHI KANAGAWA
PCT International Classification Number G06K 19/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2002-059005 2002-03-05 Japan
2 2002-022744 2002-07-11 Japan
3 2002-322708 2002-11-06 Japan