Title of Invention

PHASE-CHANGE RECORDING MATERIAL AND INFORMATION RECORDING MEDIUM

Abstract A phase-change recording material on which high velocity recording/erasing is possible, which provides excellent recording signal characteristics, which provides a high storage stability of the recording signals, with which the change in the reflectivity of the recorded signals is small even after a long term storage, and which provides excellent recording signal characteristics even if overwriting is carried out again, and an information recording medium employing the above material, are provided. it is characterized by containing as the main component a composition represented by Gex(InwSn1-w)yTezSb1-x-y-z (wherein the Sb content is higher than any one of the Ge content, the In content, the Sn content and the Te content, and x, y, z and w representing atomicity ratios satisfy (i) 0=x=0.3, (ii) 0.07=y-z, (iii) wxy-z=0.l, (iv) 0<z, (v) (1-w) xy=0.35 and (vi) 0.35=l-x-y-z).
Full Text DESCRIPTION
PHASE-CHANGE RECORDING MATERIAL AND INFORMATION RECORDING
MEDIUM
TECHNICAL FIELD
The present invention relates to a phase-change
recording material and an information recording medium
employing it.
BACKGROUND ART
As a recording method utilizing the phase change, a
method has been known wherein the crystal structure of a
metal or a semiconductor is reversibly changed by
affecting energy beams or an energy flow such as light or
electric current (Joule heat) (Appl. Phys. Lett., Vol. 18
(1971), pp. 254-257, U.S. Patent 3,530,441).
Used practically at present as a means for recording
on an information recording medium employing a phase-
change recording material, is a means to utilize a
reversible change between the crystalline phase and the
amorphous phase. Specifically, it is a means to let the
crystalline state in a non-recorded/erased state and to
form amorphous marks at the time of recording. Usually,
a recording layer is locally heated to a temperature
higher than the melting point and then rapidly cooled to
form amorphous marks. On the other hand, the recording
layer is heated at a temperature of approximately at most
the melting point and at least the crystallization
temperature, and slowly cooled so that the recording
layer is kept at a temperature of at least the
crystallization temperature for a certain retention time
to carry out recrystallization. Namely, in general, a
reversible change between the stable crystalline phase
and the amorphous phase is utilized, and the information
is recorded or retrieved by detecting the difference in
physical parameters such as refractive index, electric
resistance, volume and change in density, between the
crystalline state and the amorphous state.
On the optical information recording medium among
information recording mediums, recording/retrieving is
carried out by utilizing a change in the reflectivity
accompanying the reversible change between the
crystalline state and the amorphous state caused locally
by irradiation with a focused light beam. Such an
optical information recording medium having a phase-
change recording layer is being developed and used
practically as a low cost large capacity recording medium
excellent in portability, weather resistance, impact
resistance, etc. For example, a rewritable phase-change
type optical information recording medium (hereinafter "a
rewritable phase-change type optical information
recording medium" may sometimes be referred to as phase-
change type optical disk, optical disk or disk) such as
CD-RW, DVD-RW, DVD+RW and DVD-RAM is widely used.
Further, it has been developed to achieve a high density
by the use of blue laser or by an increase in NA of an
objective lens, or to make high speed recording possible
by improvement of the recording pulse waveform.
As a material for such a phase-change recording
layer, a chalcogenide alloy is used in many cases. As
such a chalcogenide alloy, a Ge-Sb-Te type, In-Sb-Te
type, Ge-Sn-Te type or Ag-In-Sb-Te type alloy may, for
example, be mentioned. Such an alloy is usually an
overwritable material also.
Overwriting is a means wherein when recording is
carried out again on a once-recorded optical information
recording medium, writing is carried out without erasing
before the recording, that is, a means of recording while
erasing. On an optical information recording medium
having a phase-change recording layer, recording is
carried out usually by overwriting, and accordingly
recording while erasing (i.e. overwriting) may sometimes
be referred to simply as recording.
It is possible to obtain an optical information
recording medium on which high velocity recording at 10-
times velocity is possible by increasing the
crystallization speed, by employing for the recording
layer a composition which comprises as a matrix a Sb70Te30
alloy comprising a Sb70Te3o eutectic composition as the
base and containing gb in large excess, among the above
chalcogenide alloys. Particularly, preferred for the
recording layer is a composition which comprises a
Sb70Te3o eutectic composition containing Sb in large
excess and contains Ge (JP-A-2001-229537 (paragraph
0031)).
DISCLOSURE OF THE INVENTION
In recent years, along with increase in the amount
of information, it has been desired to develop an optical
information recording medium on which recording, erasing
and retrieving at a higher velocity are possible.
Namely, it is necessary to employ for the recording layer
a phase-change recording material capable of being
crystallized at a higher speed. However, if the above
phase-change recording material has a composition with
which an adequately high crystallization speed is
obtained, it tends to be difficult to satisfy both
characteristics of excellent jitter characteristics
(recording signal quality) and the storage stability of
amorphous marks, from such a reason that noises of the
signal of the optical information recording medium become
significant. This problem is particularly remarkable
with an optical information recording medium on which
high velocity recording/erasing of information signals is
carried out at a reference clock period of at most 15 ns.
For example, when the above composition which
comprises a Sb7oTe3o eutectic composition containing Sb in
large excess and contains Ge is represented by
(SbcTe1-c)1-dGed, it is possible to increase the
crystallization speed by decreasing the ratio of the Te
content relative to Sb by increasing the value c and
bringing it to be close to 0.9. However, the noises of
the optical information recording medium tend to be
significant, and no favorable jitter characteristics will
be obtained. Further, when the Ge content is reduced,
although the noise increase tends to be suppressed, the
storage stability of the amorphous marks will decrease.
The present invention has been made to overcome the
above problems, and its object is to provide a phase-
change recording material on which high velocity
recording/erasing is possible, which provides excellent
recording signal characteristics such as the reflectivity
and the signal amplitude or the jitter characteristics,
and which provides a high storage stability of the
recording signals, and an information recording medium
employing the above material. Further, it is to provide
a phase-change recording material with which the change
of e.g. the reflectivity of the recorded signals is small
even when the information recording medium is stored for
a long time, and which provides excellent recording
signal characteristics when the information recording
medium on which signals are recorded is stored for a long
time and then overwriting is carried out again, and an
information recording medium employing the above
material. Particularly, it is to provide an optical
information recording medium which is one mode of the
applications of the information recording medium.
Under the above circumstances, the present inventors
have conducted extensive studies and as a result, have
found that when the Sb, In, Sn, Te and Ge compositions
satisfy predetermined relational formulae, both recording
signal quality such as the jitter characteristics and the
stability of amorphous marks can be satisfied even if
recording/erasing is carried out at a high velocity, and
excellent recording signal characteristics can be
maintained even when overwriting is carried out again
after long term storage, and they have achieved the
present invention.
Namely, the present invention provides, as disclosed
in Claim 1, a phase-change recording material
characterized by containing a composition represented by
the following formula (1) as the main component:
Gex(InwSn1-w)yTezSb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge
content, the In content, the Sn content and the Te
content, and x, y, z and w representing atomic ratios,
The phase-change recording material of the present
invention, by containing the composition represented by
the formula (1) as the main component, is excellent in
the recording signal characteristics even when
recording/erasing is carried out at a high velocity,
provides a high storage stability of the recording
signals, provides a small decrease in the reflectivity of
the recorded signals even after long term storage, and
provides excellent recording signal characteristics even
when overwriting is carried out again.
The present invention further provides, as disclosed
in Claim 2, the phase-change recording material according
to Claim 1, wherein in the formula (1), x further
satisfies 0 The present invention further provides, as disclosed
in Claim 3, the phase-change recording material according
to Claim 1 or 2, wherein in the formula (1), x further
satisfies x=O.1.
The present invention further provides, as disclosed
in Claim 4, the phase-change recording material according
to any one of Claims 1 to 3, wherein in the formula (1),
w further satisfies 0 The present invention further provides, as disclosed
in Claim 5, the phase-change recording material according
to any one of Claims 1 to 4, wherein in the formula (1),
z further satisfies 0.1 The present invention further provides, as disclosed
in Claim 6, the phase-change recording material according
to any one of Claims 1 to 5, wherein of the above
information recording material, the crystalline state
corresponds to a non-recorded state, and the amorphous
state corresponds to a recorded state.
The present invention further provides, as disclosed
in Claim 7, an information recording medium having a
recording layer, characterized in that the above
recording layer contains a composition represented by the
following formula (1) as the main component:
Gex(InwSn1-w)yTezSb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge
content, the In content, the Sn content and the Te
content, and x, y, z and w representing atomic ratios,
The present invention further provides, as disclosed
in Claim 8, the information recording medium according to
Claim 7, wherein in the formula (1), x further satisfies
0 The present invention further provides, as disclosed
in Claim 9, the information recording medium according to
Claim 7 or 8, wherein in the formula (1), x further
satisfies x=0.1.
The present invention further provides, as disclosed
in Claim 10, the information recording medium according
to any one of Claims 7 to 9, wherein in the formula (1),
w further satisfies 0 The present invention further provides, as disclosed
in Claim 11, the information recording medium according
to any one of Claims 7 to 10, wherein in the formula (1),
z further satisfies 0.1 The present invention further provides, as disclosed
in Claim 12, the information recording medium according
to any one of Claims 7 to 11, wherein of the above
information recording medium, the crystalline state
corresponds to a non-recorded state, and the amorphous
state corresponds to a recorded state.
The present invention further provides, as disclosed
in Claim 13, the information recording medium according
to any one of Claims 7 to 12, wherein the information
recording medium is an optical information recording
medium, on which recording is carried out by a laser
beam.
The present invention further provides, as disclosed
in Claim 14, the information recording medium according
to Claim 13, wherein the optical information recording
medium has a protective layer A in contact with the
recording layer, and the protective layer A contains a
metal oxysulfide and/or a metal nitride.
The present invention further provides, as disclosed
in Claim 15, the information recording medium according
to Claim 14, wherein the metal oxysulfide is an
oxysulfide of yttrium, and the metal nitride is a nitride
of an alloy containing germanium as the main component.
The present invention further provides, as disclosed
in Claim 16, the information recording medium according
to Claim 14 or 15, wherein the protective layer A is
formed in contact with each side of the recording layer.
The present invention further provides, as disclosed
in Claim 17, the information recording medium according
to any one of Claims 14 to 16, wherein the above
protective layer A is formed in contact with the side of
the recording layer from which a laser beam enters, and
the above protective layer A has a thickness of at most
50 nm.
The present invention further provides, as disclosed
in Claim 18, the information recording medium according
to any one of Claims 14 to 16, wherein the protective
layer A is formed in contact with the side of the
recording layer from which a laser beam enters, and
further, a protective layer B is formed on the side
opposite to the above recording layer in contact with the
protective layer A, and the total thickness of the
thickness of the protective layer A and the thickness of
the protective layer B is at most 5 0 nm.
The present invention further provides, as disclosed
in Claim 19, the information recording medium according
to any one of Claims 14 to 18, wherein the recording
layer has a thickness of at least 5 ran and at most 15 nm.
The present invention further provides, as disclosed
in Claim 20, the information recording medium according
to any one of Claims 13 to 19, wherein the optical
information recording medium further has a reflective
layer, and the reflective layer contains Ag as the main
component.
EFFECTS OF THE INVENTION
According to the present invention, a phase-change
recording material on which high velocity
recording/erasing is possible, which has excellent
recording signal characteristics and which provides a
high storage stability of the recording signals, and an
information recording medium employing the above material
can be provided.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. 1 is schematic views illustrating the layer
structure of an optical information recording medium.
Fig. 2 is schematic views illustrating the power
pattern of a recording laser beam in the recording method
of an optical information recording medium.
Fig. 3 is a schematic view illustrating the
temperature history at the time of recording or at the
time of erasing the rewritable information recording.
Fig. 4 is a schematic view illustrating the
structure of one cell of a non-volatile memory.
Fig. 5 is schematic views illustrating the layer
structure of an optical information recording medium.
Fig. 6 is schematic views illustrating the layer
structure of an optical information recording medium.
Fig. 7 is a graph illustrating the decrease in the
reflectivity during acceleration relative to the amount
of (In-Te).
Fig. 8 illustrates the repeated overwriting
characteristics of an optical information recording
medium.
Fig. 9 illustrates the repeated overwriting
characteristics of an optical information recording
medium.
Fig. 10 illustrates the repeated overwriting
characteristics of an optical information recording
medium.
Fig. 11 illustrates the repeated jitter
characteristics of an optical information recording
medium.
Fig. 12 illustrates the repeated overwriting
characteristics of an optical information recording
medium.
Fig. 13 illustrates the repeated jitter
characteristics of an optical information recording
medium.
BEST MODE FOR CARRYING OUT THE INVENTION
Now, the embodiments of the present invention will
be explained in detail below. However, the present
invention is by no means restricted to the following
embodiments, and various modifications are possible
within the a range of the gists.
[1] Phase-change recording material
[1-1] General explanation
The phase-change recording material of the present
invention is characterized by containing a composition
represented by the following formula (1) as the main
component:
Gex(InwSn1-w)yTezSb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge
content, the In content, the Sn content and the Te
content, and x, y, z and w representing atomic ratios,
predetermined composition as the main component" means
that the content of the predetermined composition is at
least 50 atomic% based on the entire materials or the
entire layer in which the predetermined composition is
contained. In order to effectively obtain the effect of
the present invention, the composition represented by the
above formula (1) is contained in an amount of preferably
at least 80 atomic%, more preferably at least 90 atomic%,
particularly preferably at least 95 atomic%, based on the
entire phase-change recording material.
In the present invention, in order to increase the
crystallization speed so that high velocity
recording/erasing is possible, a composition containing
mainly Sb is employed for the above phase-change
recording material. Accordingly, the Sb content is
higher than any of the contents of the other atoms. The
reason why Sb is mainly contained is that the amorphous
phase of Sb can be crystallized at a very high speed,
whereby it becomes possible to crystallize the amorphous
marks in a short time. Namely, the amorphous state
recording marks will be easily erased when Sb is mainly
contained.
Further, in the present invention, an additional
element to facilitate formation of an amorphous phase and
to increase the archival stability of the amorphous state
is used together with Sb, rather than using Sb alone.
Accordingly, Ge is employed together with Sb. Namely,
when the Ge content is high, the amorphous phase
formation tends to be easy, and the archival stability of
the amorphous state tends to increase. Further,
according to the studies by the present inventors, it was
found that the recording signal characteristics when
overwriting is carried out after the recorded medium is
stored for a long time is also related to the Ge content.
Further, in the present invention, of the phase-
change recording material containing mainly Sb, the total
amount of In and/or Sn and the total amount of Te are in
a predetermined relation.
Here, as the phase-change recording material
containing Sb as the main body, the above-described
composition comprising a Sb70Te30 eutectic composition and
containing Sb in large excess, and further containing Ge
in an amount of about 10 atomic%, has been known. It can
be considered that the material of the present invention
is a material having a large amount of In and/or Sn added
to the above conventional composition (hereinafter
sometimes referred to as a conventional SbTe eutectic
type composition) so as to satisfy the predetermined
relation. With the conventional SbTe eutectic type
composition having In or Sn added thereto, deterioration
of e.g. the jitter due to the crystal grain boundary
noise tends to be somewhat suppressed, however, the
reflectivity at the crystalline state tends to be low,
whereby the difference in the reflectivity (signal
amplitude) between the crystalline and amorphous states
tends to be small. Particularly when the In content is
high, such a phenomenon that the reflectivity at the
crystalline state decreases with time is observed. This
is considered to indicate a possibility that when the In
content is high, the crystalline state which is
originally supposed to be stable is formed into an
unstable quasi-stable phase.
Further, with respect to the conventional SbTe
eutectic type composition containing In and Sn, along
with increase in the number of repeated overwriting, the
performance of formation of an amorphous state (easiness
of formation of an amorphous state, storage stability of
the formed amorphous state, etc.) and the crystallization
speed tend to change (hereinafter sometimes referred to
as the change in the phase-change performance). The
reason is supposed that In or Sn and Te are in a repeated
melted/cooled state in the process of the repeated
overwriting, whereby an intermetallic compound
(telluride) is formed to cause segregation, and the
properties as an alloy change. This change in the phase-
change performance is a more serious problem when
recording by overwriting at a higher density and at a
higher recording linear velocity is to be realized.
Accordingly, it has been considered that In or Sb can be
added in only a slight amount (at most about 10 atomic%)
to the conventional SbTe eutectic type composition.
Particularly, it has been considered that In or Sn can be
added in an amount of at most about half the amount of
Te. Practically, as disclosed in Examples of JP-A-10-
326436 and JP-A-2002-79757, the addition amount of In or
Sn in the conventional SbTe eutectic type composition is
smaller than 10 atomic%. Further, the content of In or
Sn is considerably lower than Te.
As mentioned above, the purpose of addition of In,
Sn or the like to the conventional SbTe eutectic type
composition is to provide an additional improving effect
to the SbTe eutectic type composition as the main
component, and according to these circumstances, their
addition has been studied with a small addition amount.
Accordingly, the contents of In and Sn have been studied
below a level where various adverse effects have been
confirmed when their contents are close to the same as
the Te content, and it has been considered that it is not
necessary to positively incorporate In or Sn exceeding
the Te content.
However, according to the studies by the present
inventors, it has been found that when the content of In
and/or Sn is considerably increased relative to Te, the
reflectivity at the crystalline state increases on the
contrary, and the difference in the reflectivity between
the crystalline and amorphous states (signal amplitude)
increases again. Further, it has been found that when
the content of In and/or Sn is considerably increased
relative to Te, the archival change of the reflectivity
is small. Still further, it has been found that in such
a case, it is possible to satisfy both recording signal
characteristics at a high velocity and stability of the
amorphous state.
Namely, when the Sb/Te ratio is increased
(particularly the Sb/Te ratio exceeds 4) for the purpose
of increasing the crystallization speed so as to realize
high velocity overwriting, such a tendency that the
crystal grain boundary noise becomes significant and the
signal quality such as the jitter deteriorates, and a
decrease in the archival stability of the amorphous state
(the amorphous state is crystallized during a long term
storage at room temperature), are observed. However,
there is a prospect of resolution of all the above
problems when the content of In and/or Sn is considerably
increased relative to Te. For example, with respect to
the stability of the amorphous state, it was found that
the stability of the amorphous state is extremely high
under usual storage conditions in the vicinity of room
temperature.
Further, the change in the phase-change performance
occurred when the repeated overwriting is carried out is
supposed to be due to the segregation of the Te compound
occurred when the repeated overwriting is carried out.
Accordingly, it is usually considered that addition of In
or Sn in a large amount further deteriorates the above
problem of the segregation of the Te compound. However,
according to the studies by the present inventors,
contrary to such a concept, it was found that when the
content of In and/or Sn is considerably increased
relative to Te, the change in the phase-change
performance due to the repeated overwriting is
suppressed.
The phase-change recording material of the present
invention wherein In, Sn, Sb, Te and further Ge satisfy
the respective predetermined relations cannot be
considered as one having a SbTe eutectic composition and
having additional elements merely added thereto. This is
because the phase state of the above phase-change
recording material is expected to be very complicated,
and the presence or absence of the above segregation due
to the repeated overwriting is not clear also. However,
stabilization of the crystallization speed (suppression
of the change in the crystallization speed) when the
repeated overwriting is carried out on the phase-change
recording material of the present invention is thought to
be achieved by either of the following two mechanisms.
That is, the first mechanism is that in the phase-change
recording material of the present invention, a relatively
stable solid-solution state, even if it is quasi-stable,
is formed within a specific composition range, and thus
the segregation itself of the phase-change recording
material is less likely to occur, and accordingly the
change in the phase-change performance is suppressed.
Further, the second mechanism is that even if the
segregation occurs, the phase which undergoes the
segregation is limited to a phase having a specific
compositional ratio, and this phase having a specific
compositional ratio does not have bad influences over the
crystallization speed etc., and accordingly the change in
the phase-change performance is suppressed.
Accordingly, in the present invention, it is
important to control the Te content and the In and/or Sn
content in predetermined ranges.
In the present invention, there is one more reason
why it is important to control the Te content and the In
and/or Sn content. That is, the elemental composition of
the present invention may be considered as a material
which comprises a GeSbSn type material or GeInSb type
material containing mainly Sb and has Te added. In and
Te are elements which facilitate the amorphous mark
formation and reduce the fluctuation at the edge of the
formed amorphous mark shape. Accordingly, by employing
such elements, the jitter in the mark length recording
when the present invention is applied to an optical
information recording medium can be decreased. Further,
Te increases the repeated recording durability. However,
by addition of Te also, the reflectivity of the
crystalline state tends to be low and the difference in
the reflectivity between the crystalline and amorphous
states (signal amplitude) tends to be small, and
accordingly it is important to control the Te addition
amount. According to the studies by the present
inventors, it was found that by setting the relation
between the Te content and the total amount of the In
content and the Sn content to be within a predetermined
range, decrease in the reflectivity of the crystalline
state and the signal amplitude due to Te addition can be
suppressed. Further, by setting the relation between the
Te content and the total amount of the In content and the
Sn content to be within a predetermined range, it becomes
possible to satisfy both erasure of the amorphous marks
(recording signals) by recrystallization in a short time
in a case of high velocity recording and stability of the
amorphous marks (recording signals) during storage.
Further, by setting the relation between the Te content
and the total amount of the In content and the Sn content
to be within a predetermined range, it becomes possible
to form amorphous marks with small noises (the jitter in
the mark length recording when the present invention is
applied to an optical information recording medium) due
to the fluctuation in the mark shape.
Further, when the In content is high, the
reflectivity of the crystalline state of a phase-change
type disk tends to decrease by a long term storage. This
is considered to be because the quasi-stable crystalline
state is formed, and the crystal structure subtlely
changes. The amount of decrease in the reflectivity may
exceed 10% of the reflectivity of the initial crystalline
state in some cases. Such an archival change of the
crystalline state is considered to cause changes in not
only optical characteristics but also other physical
characteristics such as electrical characteristics.
Accordingly, the above archival change of the crystalline
state is a cause of a decrease in the storage stability
of the recorded information.
However, according to the studies by the present
inventors, it was found that even when the In content is
high to a certain extent, by defining the relation of the
In and Te contents, the decrease in the reflectivity due
to a long term storage can be reduced.
Namely, by adjusting the recording layer
composition, an information recording medium excellent in
recording signal characteristics at a high velocity and
excellent in stability of the crystalline state and the
amorphous state can be obtained. Accordingly, an
information recording medium excellent in stability of
the optical characteristics, the electrical
characteristics etc. derived from the difference in the
physical characteristics between both states and also
excellent in recording signal characteristics when the
recorded medium is stored for a long time and then
overwriting is carried out, can be obtained.
Further, in the present invention, it is preferred
that of the phase-change recording material, the
crystalline state corresponds to a non-recorded state,
and the amorphous state corresponds to a recorded state.
This is because it is supposed that not many crystal
nuclei are present in the amorphous state of the phase-
change recording material of the present invention. That
is, in a case where the amorphous state corresponds to a
non-recorded state and crystalline state marks are formed
in this amorphous state, it is preferred to use a phase-
change recording material in which many crystal nuclei
are present. This is because when many crystal nuclei
are present in the phase-change recording material, the
shape of the crystalline state marks is less likely to be
influenced by the position of the crystal nuclei. On the
other hand, as described above, not many crystal nuclei
are present in the phase-change recording material of the
present invention, and accordingly favorable recording is
likely to be carried out when the crystal state
corresponds to a non-recorded state and amorphous state
recording marks are formed in the crystalline state,
rather than when the amorphous state corresponds to a
non-recorded state and crystalline state recording marks
are formed in the amorphous state.
Now, the relation between the contents of the
respective elements and the characteristics are explained
in detail below.
In the following explanation, the effect of addition
of the respective elements (particularly In and Sn) is
described mainly in view of the optical characteristics.
However, the difference in the reflectivity between the
crystalline state and the amorphous state observed as the
optical characteristics, and the archival stability of
the difference in the reflectivity, are considered to
have influences over the difference in the
characteristics between the crystalline state and the
amorphous state and the stability (accordingly, the
amplitude of the recording signals, the degree of the SN
ratio and its stability) observed in view of e.g. the
electrical characteristics also. Further, the noises due
to the scattering at crystal grain boundaries which are
understood as the optical characteristics, are considered
to be observed electrically also as noises due to the
scattering of electron at crystal grain boundaries.
Accordingly, the following explanation in view of the
optical characteristics can be considered to be similarly
applicable to the electrical characteristics also.
(Sb, Formula (vi))
The Sb content is higher than any of the Ge content,
the In content, the Sn content and the Te content.
Namely, the recording material of the present invention
contains mainly Sb. Sb itself is effective to
crystallize the amorphous state in a short time, but its
amorphous state formation ability is low, and the
resulting amorphous state tends to be unstable, and
accordingly it is necessary to use it together with an
additional element as described hereinafter. The
crystallization speed is high when the Sb content is
high. Particularly in the high velocity recording for
which crystallization in a short time is required, the Sb
content is relatively increased. Specifically, the Sb
content is at least 3 5 atomic% and is higher than the
content of any other element contained. In order to
adequately obtain the effect of the present invention,
the Sb content is preferably at least 40 atomic%, more
preferably at least 45 atomic%.
Further, in the present invention, it is also
important to control the Sb/Te ratio. With a view to
carrying out the high velocity recording, the Sb/Te ratio
is usually at least 2.3, preferably at least 3, more
preferably at least 4. On the other hand, in view of the
balance between the high velocity recording
characteristics and the characteristics other than the
high velocity recording characteristics, the Sb/Te ratio
is usually at most 9.5, preferably at most 9.
(Sn, Formulae (ii) and (v))
The influence of the Sn content over the
reflectivity of the crystalline state and the difference
in the reflectivity between the crystalline and amorphous
states (signal amplitude) and the influence of the In
content over the reflectivity of the crystalline state
and the difference in the reflectivity between the
crystalline and amorphous states (signal amplitude) are
substantially the same. Accordingly, to the phase-change
recording material, one of Sn and In is contained.
Further, the reflectivity of the crystalline state and
the signal amplitude can be increased by making the total
amount of the Sn content and the In content be larger
than the Te amount within a certain range. On the other
hand, when the Te content is high, the reflectivity of
the crystalline state and the signal amplitude decrease.
Accordingly, in order to obtain the desired reflectivity
of the crystalline state and signal amplitude, it is
important to control the relation between the Sn and/or
In content and the Te content.
Accordingly, the value (y-z) in the above formula
(1) is at least 0.07, and preferably at least 0.1, more
preferably at least 0.13, particularly preferably at
least 0.15. When the value y is high, the optimum power
will be low, such being favorable.
Further, if the Sn amount is too large, the boundary
shape of the amorphous mark tends to fluctuate
particularly when the present invention is applied to an
optical information recording medium, or the jitter
characteristics which are considered to be due to the
crystal grain boundaries tend to deteriorate.
Accordingly, the value (l-w)xy in the above formula (1)
is at most 0.35, and preferably at most 0.3.
Accordingly, when Te is contained in a large amount, it
is necessary to make the total amount of the In content
and the Sn content large with a view to controlling the
signal amplitude. However, the Sn amount cannot be so
large taking the jitter characteristics into
consideration. Accordingly, when the Te content is high,
it is preferred to incorporate In in addition to Sn.
Specifically, in a case where the Te content is so high
that the decrease in the reflectivity of the crystalline
state and the signal amplitude due to Te cannot be
suppressed unless Sn is contained in an amount exceeding
3 5 atomic%, In may be contained.
(In, Formula (iii))
By using In, the reflectivity of the crystalline
state and the difference in the reflectivity between the
crystalline and amorphous states (signal amplitude) can
be increased, and accordingly in the present invention,
it is preferred to use In as an element to be contained
in the recording layer.
By using In, the reflectivity of the crystalline
state and the difference in the reflectivity between the
crystalline and amorphous states (signal amplitude) can
be increased, and in addition, there is such an advantage
that the influence over the jitter characteristics can be
reduced as compared with Sn. In is supposed to have a
function to decrease the crystal grain boundary noise as
compared with Sn and Te. On the other hand, In causes
decrease in the reflectivity due to the long term storage
which is supposed to be attributable to the quasi-stable
crystalline state. On the contrary, Te tends to suppress
the decrease in the reflectivity due to the long term
storage. Accordingly, with a view to suppressing the
decrease in the reflectivity of the optical information
recording medium due to the long term storage, it is
important that the In content and the Te content are in a
predetermined relation. The present inventors have
prepared and studied optical information recording
mediums having various recording layer compositions and
as a result, found that a decrease in the reflectivity
due to the long term storage occurs when the In content
is too high relative to the Te content. Namely, the
decrease in the reflectivity due to the long term storage
can be suppressed by making the value {(In content) - (Te
content)} within a predetermined range in the above
formula (1) . Specifically, when the value wxy-z in the
above formula (1) is low, the rate of decrease in the
reflectivity due to the long term storage tends to be
low. Accordingly, the value wxy-z is preferably at most
0.1, more preferably at most 0.05, furthermore preferably
at most 0. Here, wxy-z=0 means that the In content and
the Te content are the same. Accordingly, it is further
preferred in the present invention that the In content is
the same as the Te content or the In content is lower
than the Te content.
Accordingly, when the decrease in the reflectivity
due to the long term storage is to be made as small as
possible, In cannot be contained in an excessively large
amount relative to Te, and accordingly in order to
satisfy the above-described relational formula 0.07=y-z,
it is preferred that the phase-change recording material
of the present invention contains Sn in addition to In.
Specifically, in a case where wxy-z be satisfied unless Sn is contained in addition to In.
Further, it is preferred that both In and Sn are
contained from such a viewpoint also that the
crystallization speed suitable for the high velocity
recording is less likely to be obtained when the In and
Te contents are high while Sn is not contained. Namely,
it is preferred that 0 If the In amount is excessively large, the signal
quality during the long term storage of the information
recording medium tends to deteriorate (for example, the
reflectivity tends to decrease during the long term
storage when the information recording medium is used as
an optical information recording medium). Further, if
the In amount is large while Sn is not contained, a
stable crystal layer with a low reflectivity as observed
in the In-Sb system may appear in some cases.
Accordingly, the In content i.e. the value wxy is
preferably at most 0.35.
(Te, Formula (iv))
The phase-change recording material of the present
invention contains Te.
The phase-change material of the present invention
comprises a SbTe eutectic type containing Sb in large
excess over Sb70Te30 as the base and provides its phase
change performance, and thus Te is an essential element.
Te bonded to Sb stabilizes the phase-change
performance in the repeated recording and improves the
repeated recording durability. Further, Te has an effect
to maintain the erasing performance (to maintain the
crystallization speed) and resultingly to improve the
rebeated recording durability, after an information
recording medium employing the phase-change recording
material of the present invention is stored for a long
time.
In a case where Te is contained, if In, Sn or the
like is added for the purpose of improving other
characteristics, there is a possibility that In or Sn
forms a compound with Te to cause segregation. However,
in order to maintain basic phase-change performance, Te
together with Sb is an essential element. Namely, even
in a case where In or Sn is employed for the phase-change
recording material of the present invention, Te cannot be
excluded, and in order to further improve the
characteristics with the SbTe binary composition, In or
Sn has to be contained. Accordingly, one of the
important significances of the present invention is that
the In or Sn is contained in a predetermined range
relative to Te so as to suppress the bad influence of the
segregation to a negligible level.
Accordingly, although the Te amount is preferably
high to a certain extent, it is necessary to control the
relation between In and/or Sn and Te and the relation
between In and Te in predetermined ranges. Specifically,
z indicating the Te content in the above formula (1) is
0 furthermore preferably 0.08=cz, particularly preferably
0.l=z, most preferably 0.1 z indicating the Te content is usually less than
0.29, which is a value necessarily determined by other
relational formulae defined for the above formula (1).
As described above, it is preferred that the In and Te
contents are high to a certain extent, however,
particularly Te has a function to lower the
crystallization speed, and accordingly in order to obtain
the crystallization speed suitable for the high velocity
recording, z indicating the Te content is preferably at
most 0.25, more preferably at most 0.20.
(Ge, Formula (i))
In the present invention, Ge may be used so as to
adjust the crystallization speed. Namely, Ge is not so
largely related to the characteristics such as the
reflectivity, the signal amplitude (the difference in the
reflectivity between the crystalline and amorphous
states) and the decrease in the reflectivity due to the
long term storage of the medium. Accordingly, Ge may be
used so as to obtain the crystallization speed suitable
for the recording conditions which are to be employed.
When the Ge amount is large, the crystallization speed
tends to be low, and accordingly for an information
recording medium for higher velocity recording for
example, the Ge content may be reduced to adjust the
crystallization speed. However, the crystallization
speed relates to the other element contents also, and
when the Sb or Sn amount is large, the crystallization
speed tends to be high, and the In or Te amount is large,
the crystallization speed tends to be low. Accordingly,
it is preferred to adjust the Ge content after the ratio
of the contents of the elements other than Ge is
determined taking the above described various
characteristics into consideration, thereby to adjust the
crystallization speed in accordance with the recording
conditions. If the Ge content is too high, the
crystallization speed tends to be too low, and
accordingly x in the above formula (1) is at most 0.3,
and preferably at most 0.25, more preferably at most 0.2.
Here, the Ge and Te contents have particularly
significant influence over the crystallization speed.
Further, if the Ge content is high, when the
recorded amorphous marks are stored for a long term, they
tend to be hardly crystallized as compared with
immediately after the recording before the storage. If
this phenomenon is remarkable, the signal quality of the
overwritten recording signals tends to be insufficient
when the overwriting is carried out after the recorded
information recording medium is stored for a long term.
Namely, the signal quality of the new recording marks is
deteriorated since the old marks after the long term
storage are not adequately erased. This phenomenon that
the crystallization is less likely to take place is
problematic only at the first recording after the long
term storage, and the amorphous marks which are newly
recorded after the long term storage have normal
crystallization speed. At any rate, this phenomenon is
reduced by decreasing the Ge content. In this view, the
Ge content is preferably small, and the value x in the
above formula (1) is particularly preferably at most 0.1,
most preferably at most 0.07. In the present invention,
the above various characteristics are satisfied, and in
addition, reduction of the phenomenon was successful.
As described above, Te and In have an effect to
lower the crystallization speed, and the Ge content can
be reduced when the Te or In content is high, in order to
obtain the same crystallization speed when the
crystallization speed is made low. In this view, the Te
content i.e. the value z is preferably at least 0.05,
more preferably at least 0.08, most preferably at least
0.1. Still further, the In content i.e. the value wxy is
preferably at least 0.05, more preferably at least 0.08.
Further, if the Te content is high, it is preferred that
both In and Sn are contained as mentioned above. Namely,
in the most preferred composition, all of Ge, In, Sb, Sn
and Te are contained.
On the other hand, if the Ge content is too low, the
storage stability of the amorphous marks tends to
deteriorate, and the amorphous marks tend to be
crystallized by the long term storage. The storage
stability of the amorphous marks tends to be improved
also by increasing the In amount, but the influence of Ge
tends to be more significant. On the other hand, the
storage stability of the amorphous marks may be
relatively favorable in some cases even if the Ge content
is zero, by influences of other elements. Accordingly,
the value x in the above formula (1) is at least 0,
preferably higher than 0, more preferably at least 0.01,
furthermore preferably at least 0.02.
[1-2] The contents of Ge, In, Sn, Te and Sb in the
phase-change recording material of the present invention
In the present invention, the possible maximum and
minimum contents of the respective elements Ge, In, Sn,
Te and Sb constituting the phase change recoding material
of the present invention are necessarily determined from
the conditions in the above formula (1) i.e. seven
conditions (a) the Sb content is higher than any one of
the Ge content, the In content, the Sn content and the Te
content, (b) 0=x=0.3, (c) 0.07=y-z, (d) wxy-z=0.1,
(e)0=z, (f) (l-w)xy=0.35 and (g) 0.35=l-x-y-z.
Specifically, a computer program to judge whether or
not the above seven conditions are satisfied when the
values x, y, z and w are independently changed from 0 to
1 by 0.001 each time is prepared and executed to obtain
the possible maximum and minimum contents of Ge, In, Sn,
Te and Sb. Needless to say, the total of the atomicity
ratios of Ge, In, Sn, Te and Sb is 1. Further, by
reducing the degree of the changes of the value to e.g.
by 0.0001 or by 0.00001, more detailed ranges of the
respective atoms Ge, In, Sn, Te and Sb can be obtained.
In Table 1, an example of the above computer program
prepared by means of Visual Basic is shown.
TABLE 1
Example of a program to obtain the minimum value and
the maximum value regarding each element content by
numerical calculation (prepared by Visual Basic)
minGe=l 'minimum value of x
Further, according to the above program, the
possible range of y-z which is the difference between the
total of the In content and/or the Sn content and the Te
content is from 0.070 to 0.449, and the possible range of
wxy-z which is the difference between the In content and
the Te content is from -0.279 to 0.100.
The numbers indicating the ranges of the contents of
the respective elements according to the above program
somewhat change depending upon the significant digit at
the time of the program execution.
Further, the above conditions (a) to (g) may change
in accordance with the changes of the conditions of the
preferred range, the more preferred range etc., as
explained in the above [1-1], and when the conditions are
changed, the above computer program is executed again
employing the new conditions to obtain the upper limit
and the lower limit of the respective elements Ge, In,
Sn, Te and Sb.
Here, the composition cannot freely be changed
independently within the range of the composition of each
element alone, and needless to say, priority is given to
the conditions of the formulae (a) to (g).
[1-3] Other elements
To the phase-change recording material of the
present invention, Au, Ag, Al, Ga, Zn, Si, Cu, Pd, Pt,
Rh, Pb, Cr, Mo, W, Mn, Co, 0, N, Se, V, Nb, Ta, Ti, Bi or
B, or a rare earth element such as Tb, Dy or Gd may, for
example, be added as the case requires to improve various
characteristics. In order to obtain the effect of
improving the characteristics, the addition amount is
preferably at least 0.1 at.% (atomic%) of the entire
composition of the alloy. However, it is preferably at
most 10 at.% in order not to impair the preferred
characteristics of the phase-change recording material of
the present invention. Particularly preferred is
addition of N (nitrogen), and an addition of at least 0.1
atomic% and at most 5 atomic% of the entire composition
is effective to improve the repeated overwriting
durability.
Ag, Cu, Si, Pb, Cr, Mo, W, Mn, Nb, Ta, V, B and a
rare earth element may be used to further finely adjust.
the crystallization temperature or the crystallization
speed.
Al, Ga, Zn, Bi, Pd, Pt and Rh may function as
crystal nuclei for the phase-change recording material of
the present invention which undergoes the crystal growth-
based crystallization process, and can finely adjust the
crystallization process. The above other additional
elements may function as crystal nuclei in some cases.
0 and Se may be used to finely adjust the optical
characteristics.
Here, a rare earth element (rare earth metal
element) is a Group 3B element of the Periodic Table, and
specifically it includes Sc, Y, lanthanoids and
actinoids.
[2] Information recording medium
Now, the information recording medium of the present
invention will be explained below.
The information recording medium of the present
invention is an information recording medium having a
recording layer, characterized in that the above
recording layer contains a composition represented by the
following formula (1) as the main component:
Gex(InwSni-w)yTezSb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge
content, the In content, the Sn content and the Te
content, and x, y, z and w representing atomic ratios,
satisfy the following (i) to (vi):
In the present invention, it is preferred that of
the information recording medium, the crystalline state
corresponds to a non-recorded state, and the amorphous
state corresponds to a recorded state. This is because
it is estimated that not many crystal nuclei are present
in the recording layer composition of the present
invention. That is, in a case where the amorphous states
corresponds to a non-recorded state and crystalline state
marks are formed in the amorphous state, it is preferred
to use a recording layer composition in which many
crystal nuclei are present. This is because when a large
number of crystal nuclei are present in the recording
layer, the shape of the crystalline state marks is less
likely to be influenced by the position of the crystal
nuclei. On the other hand, as described above, not many
crystal nuclei are present in the recording layer
composition of the present invention, and accordingly
favorable recording is likely to be carried out when the
crystalline state corresponds to a non-recorded state and
amorphous state recording marks are formed in the
crystalline state, rather than when the amorphous state
corresponds to a non-recorded state and crystalline state
recording marks are formed in the amorphous state.
By using the composition represented by the above
formula (1) for the recording layer, excellent recording
signal characteristics such as the reflectivity, the
signal amplitude and the jitter characteristics can be
obtained even when recording/erasing is carried out at a
high velocity, and it is possible to obtain favorable
storage stability of the amorphous marks (recording
signals). Further, when the information recording medium
of the present invention is stored for a long term also,
the change in the reflectivity of the recorded signals is
small, and excellent recording signal characteristics can
be maintained even when overwriting is carried out again.
Further, the information recording medium of the present
invention, by employing the above composition, can
provide excellent repeated recording durability. The
explanation regarding the formula (1) is the same as in
the above [1], and explanation is omitted here.
Such an information recording medium is not
particularly limited so long as recording and retrieving
of the information are carried out by detecting the
difference in physical parameters between the crystalline
state and the amorphous state, and an information
recording medium detecting the difference in the
refractivity, the electrical resistance, the volume, the
change in density, etc. may, for example, be mentioned.
Particularly, the information recording medium employing
the phase-change recording material of the present,
invention is suitable for an application to an optical
information recording medium on which recording is
carried out by means of a laser beam. Particularly, it
is suitable for an application to a phase-change type
optical information recording medium utilizing the change
in the reflectivity accompanying a reversible change of
the crystalline state caused by irradiation with a laser
beam.
Now, the specific structure of the optical
information recording medium of the present invention,
the recording and retrieving method, etc. will be
explained below.
[2-1] Optical information recording medium
(Layer structure)
As the optical information recording medium, usually
one having a multilayer structure as shown in Fig. l(a)
or Fig. 1(b) is employed. Namely, it is preferred that
on a substrate, a recording layer containing a
composition represented by the above formula (1) as the
main component is formed, and a protective layer is
further formed, as evident from Fig. 1(a) and Fig. l(b).
The more preferred layer structure of the optical
information recording medium is such a structure that a
first protective layer, a recording layer, a second
protective layer and a reflective layer are formed in
this order along the incident direction of the retrieving
laser beam. Namely, in a case where the retrieving laser
beam enters from the substrate side, preferred is a layer
structure of a substrate, a first protective layer (lower
protective layer), a recording layer, a second protective
layer (upper protective layer) and a reflective layer
(Fig. l(a)), and in a case where the retrieving laser
beam enters from the recording layer side, preferred is a
layer structure of a substrate, a reflective layer, a
second protective layer (lower protective layer), a
recording layer, a first protective layer (upper
protective layer) and a covering layer (Fig. l(b)).
Needless to say, each layer may consist of more than
two layers, and an interlayer may be formed between the
respective layers. For example, between the substrate
and the protective layer when the retrieving laser beam
enters from the substrate side, or on the protective
layer when the retrieving laser beam enters from the side
opposite to the substrate, a transparent and extremely
thin metal, semiconductor or dielectric layer having
absorption, etc. may be formed so as to control the
amount of the laser energy which enters the recording
layer.
Further, a reflective layer is formed on the side
opposite to the incident side of the recording/retrieving
laser beam in many cases as mentioned above, but this
reflective layer is not essential. Further, the
protective layer which is preferably formed on at least
one side of the recording layer may be made to have a
multilayer structure with materials having different
characteristics.
Now, the respective layers will be explained in
detail.
(A) Recording layer
(A-l) Materials contained in recording layer and their
amount
The materials contained in the recording layer
comprise a composition represented by the above formula
(1) as the main component. This composition was already
explained in detail, and the explanation is omitted here.
In order to effectively obtain the effect of the present
invention, the composition represented by the above
formula (1) is contained usually in an amount of at least
50 atomic%, preferably at least 80 atomic%, more
preferably at least 90 atomic%, particularly preferably
at least 95 atomic%, based on the entire recording layer.
The higher the content is, the more remarkably the effect
of the present invention can be obtained. However, even
if another component such as O or N is contained at the
time of film formation of the recording layer, the
effects of the present invention such as high speed
recording/erasing can be securely obtained when the
content is within a range of from several atomic% to 20
atomic%.
(A-2) Film thickness of recording layer
The thickness of the recording layer is usually at
least 1 nm, preferably at least 5 nm. With such a
thickness, the difference in the reflectivity (contrast)
between the crystalline state and the amorphous state
will be adequate, and the crystallization speed will be
adequate, whereby it will be possible to erase the record
in a short time. Further, the reflectivity itself will
be adequate. On the other hand, the thickness of the
recording layer is usually at most 30 nm, preferably at
most 25 nm, more preferably at most 20 nm, particularly
preferably at most 15 nm. With such a thickness, an
adequate optical contrast will be obtained, and cracks
are less likely to form on the recording layer. Further,
deterioration of the recording sensitivity due to
increase in the thermal capacity is less likely to occur.
Further, within the above film thickness range, the
volume change due to the phase change can be moderately
suppressed, and microscopic and irreversible deformation
of the recording layer itself or the protective layer to
be formed on or below the recording layer, which may
cause noises when recording is repeatedly carried out, is
less likely to be accumulated. Such accumulation of the
deformation tends to decrease the repeated recording
durability, and by bringing the film thickness of the
recording layer to be within the above range, this
tendency can be suppressed.
In a case of an optical information recording medium
for high density recording on which recording/retrieving
is carried out by means of a focused laser beam of an
object lens having a numerical aperture of from about 0.6
to about 0.65 from a LD (laser diode) having a wavelength
of about 650 nm, such as rewritable DVD, or an optical
information recording medium for high, density recording
on which recording/retrieving is carried out by means of
a focused laser beam of an object lens having a numerical
aperture of from about 0.7 to about 0.85 from a blue LD
having a wavelength of about 400 nm, the requirement
against noises is more strict. Accordingly, in such a
case, the more preferred thickness of the recording layer
is at most 25 nm.
(A-3) More preferred embodiment regarding recording
layer film thickness
In the present invention, it is considered that with
respect to an optical information recording medium having
a recording layer containing the predetermined Ge-In-Sb-
Sn-Te type composition as the main component, on which
high velocity recording/erasing is possible, by making
the film thickness of the recording layer extremely thin,
the recording characteristics at the second recording
after the optical information recording medium is stored
for a long time can be made good, and decrease in the
reflectivity after the long term storage can be reduced.
Specifically, it seems that by making the film thickness
of the recording layer preferably at most 11 nm, of the
optical information recording medium employing the
recording layer of the above predetermined Ge-In-Sb-Sn-Te
type composition, the recording characteristics at the
second recording after the long term storage tend to be
improved, and the decrease in the reflectivity after the
long term storage tend to be reduced.
Regarding the optical information recording medium
employing the recording layer of the above predetermined
Ge-In-Sb-Sn-Te type composition, the jitter at the second
recording after the long term storage (preservation) is
somewhat poor in some cases.
The recording characteristics at the second
recording after the long term storage (preservation) mean
the characteristics in the following two cases (shelf
second recording, archival second recording).
First, to carry out recording on a medium which is
stored for a long time after the initial crystallization
in a non-recorded state, for the first time after the
preservation, is referred to as shelf first recording,
and to successively carry out overwriting thereon is
referred to as shelf second recording. In a case where
the preservation period is relatively short,
substantially no increase in the jitters is observed when
the shelf second recording is carried out. However, in a
case where the preservation period is long, the increase
in the jitters may be remarkable at the shelf second
recording in some cases. The increased jitters decrease
when the overwriting is carried out repeatedly several
times, and the overwriting recording characteristics
before the preservation recovers. The reason is not
necessarily clear, but is supposed to be related to such
a tendency that the signal intensity at the shelf first
recording after the long term storage is low. Namely,
when recording is carried out after an optical
information recording medium is stored for a long term,
the signal amplitude at the shelf first recording tends
to be low. The signal amplitude recovers by further
recording several times, and accordingly, the decrease in
the signal amplitude at the shelf first recording is
supposed to be caused by that the recording mark is less
likely to be large when the crystalline portion after the
long term storage is formed into an amorphous phase for
the first time. Further, the reason why the jitter is
likely to deteriorate at the shelf second recording after
the long term storage is supposed to be because a portion
which is formed into an amorphous phase for the first
time (a portion which is not irradiated with the
recording laser beam at the shelf first recording) and a
portion which is formed into an amorphous phase again
(for a second time) are both present. Namely, it is
considered that there is a dispersion of the size of the
amorphous marks due to the above presence of two portions
in the shelf second recording.
Further, the cause of such a tendency that the
amorphous marks are less likely to be large at the shelf
first recording after the long term storage is not clear,
but it is supposed that a certain change occurs at the
crystalline portion of the recording layer by the long
term storage, since the characteristics recover after
recording several times. By making the recording layer
extremely thin (preferably at most 11 nm), the
characteristics at the shelf second recording after the
long term storage are improved, and this is considered to
be because the above change at the recording layer
crystalline portion tends to be suppressed.
On the other hand, the other second recording after
the long term storage (preservation) on an overwritable
information recording medium on which amorphous marks are
formed, is a recording in a case where a once recorded
information (a state where amorphous marks are formed) is
preserved for a long term, and overwriting is carried out
again to rewrite the information.
Recording which is carried out on an information
recording medium on which recording is carried out before
the preservation, for the first time after the long term
preservation, will be referred to as the archival second
recording. In this case, in a case where the
preservation period is relatively short, substantially no
increase in the jitters is observed when the archival
second recording is carried out. However, at the
archival second recording in a case where the
preservation period is long, such a phenomenon that the
increase in the jitters is remarkable may be observed in
some cases. The increased jitters decrease when the
overwriting is repeatedly carried out several times.
Further, the overwriting recording characteristics before
the preservation recovers.
It is supposed that the above phenomenon occurs
because the amorphous marks recorded before the storage
are changed into a more stable amorphous state by the
long term storage, and erasure by the recrystallization
will be insufficient even if recording (overwriting) is
further carried out. Since the amorphous state is in a
quasi-stable state, it is possible that the amorphous
state is changed into a more stable amorphous state by
the long term storage. Stable amorphous marks tend to be
less likely to be erased in general, and noises due to
unerased amorphous marks occur.
From the above point of view, the fact that the
jitter decreases when overwriting is successively carried
out after the archival second recording is carried out is
explainable. Namely, when the archival second recording
is carried out, the formed amorphous marks are in "newly
formed" amorphous state, and recover to the initial
amorphous state which is relatively easily erased.
When the recording layer is made to be extremely
thin, it is likely to be influenced by the interface of
another layer which is in contact with the recording
layer. Accordingly, the improvement in the stability of
the amorphous state may be considered to be brought about
by the amorphous state being maintained in a certain
quasi-stable state due to the above effect of the
interface.
Here, regarding the above two second recordings
(shelf second recording, archival second recording), it
is not clear whether either one mainly has influences,
and there is a possibility that both have influences at
the same time.
At any rate, the long term storage stability of
recorded amorphous marks itself is considered to depend
on the above-described subtle change of the crystalline
state and/or the amorphous state of the recording layer.
Further, the first recording on the; non-recorded state
which is stored for a long term is also considered to
depend on the above-described subtle change of the
crystalline state and/or the amorphous state of the
recoding layer. Further, the storage stability of the
recording medium including the shelf and archival second
recordings on a medium which is preserved for a long term
after the recording is also considered to depend on the
above-described subtle change of the crystalline state
and/or the amorphous state of the recording layer.
The above phenomenon is particularly remarkable when
the phase-change recording material of the present
invention is employed particularly for high velocity
recording (approximately, a linear velocity of at least
20 m/s at recording). Heretofore, the above phenomenon
is hardly problematic with respect to an information
recording medium employed for low linear velocity
recording. This is because the recording linear velocity-
has conventionally been low. It is considered that the
above phenomenon is a newly found problem since the
phase-change recording material of the present invention
is applicable for high velocity recording.
With respect to the phase-change recording material
of the present invention, the increase in the jitter at
the shelf second recording and the archival second
recording in high linear velocity recording can be
suppressed low as compared with a conventional eutectic
type material in the vicinity of Sb70Te3O or eutectic type
material in the vicinity of Sb85Ge15. Further, by making
the recording layer thin, the above increase in the
jitter can be suppressed more effectively.
Further, by making the recording layer extremely
thin (preferably at most 11 nm), the decrease in the
reflectivity due to the long term storage tends to be
suppressed. The reason is not clear also, but is
considered that the change of the recording layer at the
long term storage is suppressed in the same manner as in
the case of improvement in the recording characteristics
at the second recording after the long term storage.
With respect to the recording layer having the above
predetermined Ge-In-Sb-Sn-Te type composition, if the In
content is high and the Te content is low, the
reflectivity may decrease after the optical information
recording medium is subjected to an environment
resistance test (in a state similar to the state after
the optical information recording medium is stored for a
long term) in some cases. Accordingly, it is preferred
that the In content and the Te content are in a specific
relation (wxy-z=0.1 in the above formula (1)). However,
the decrease in the reflectivity after the above
environment resistance test (after the long term storage)
tends to be suppressed by making the recording layer
extremely thin, and thus there is a possibility that In
and Te may not be in the above predetermined relation.
This means that the possible recording layer composition
range widens by making the recording layer extremely
thin. From this viewpoint also, it is preferred to make
the recording layer thin.
However, the recording characteristics such as the
signal amplitude may be impaired in some cases if the
recording layer is extremely thin. Regarding this point,
the recording characteristics such as the signal
amplitude can be at an adequately satisfactory level by
adjusting the layer structure and the film thicknesses of
the optical information recording medium.
Namely, in a case of an optical information
recording medium in which on a substrate, a protective
layer, a Ge-In-Sb-Sn-Te type recording layer having a
predetermined composition, a protective layer and a
reflective layer are formed in this order or in the
opposite order, the signal intensity tends to be low when
the recording layer is made extremely thin (thinner than
about 12 nm for example). Accordingly, a device is
required to obtain a high signal intensity, in a case
where the recording layer is made extremely thin (at most
11 nm for example).
For example, one method is to change the film
thickness of the protective layer located on the side
from which the laser beam enters the recording layer.
Namely, the film thickness of the protective layer is
made thinner than the film thickness of the protective
layer with which the reflectivity of the optical
information recording medium reaches the minimum value.
The film thickness with which the reflectivity reaches
the minimum value various depending upon the laser
wavelength to be employed, however, it is in the vicinity
of 50 nm at the film thickness in the vicinity of 650 nm
in DVD. By employing such a film thickness, the signal
intensity becomes optically high.
However, it is known that when the film thickness of
the protective layer on the laser beam incident side
becomes thin, the thermal influence over e.g. the
substrate tends to be significant, and the repeated
recording durability tends to deteriorate in general.
Accordingly, the above method of making the film
thickness of the protective layer thin (in the vicinity
of 50 nm for example) can be hardly employed. It is
considered that a favorable repeated recording durability
of an optical information recording medium can be
obtained by employing a protective layer A (a protective
layer containing a metal oxysulfide and/or a metal
nitride) as described hereinafter for the entire
protective layer or by employing the protective layer A
as described hereinafter for the protective layer region
of the protective layer which is in contact with the
recording layer, even if the film thickness of the
protective layer on the side from which the laser beam
enters relative to the recording layer is made thin (at
most 50 nm for example), against the above tendency. The
details about the protective layer A will be explained
below.
Under the above situation, the film thickness of the
recording layer of the present embodiment is preferably
at most 15 nm, more preferably at most 14 nm, furthermore
preferably at most 13 nm, particularly preferably at most
12 nm, most preferably at most 11 nm.
On the other hand, as mentioned above, also in a
case where the film thickness of the recording layer is
made extremely thin in order to improve the recording
characteristics after the long term storage, no adequate
signal intensity can be obtained even by adjusting the
layers other than the recording layer if the film
thickness of the recording layer is excessively thin.
The lower limit of the signal intensity depends on the
performance of the retrieving apparatus, and in a case of
rewritable DVD, the signal intensity tends to be low and
the use tends to be difficult if the recording layer film
thickness is less than 3 run. Accordingly, the recording
layer film thickness is at least 3 run in rewritable DVD
for example. Usually preferred is a recording layer film,
thickness of at least 5 run.
(A-4) Method for producing recording layer
The above recording layer can be obtained by DC or
RF sputtering of a predetermined alloy target in an inert
gas, particularly in an Ar gas.
Further, the density of the recording layer is
usually at least 80%, preferably at least 90% of the bulk
density. As the bulk density p, an approximate value
from the following mathematical formula (2) is usually
employed, but it may be actually measured by preparing a
mass having an alloy composition constituting the
recording layer:
(2)
wherein mi is the molar concentration of each element i,
and pi is the atomic weight of the element i.
In the sputtering deposition method, the high energy
Ar amount to be irradiated on the recording layer is
increased by lowering the pressure of the sputtering gas
(usually rare gas such as Ar, hereinafter explanation
will be made with reference to the case of Ar) at the
time of deposition, or by disposing the substrate in the
vicinity of the front of the target, thereby to increase
the density of the recording layer. The high energy Ar
is usually either part of Ar ions to be irradiated on the
target for sputtering which are bounced off and reach the
substrate side, or the Ar ions in the plasma which are
accelerated by the sheath voltage of the entire substrate
face and reach the substrate.
Such an irradiation effect of the high energy rare
gas is referred to as an atomic peening effect, and in
the sputtering by an Ar gas which is commonly employed,
Ar is incorporated into the sputtering film by the atomic
peening effect. Accordingly, the atomic peening effect
can be appraised by the Ar amount in the film. Namely,
the small Ar amount indicates a small high energy Ar
irradiation effect, and a film with a low density is
likely to form.
On the other hand, if the Ar amount is large,
irradiation of the high energy Ar tends to be intense,
and the density of the film tends to be high. However,
Ar incorporated in the film is likely to precipitate as a
void at the time of repeated recording, and is likely to
deteriorate the repeated recording durability.
Accordingly, the discharge is carried out under an
appropriate pressure, usually between the order of from
10-2 to 10-1 Pa.
Now, other constituting elements in the structure of
the optical information recording medium which is the
preferred embodiment of the present invention will be
explained below.
(B) Substrate
As the substrate to be used in the present
invention, a resin such as a polycarbonate, an acrylic
resin or a polyolefin, or glass, or a metal such as
aluminum may be employed. Usually guide grooves with a
depth of a level of from 20 to 80 ran are formed on the
substrate, and thus preferred is a substrate made of a
resin on which the guide grooves can be formed by
molding. Further, in the case of a so-called substrate
face incidence (Fig. l(a)) wherein the focused laser beam
for erasing/retrieving the record enters from the
substrate side, the substrate is preferably transparent.
The thickness of the substrate is usually at least
0.05 mm and at most 1.5 mm, however, one of about 1.2 mm
for CD or one of about 0.6 mm for DVD is employed.
Further, in a case where the optical head of the laser
has a high NA and a short wavelength is employed to
achieve a high density, a thin substrate of about 0.1 mm
may also be used.
(C) Protective layer
(C-l) General explanation regarding protective layer used
in the present invention
In order to prevent evaporation and deformation due
to the phase change of the recording layer, thereby to
control the thermal diffusion at that time, usually a
protective layer is formed on one or both sides of the
recording layer, preferably on both sides. The material
of the protective layer is determined taking into
consideration the refractive index, the thermal
conductivity, the chemical stability, the mechanical
strength, the adhesive properties, etc. Usually, a
dielectric such as an oxide, sulfide, nitride or carbide
of a metal or semiconductor, having high transparency and
high melting point, or a fluoride of Ca, Mg, Li or the
like may be employed.
In this case, such an oxide, sulfide, nitride,
carbide or fluoride may not necessarily take a
stoichiometrical composition, and the composition may be
controlled to adjust the refractive index, etc., and it
is effective to use them as a mixture. When repeated
recording characteristics are taken into consideration, a
mixture of dielectrics is preferred. More specifically,
a mixture of ZnS or a chalcogen compound such as a rare
earth sulfide with a heat resistant compound such as an
oxide, nitride, carbide or fluoride may be mentioned.
For example, a mixture of heat resistant compounds
containing ZnS as the main component, or a mixture of
heat resistant compounds containing an oxysulfide of the
rare earth, particularly Y2O2S as the main component is
one example of the preferred protective layer
composition.
As the material to form the protective layer,
usually a dielectric material may be mentioned. The
dielectric material may, for example, be an oxide of e.g.
Sc, Y, Ce, La, Ti, Zr, Hf, V, Nb, Ta, Zn, Al, Cr, In, Si
or Ge, a nitride of e.g. Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Zn, B, Al, Si, Ge or Sn, a carbide of e.g. Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W or Si, or a mixture thereof.
Further, as the dielectric material, a sulfide, selenide
or telluride of e.g. Zn, Y, Cd, Ga, In, Si, Ge, Sn, Pb,
Sb or Bi, an oxysulfide of e.g. Y or Ce, a fluoride of
e.g. Mg or Ca, or a mixture thereof, may be mentioned.
Further, as a specific example of the dielectric
material, ZnS-SiO2, SiN, SiO2, TiO2, CrN, TaS2 or Y2O2S
may, for example, be mentioned. Among these materials,
ZnS-SiO2 is widely used in view of the high film
deposition rate, the small film stress, the low rate of
change of the volume due to the change in the temperature
and the excellent weather resistance. In a case where
ZnS-SiO2 is used, the compositional ratio of ZnS to SiO2
i.e. ZnS:SiO2 is usually from 0:1 to 1:0, preferably from
0.5:0.5 to 0.95:0.05, more preferably from 0.7:0.3 to
0.9:0.1. Most preferably ZnS:SiO2 is 0.8:0.2.
Taking the repeated recording characteristics into
consideration, the film density of the protective layer
is preferably at least 80% of the bulk state in view of
the mechanical strength. In a case where a mixture of
dielectrics is used, the theoretical density of the
above-described mathematical formula (2) is employed as
the bulk density.
The thickness of the protective layer is usually at
least 1 nm and at most 500 nm in general. When it is at
least 1 nm, the effect of preventing the deformation of
the substrate or the recording layer can be secured, and
a role as the protective layer can be fulfilled.
Further, when it is at most 50 0 nm, while the role as the
protective layer can be fulfilled, such a phenomenon can
be prevented that the internal stress of the protective
layer itself, the difference in the elastic
characteristics with the substrate or the like will be
remarkable, and thus cracks are formed.
Particularly when a first protective layer is
formed, the first protective layer is required to
suppress e.g. deformation of the substrate (deformation
of the covering layer) due to heat, and thus its
thickness is usually at least 1 nm, preferably at least 5
nm, particularly preferably at least 10 nm. With such a
thickness, accumulation of the microscopic deformation of
the substrate during the repeated recording can be
suppressed, and no remarkable noise increase by
scattering of the retrieving laser beam will occur.
On the other hand, the thickness of the first
protective layer is preferably at most 200 nm, more
preferably at most 150 nm, furthermore preferably at most
100 nm, with relation to the time required for film
formation. With such a thickness, e.g. the change of the
groove shape of the substrate as viewed on the recording
layer plane is less likely to occur. For example, such a
phenomenon that the depth or width of the grooves is
smaller than the intended shape on the substrate surface
is less likely to take place.
On the other hand, in a case where a second
protective layer is formed, the thickness of the second
protective layer is usually at least 1 nm, preferably at
least 5 nm, particularly preferably at least 10 nm so as
to suppress the deformation of the recording layer.
Further, it is preferably at most 200 nm, more preferably
at most 150 nm, furthermore preferably at most 100 nm,
particularly preferably at most 50 nm, so as to prevent
accumulation of the microscopic plastic deformation in
the interior of the second protective layer which occurs
due to the repeated recording and to suppress the noise
increase due to the scattering of the retrieving laser
beam.
The thicknesses of the recording layer and the
protective layers are selected taking into consideration
the interference effects attributable to the multilayer
structure in addition to the restrictions from the
viewpoint of the mechanical strength and reliability, so
that the efficiency for absorption of the laser beam will
be good, and the amplitude of recording signals, i.e. the
contrast between the recorded state and the non-recorded
state, will be large.
The protective layer is produced usually by a known
sputtering method.
The protective layer may be constituted by a
plurality of layers made of different materials as
described above. Particularly, it is preferred to form
an interfacial layer containing no sulfur or having a low
sulfur content at the interface on the side which is in
contact with the recording layer and/or at the interface
on the side which is in contact with the reflective layer
containing Ag as the main component.
The interfacial layer to be formed on the interface
on the side which is in contact with the recording layer
containing Ag as the main component is usually used to
suppress the reaction of Ag with sulfur (corrosion of Ag)
in a case where the protective layer contains sulfur.
The material of the interfacial layer may be Ta, Nb
or Mo. Among these materials, preferred is Nb or Mo.
The atomic weight of Nb or Mo is relatively close to that
of Ag contained in the reflective layer, and the exit
angle of each element from the target will be
substantially the same as that of Ag at the time of
deposition by means of a sputtering method, and thus
there is such an advantage that the film thickness
distribution on the substrate which faces the target can
be secured, and uniformity is easily secured. Further,
the cost of Nb or Mo per 1 kg of the raw material is 1/10
to 1/100 and is very low, and the target can be produced
at a low cost, such being favorable.
The content of the material in the interfacial layer
is preferably at least 80 atomic%, more preferably at
least 90 atomic%, particularly preferably at least 95
atomic%, and it is most preferably 100 atomic% (that is,
the interfacial layer is made of pure Nb in an example of
using Nb for the interfacial layer).
The interfacial layer may contain other elements to
such an extent that the characteristics of the layer are
not impaired, as the case requires. In a case where
other elements are contained, the content of the above
elements is preferably at most 2 0 atomic%, more
preferably at most 10 atomic%, particularly preferably at
most 5 atomic%, most preferably at most 2 atomic%.
Further, the above elements may, for example, be Ni, Pd,
Pt, Si, O, Se, V, Ti or Ta.
The interfacial layer may be made of a dielectric
material containing no sulfur, other than the above.
Specifically, an oxide, nitride or carbide of a metal or
semiconductor, such as SiC, Si3N4, SiC, GeN, Ta2O5,
ZrO2AlN or Al2O3 may, for example, be employed. They may
not necessarily take a stoichiometrical composition, and
a mixture may also be used.
The film thickness of the interfacial layer is
preferably at least 1 nm, more preferably at least 2 nm.
The reaction between the protective layer and the
reflective layer may not effectively suppressed in some
cases if the interfacial layer is excessively thin.
However, within the above range, the reliability of the
optical information recording medium will be favorably
secured even in a reliability test in a severe
environment at a high temperature in high humidity
(80°C/85%RH for example).
On the other hand, the film thickness of the
interfacial layer is preferably at most 10 run, more
preferably at most 8 nm, furthermore preferably at most 6
nm. Within the above range, the reaction between Ag in
the reflective layer and S in the protective layer can be
suppressed while the transmittance of the interfacial
layer is favorably secured.
The interfacial layer is formed usually by a
sputtering method.
(C-2) Preferred embodiment of protective layer
It is preferred that the information recording
medium used in the present invention has a protective
layer A in contact with the recording layer employing the
predetermined Ge-In-Sb-Sn-Te type material, and the
protective layer A contains a metal oxysulfide and/or a
metal nitride.
In a case where the information recording medium of
the present invention is used as a phase-change type
optical information recording medium, as the material of
the protective layer, usually (ZnS)80(SiO2)20 is used.
This is because this material is excellent in
transparency, the adhesive properties to a conventional
recording layer, the sputtering rate, the cost, etc.
However, when the protective layer of the above
(ZnS)80(SiO2) 20 is used for the recording layer having the
predetermined Ge-In-Sb-Sn-Te type composition on which
high speed recording/erasing is possible, an object to
further improve the repeated recording durability arises
in some cases. It is considered that one cause is that a
quick change in temperature is brought about in erasing
the record of an optical information recording medium for
high speed recording, as compared with an optical
information recording medium for low speed recording.
For example, in a case where the recording linear
velocity doubles, the time to increase the temperature of
the recording layer by irradiation with the laser beam
will be 1/2, and further, the cooling rate tends to be
high also. This is because the temperature distribution
of the melted region of the recording layer is gentle
when the recording is carried out at a low linear
velocity, whereas it tends to be sharp when the recording
is carried out at a high linear velocity. Further, the
distance between the melted region and the laser beam
tends to be relatively long in the recording at a high
linear velocity as compared with the recording at a low
linear velocity. Of course, as the cause of the above
repeated recording durability not being adequate, a cause
resulting from the recording layer material itself, such
as a difference in properties regarding the material flow
due to the melting and solidification, or such a cause
that the atomic diffusion of e.g. sulfur which is
reported in the case of the combination with a
conventional recording material is more likely to occur,
may also be considered.
In the present invention, by forming a protective
layer A containing GeN for example as the metal nitride
or Y2O2S for example as the metal oxysulfide in contact
with the recording layer containing a Ge-In-Sb-Sn-Te type
recording layer material, further improvement of the
repeated recording durability of the information
recording medium can be expected. The reason why the
improvement of the repeated recording durability can be
expected by forming a protective layer A containing a
metal nitride such as GeN or a metal oxysulfide such as
Y2O2S is not necessarily clear, but is supposed to be
because effects to suppress the deformation of the
recording layer due to the quick change in the
temperature by carrying out the high speed recording as
compared with a conventional one, the material flow in
the recording layer, the atomic diffusion between the
layers, can be obtained.
As mentioned above, when the protective layer A in
contact with the recording layer contains a metal
oxysulfide or a metal nitride, the repeated recording
characteristics (repeated overwriting characteristics)
tend to improve. Accordingly, it is considered that the
above protective layer A has a high affinity with Sb, Ge,
In and Sn constituting the phase-change recording
material of the present invention.
(1) Protective layer A
In the present invention, it is preferred to
incorporate a metal oxidesulfide and/or a metal nitride
into the protective layer A in contact with the recording
layer. Of course, a metal oxysulfide and a metal nitride
may be used together. Now, explanation will be made in
further detail.
(1-1) Protective layer A containing metal oxysulfide
In the present invention, it is preferred to use the
protective layer A containing a metal oxysulfide.
Containing a metal oxysulfide means that the constituting
element is present while maintaining the form of the
metal oxysulfide.
In the present invention, it is expected that the
durability when recording is carried out repeatedly on
the information recording medium further improves by
forming the protective layer A containing a metal
oxysulfide in contact with the recording layer having a
specific composition. The reason is not clearly
understood yet, but is supposed to be related with high
thermal conductivity and hardness of the protective layer
A containing a metal oxysulfide and high uniformity of
the distribution of the constituting element. Namely,
the protective layer A in the present invention has high
thermal conductivity and hardness as compared with a
protective layer employing a composite dielectric
containing ZnS as the main component, as represented by a
ZnS-SiO2 film which has conventionally been commonly
used. On the other hand, the refractive index of the
protective layer A is usually from about 1.7 to about
2.4 although it depends on the compositional ratio, and
is substantially the same as that of a protective layer
employing a composite dielectric containing ZnS as the
main component.
Further, it is supposed that deformation of the
recording layer due to thermal expansion tends to be
small since the thermal conductivity of the protective
layer A containing a metal oxysulfide is high. Namely,
since the thermal conductivity of the protective layer A
is high, the heat of the recording layer which is heated
when the recording marks are formed by the laser can be
let loose quickly. Accordingly, the difference in
temperature between the interfacial region which is in
contact with the recording layer of the protective layer
A and the region of the protective layer A which is apart
from the recording layer, or the difference in
temperature between the mark-formed region and the
peripheral region can be instantaneously dissolved. As a
result, peeling of the film or occurrence of the cracks
resulting from the difference in temperature can be
suppressed. In other words, it is thought that the
overwriting deterioration can be delayed. The thermal
conductivity can be indirectly known from the value of
the laser power when amorphous marks are formed on the
prepared disk. Namely, the higher the thermal
conductivity, the higher the laser power required to heat
the recording layer tends to be high. For example, in a
case where a protective layer A containing a metal
oxysulfide is used, the power required for mark formation
tends to be high as compared with a case where a
protective layer of ZnS:SiO2=80:20 (mol%) is used. This
is because the function of the protective layer A as a
heat dissipation layer is increased due to a high thermal
conductivity.
Further, the JIS Knoop hardness of the protective
layer using ZnS:SiO2=80:20 (mol%) is 280, whereas the JIS
Knoop hardness of the protective layer A using Y2O2S for
example as the metal oxysulfide is 520. The protective
layer A having a high hardness is important with a view
to preventing the deformation of the recording layer. If
the hardness is low, it is difficult to appropriately
suppress the change in the volume of the recording layer
due to recording/erasing, i.e. the deformation resulting
from the difference in the volume between the amorphous
state and the crystalline state, and the deformation is
accumulated along with the increase in the number of the
overwriting, thus causing decrease in the signal
intensity.
Further, in the protective layer A containing a
metal oxysulfide, the metal atom is bonded to both sulfur
and oxygen, and accordingly the mixing properties of
sulfur with oxygen are incomparably high in comparison
with a protective layer employing a mixture of a sulfide
and an oxide such as ZnS-SiO2 or ZnS-Y2O3. Accordingly,
it is supposed that the protective layer A has stably
high performance since the dispersibility of sulfur and
oxygen with metal atoms such as selenium atoms is higher
than conventional ZnS-SiO2- Accordingly, it is thought
that such a phenomenon that sulfur diffusion from the
protective layer to the recording layer during the
repeated overwriting to cause a decrease in the
reflectivity or a change in the crystallization speed is
suppressed.
Further, in a case where the protective layer A
containing a metal oxysulfide such as Y2O2S is formed in
contact with the predetermined Ge-In-Sb-Sn-Te type
recording layer to be used in the present invention, the
signal amplitude of the information recording medium
tends to be high as compared with a case where the
protective layer A contains a metal nitride such as GeN.
The reason is not clear, but such a reason that the
properties of the crystal growth of the recording layer
are slightly changed by the protective layer A in contact
with the recording layer, and the size of the amorphous
marks to be formed varies, may be considered. Such
properties are considered to be determined by the
combination of the recording layer material and the
material of the protective layer A, and with respect to
the conventional recording layer material, the change of
the signal intensity by the material of the protective
layer A has not attracted an attention.
As the metal element used for the metal oxysulfide,
a rare earth metal element such as Sc, yttrium or a
lanthanoid element such as La or Ce; or a transition
metal element such as Ti may, for example, be mentioned.
Among them, a rare earth metal element is preferred, a
rare earth metal element selected from the group
consisting of yttrium and La, Ce, Nd, Sm, Eu, Gd, Tb and
Dy is particularly preferred, and most preferred is
yttrium or Ce. The oxysulfide of yttrium (Y2O2S) is
thermochemically more stable than Y2O3 or Y2S3 up to about
1000°C, and accordingly the most preferred element is
yttrium.
The content of the metal oxysulfide in the
protective layer A is preferably at least 5 mol%, more
preferably at least 10 mol%, most preferably at least 15
mol%. If the content of the metal oxysulfide is too low,
the overwriting characteristics may be insufficient in
some cases. On the other hand, in view of the repeated
overwriting characteristics etc., the content of the
metal oxysulfide in the protective layer A is preferably
as high as possible, and the content of the metal
oxysulfide in the protective layer A may be at most 100
mol%.
Further, the content of the metal element
constituting the metal oxysulfide in the protective layer
A is usually at least 10 atomic%, preferably at least 20
atomic%, more preferably at least 2 5 atomic%. The
content of the metal element constituting the metal
oxysulfide is an index indicating the content of the
metal oxysulfide in the protective layer A, and if the
metal element is too small, the effect for further
improving the overwriting characteristics may not be
adequate in some cases. On the other hand, in view of
the repeated overwriting characteristics, the content of
the metal oxysulfide in the protective layer A is
preferably as high as possible, and thus the upper limit
of the content of the metal element constituting the
metal oxysulfide is the content of the metal element when
the protective layer A consists entirely of the metal
oxysulfide.
Further, for the protective layer A, a metal
oxysulfide and another material may be used together.
Said another material is not particularly limited so long
as it is a material which is commonly used for the
protective layer. For example, a material exemplified in
the above "General explanation regarding protective layer
used in the present invention" may optionally be used.
More specifically as another material, an oxide,
sulfide, nitride, carbide or fluoride of a metal or
semiconductor, as represented by zinc sulfide, zinc
oxide, silicon oxide, silicon nitride, aluminum nitride,
aluminum oxide, a rare earth oxide, a rare earth sulfide,
a rare earth fluoride, magnesium fluoride, etc. may, for
example, be mentioned. Among them, particularly
preferred is a zinc compound such as zinc sulfide or zinc
oxide, which is excellent in the adhesive properties to
the recording layer. As a result, a more stable and
higher durability can be obtained.
In a case where another material is contained in the
protective layer A other than the metal oxysulfide, the
content of the material is usually at most 99 mol%,
preferably at most 90 mol%. On the other hand, it is
usually at least 1 mol%, preferably at least 5 mol%.
However, the appropriate content varies depending
upon the type of the material to be mixed. For example,
in a case where zinc sulfide is used as the above
material, its amount may be high, and it is usually at
least 20 mol%, preferably at least 30 mol%, furthermore
preferably at least 50 mol%, most preferably at least 60
mol%.
On the other hand, in a case where zinc oxide is
used as the above material, a too high content tends to
be unfavorable, and the content is usually at most 30
mol%, preferably at most 20 mol%, furthermore preferably
at most 10 mol%. Further, the molar content of zinc
oxide is more preferably at most half the molar content
of the metal oxysulfide.
As the particularly preferred composition of the
protective layer A, a mixed composition containing Y2O2S
and ZnS may be mentioned. In this case, particularly
excellent overwriting characteristics can be obtained.
In this case, the molar ratio of ZnS to Y2O2S is usually
at least 1%, preferably at least 5%, more preferably at
least 10%, and usually at most 1000%, preferably at most
700%, furthermore preferably at most 500%.
Further, it is possible to let zinc in the metal
form be present in the protective layer A. However, it
is contained preferably in the form of a zinc compound
such as zinc oxide or zinc sulfide as described above.
In the present invention, the purity of the
protective layer A (the content of the metal oxysulfide
or the content of a mixture of the metal oxysulfide with
another material in the protective layer A) is preferably
at least 90 mol%. The purity is preferably as high as
possible, however, the influence of impurities in an
amount less than 10 mol% over the characteristics of the
protective layer A is negligible. Particularly when the
impurities are stable compounds, the bad influence tends
to be small, however, if the amount of the impurities
exceeds 10 mol%, there is high possibility that the
physical property values such as the hardness or the
stress of the film change, and the characteristics of the
protective layer A may deteriorate.
The protective layer A containing a metal oxysulfide
can be formed by deposition by means of a sputtering
method using a target containing a metal oxysulfide.
Usually, a target having a composition within, a range
substantially the same as the preferred composition of
the protective layer A is used.
Namely, it is preferred to use one containing a
metal oxysulfide as the target for sputtering. The type
of the metal element of the metal oxysulfide to be used
for the target is optionally selected according to the
composition of the protective layer A.
Further, in a case where the protective layer A
contains a metal oxysulfide and another protective layer
material, a target of a mixture of the metal oxysulfide
and the another material may be used in accordance with
the composition of the another material to be used.
Further, a target of the metal oxysulfide and a target of
the above another material may be separately prepared,
and they are subjected to sputtering at the same time.
The content of the metal oxysulfide in the target is
usually at least 10 mol%, preferably at least 30 mol%,
more preferably at least 50 mol%. If the content of the
metal oxysulfide in the target is excessively low, the
metal oxysulfide may be decomposed in the target, whereby
the metal oxysulfide cannot be incorporated in the
protective layer A in some cases. On the other hand, the
content of the metal oxysulfide in the target varies
depending upon the content of the above another material
used. However, in a case where a target comprising only
metal oxysulfide is used, the content of the metal
oxysulfide in the target is usually 100 mol%.
Whether or not the metal oxysulfide is contained in
the target can be confirmed by measuring the X-ray
diffraction of the target.
Further, the target containing a metal oxysulfide is
produced usually by using a powder of the metal
oxysulfide or a mixed powder of an oxide and a sulfide of
the same metal, by using a known method such as hot
pressing method. Preferred as the metal element to be
used is a rare earth metal element.
As the conditions for sputtering, known conditions
may be employed.
For the analysis of the composition of the
protective layer A, usually the composition may be
identified by combination of e.g. Auger electron
spectroscopy (AES), Rutherford back scattering (RBS),
inductively-coupled plasma spectrometry (ICP) etc.
(1-2) Protective layer A containing metal nitride
In the present invention, it is preferred to use a
protective layer A containing a metal nitride.
A metal nitride tends to have a high thermal
conductivity similar to the metal oxysulfide.
Accordingly, it is considered that the high thermal
conductivity of the protective layer A suppresses peeling
of the film or occurrence of the cracks resulting from
the difference in temperature, and can delay
deterioration during the overwriting, similar to the
above case of one containing a metal oxysulfi.de as
mentioned above.
As the metal to be used for the metal nitride, at
least one element selected from the group consisting of
Si, Ge, Al, Ti, Ta, Cr, Mo, Sb, Sn, Nb, Y, Zr and Hf may,
for example, be mentioned. The nitride of such an
element is stable, and thus the storage stability of the
optical information recording medium tends to improve.
Preferred as the above element is Si, Ge, Al or Cr which
provides higher transparency and excellent adhesion
properties. A plurality of the above elements may be
used. In a case of a nitride of an alloy comprising a
plurality of the above elements, it is preferred to use a
nitride of an alloy containing Ge as the main component.
"Containing Ge as the main component" means that the Ge
content in the alloy is usually at least 50 atomic%,
preferably at least 70 atomic%, more preferably at least
80 atomic%, particularly preferably at least 90 atomic%,
most preferably at least 95 atomic%.
In a case where one type of the above elements is
used, as the material formed by the above element and
nitrogen, nitride of the above element simple substance
may be mentioned. More specifically, a composition in
the vicinity of e.g. Si-N, Ge-N, Cr-N or Al-N may be
mentioned. Among them, in view of higher effect for
preventing diffusion against the recording layer, it is
preferred to use Si-N (nitride of silicon) , Ge-N (nitride
of germanium) or Al-N (nitride of aluminum), and it is
more preferred to use Ge-N (nitride of germanium). In
this case, an nitride of an alloy containing Ge as the
main component, having part of Ge substituted by e.g. Cr
may also be used. However, the amount substituted is
preferably at most 50%, more preferably at most 3 0% of Ge
by the atomicity ratio.
In a case where at least two of the above elements
are used, as the material formed by the above elements
and nitrogen, a composite nitride of the above elements
may be mentioned. As such a compound, as representative
examples using Ge-N, one containing, together with Ge,
e.g. Al, B, Ba, Bi, C, Ca, Ce, Cr, Dy, Eu, Ga, In, K, La,
Mo, Nb, Ni, Pb, Pd, Si, Sb, Sn, Ta, Te, Ti, V, W, Yb, Zn
or Zr, such as Ge-Si-N, Ge-Sb-N, Ge-Cr-N, Ge-Al-N, Ge-Mo-
N or Ge-Ti-N may be mentioned.
The content of the metal nitride in the protective
layer A is preferably at least 5 mol%, more preferably at
least 10 mol%, most preferably at least 15 mol%. If the
content of the metal nitride is too low, the overwriting
characteristics may decrease in some cases. On the other
hand, in view of the repeated overwriting characteristics
etc., the content of the metal nitride in the protective
layer A is preferably as high as possible, and the
content of the metal nitride in the protective layer A
may be at most 100 mol%.
Further, the content of the metal element
constituting the metal nitride in the protective layer A
is usually at least 10 atomic%, preferably at least 20
atomic%, more preferably at least 25 atomic%. If the
content of the metal oxysulfide is too low, the effect
for further improving the overwriting characteristics may
not be adequate in some cases. On the other hand, in
view of the repeated overwriting characteristics etc.,
the content of the metal nitride in the protective layer
A is preferably as high as possible, and thus the upper
limit of the content of the metal element constituting
the metal nitride is the content of the metal element
when the protective layer A consists entirely of the
metal nitride.
Further, for the protective layer A, a metal nitride
and another material may be used together. As the
another material and its content, the same ones as
explained for the protective layer A containing a metal
oxysulfide may be employed.
In the present invention, the purity of the
protective layer A (the content of the metal nitride or
the content of a mixture of the metal nitride and another
material in the protective layer A) is preferably at
least 90 mol%. The purity is preferably as high as
possible, however, the influence of impurities in an
amount less than 10 mol% over the characteristics of the
protective layer A is negligible. Particularly when the
impurities are stable compounds, the bad influence tends
to be small, however, if the amount of the impurities
exceeds 10 mol%, there is high possibility that the
physical property values such as the hardness or the
stress of the film change, and the characteristics of the
protective layer A may deteriorate.
The protective layer A containing a metal nitride
can be formed by means of a sputtering method using a
target containing a metal nitride. Further, the
protective layer A may be formed also by a reactive
sputtering method in which a slight amount of a mixed gas
of Ar and N2 is flown in a vacuum chamber, and under a
predetermined vacuum pressure, a voltage is applied to a
target comprising a predetermined metal (a single metal
element or a metal element composite in the metal nitride
contained in the protective layer A) for discharge, and
the ejected single metal element or metal element
composite is reacted with N2 to convert it into a nitride
for deposition. Here, it has to be noted that the
transparency of the protective layer A is hardly secured
if the nitrogen content in the protective layer A is
excessively low, and the improvement of the repeated
recording durability of the optical information recording
medium tends to be insufficient if the nitrogen content
is excessively high. Accordingly, in a case where the
above reactive sputtering method is employed, it is
important to adjust the nitrogen flow amount. Further,
the pressure at the time of sputtering also has an
influence over the film properties. Usually, by
decreasing the pressure, the protective layer A can be
formed densely.
For the analysis of the composition of the
protective layer A, the composition can be identified
usually by combination of Auger electron spectroscopy
(AES), Rutherford back scattering (RBS), inductively-
coupled plasma spectroscopy (ICP) etc.
(1-3) Film thickness of protective layer A
The preferred range of the film thickness of the
protective layer A varies depending upon the position at
which the protective layer A is used.
Namely, in a case where the protective layer A is
formed as the first protective layer, the first
protective layer is required to suppress e.g. the
deformation of the substrate due to heat, and its
thickness is usually at least 1 nm, preferably at least 5
ran, particularly preferably at least 10 nm. With such a
thickness, accumulation of the microscopic deformation of
the substrate during the repeated recording can be
suppressed, and no remarkable noise increase by
scattering of the retrieving laser beam will occur.
On the other hand, the thickness of the first
protective layer is preferably at most 200 nm, more
preferably at most 150 nm, furthermore preferably at most
10 0 nm, with relation to the time required for film
formation. With such a thickness, e.g. a change in the
groove shape of the substrate as viewed on the recording
layer plane is less likely to occur. For example, such a
phenomenon that the depth or width of the grooves is
smaller than the intended shape on the substrate surface
is less likely to take place.
In a case where the protective layer A is formed as
the second protective layer, the thickness of the second
protective layer is usually at least 1 nm, preferably at
least 5 nm, particularly preferably at least 10 nm so as
to suppress deformation of the recording layer. Further,
in order to prevent accumulation of microscopic plastic
deformation in the interior of the second protective
layer which occurs along with the repeated recording,
thereby to suppress the noise increase by scattering of
the retrieving laser beam, it is preferably at most 200
nm, more preferably at most 150 nm, furthermore
preferably at most 100 nm, particularly preferably at
most 50 nm.
However, in the present invention, usually the
protective layer A having a high thermal conductivity and
having a high hardness is formed in contact with the
recording layer, and accordingly the film thickness of
the protective layer A located on the side from which the
laser beam enters relative to the recording layer can be
made thin, as explained above. Namely, in a case where
the protective layer A is formed in contact with the
recording layer face on the side from which the laser
beam enters, the film thickness of the protective layer A
is preferably at most 50 nm.
The sputtering rate of the material containing a
metal oxysulfide such as Y2O2S as the main component,
tends to be lower than the sputtering rate of a material
such as (ZnS)80(SiO2)20 which has conventionally been
employed. Accordingly, with a view to increasing the
productivity of the information recording medium, the
protective layer A containing a metal oxysulfide may be
formed relatively thinly in contact with the recording
layer and a protective layer B may be formed in contact
with the protective layer A. Further, a material which
has conventionally been employed (e.g. (ZnS)80(SiO2) 20)
may be used for the protective layer B. The details of
the specific embodiment of such an information recording
medium will be described hereinafter.
As mentioned above, in a case where the protective
layer has a multilayer structure by using the protective
layer A and the protective layer B, the film thickness of
the protective layer A in the present invention is
usually at least 0.1 nm, preferably at least 1 nm, more
preferably at least 5 nm. On the other hand, the film
thickness of the protective layer A is usually at most
100 run, preferably at most 50 nm, more preferably at most
2 5 nm, furthermore preferably at most 10 nm.
(1-4) Position of protective layer A and recording layer
In the present invention, it is preferred that the
protective layer A containing a metal oxysulfide and/or a
metal nitride is formed in contact with the recording
layer. More preferably, the above predetermined
protective layer A is formed on both sides of the
recording layer. It is because the repeated overwriting
characteristics can be further improved by forming the
above predetermined protective layer A on both sides of
the recording layer. In general, by forming the above
predetermined protective layer A on both sides of the
recording layer, the recording layer and the protective
layer A tend to peel off, however, it is considered that
the above problem of peeling is less likely to occur in
the recording layer employing the predetermined Ge-In-Sb-
Sn-Te type composition of the present invention.
For example, if the protective layer A containing a
metal oxysulfide such as Y2O2S is formed in contact with
a conventional recording layer of SbTe eutectic
composition, film peeling in an environment resistance
test tends to occur. This tendency becomes more
remarkable if the above protective layer A is formed on
both sides of the recording layer. For example, with
respect to a conventional recording layer employing a
SbTe eutectic type composition, if the protective layer A
containing a metal oxysulfide such as Y2O2S is formed in
contact with both sides of the recording layer, film
peeling occurs in an environment resistance test with
high humidity, and the adhesive properties and the
weather resistance of the film tend to be not necessarily
sufficient.
On the other hand, in a case where the protective
layer A containing a metal oxysulfide such as Y2O2S is
formed in contact with a recording layer employing the
predetermined Ge-In-Sb-Sn-Te type composition of the
present invention, film peeling hardly occurs in an
environment resistance test even when the protective
layer A is formed on both sides of the recording layer,
and repeated recording durability does not substantially
change as before and after the environment resistance
test.
Further, when the protective layer A containing a
metal oxysulfide such as Y2O2S is formed in contact with
the recording layer employing a conventional SbTe
eutectic type composition, the stability of the amorphous
marks tends to deteriorate. On the other hand, with the
predetermined Ge-In-Sb-Sn-Te type composition used in the
present invention, the stability of the amorphous marks
can be increased by adjusting the composition.
Accordingly, deterioration of the stability of the
amorphous marks can be suppressed even when the
protective layer A containing a metal oxysulfide such as
Y2O2S is formed in contact with the recording layer.
(2) Protective layer B
Another example of the preferred layer structure of
the optical information recording medium is to make one
or both of the first and second protective layers have a
two-layer structure comprising the protective layer A and
the protective layer B. In view of e.g. the repeated
overwriting, it is preferred to make the first protective
layer located on the laser beam incident side have a two-
layer structure (Figs. 5(a), 5(b)), and it is more
preferred to make both the first and the second
protective layers have a two-layer structure comprising
the protective layer A and the protective layer B (Figs.
6(a), 6(b)).
In the above preferred layer structure, the first
protective layer or the second protective layer has a
two-layer structure comprising the protective layer A and
the protective layer B, however, the layer structure is
not limited to such an embodiment so long as the
protective layer A is formed in contact with the
recording layer. For example, it may be optionally
carried out to make the first protective layer or the
second protective layer have a multilayer structure of at
least three layers, by further forming a protective layer
formed by another material in contact with the protective
layer B.
(2-1) Material, production method etc. of protective
layer B
As the material of the protective layer B, a
material commonly used for the protective layer may
optionally be used. Such a material has already been
explained, and the explanation is omitted here. The
protective layers A and B may be two layers comprising
different materials, or they may have a gradient
composition in which the respective components gradually
change.
Further, as the method for producing the protective
layer, a production method commonly used for the
protective layer may be used.
(2-2) Film thickness of protective layer B
The protective layer B is in contact with the
protective layer A, and plays a role as the protective
layer in a two-layer structure of the protective layer A
and the protective layer B. Accordingly, the film
thickness of the protective layer B is a film thickness
obtained by subtracting the film thickness of the
protective layer A from the film thickness which is
usually required for a protective layer.
However, in the present invention, the protective
layer A usually having a high thermal conductivity and a
high hardness is formed in contact with the recording
layer, and accordingly the film thickness of the
protective layer located on the side from which the laser
beam enters relative to the recording layer (for example,
the film thickness of the protective layer A in a case
where the protective layer is formed only by the
protective layer A, or the total film thickness of the
protective layer A and the protective layer B in a case
where the protective layer A and the protective layer B
are laminated to form the protective layer) can be made
thin, as explained above.
Namely, the total of the film thickness of the
protective layer A and the film thickness of the
protective layer B is preferably at most 50 nm, in a case
where the protective layer A is formed in contact with
the recording layer face on the side from which the laser
beam enters, and the protective layer B is further formed
in contact with the protective layer A.
As mentioned above, in a case where the protective
layer has a multilayer structure by using the protective
layer A and the protective layer B, the film thickness of
the protective layer A in the present invention is
usually at least 0.1 nm, preferably at least 1 nm, more
preferably at least 2 nm, furthermore preferably at least
3 ran, particularly preferably at least 5 nm. On the
other hand, the film thickness of the protective layer A
is usually at most 100 nm, preferably at most 50 nm, more
preferably at most 25 nm, furthermore preferably at most
10 nm. Accordingly, the film thickness of the protective
layer B is the rest obtained by subtracting the film
thickness of the protective layer A from the total film
thickness of the protective layer.
The thicknesses of the recording layer and the
protective layers are selected taking into consideration
the interference effects attributable to the multilayer
structure in addition to restrictions from the viewpoint
of the mechanical strength and reliability, so that the
efficiency for absorption of the laser beam will be good,
and the amplitude of recording signals, i.e. the contrast
between the recorded state and the non-recorded state,
will be large.
(D) Reflective layer
In the optical information recording medium, a
reflective layer may further be formed. In the present
invention, it is preferred that the optical information
recording medium further has a reflective layer with a
view to increasing the heat dissipation properties of the
recoding layer.
The position at which the reflective layer is formed
usually depends at the incident direction of the
retrieving laser beam, and it is formed on the opposite
side of the recording layer from the incident side.
Namely, in a case where the retrieving laser beam enters
from the substrate side, the reflective layer is formed
usually on the opposite side of the recording layer from
the substrate, and in a case where the retrieving laser
beam enters from the recording layer side, the reflective
layer is formed usually between the recording layer and
the substrate (Figs. l(a), l(b)).
Here, in addition to the reflective layer which
completely reflects laser beam, an extremely thin
reflective layer material layer which transmits at least
half of the laser beam may be formed on the incident side
of the recording layer in some cases, and this is used as
a transparent reflective layer and distinguished from the
reflective layer. The purpose of forming the transparent
reflective layer is usually to adjust the phase of the
incident laser beam or the reflective laser beam, or to
accelerate heat dissipation from the protective layer on
the incident laser beam side.
As the material to be used for the reflective layer,
a substance having a high reflectivity is preferred, and
particularly preferred is a metal such as Au, Ag or Al
which can be expected to have a heat dissipation effect
also. The heat dissipation properties are determined by
the film thickness and the thermal conductivity, and
since the thermal conductivity is substantially in
proportion to the volume resistivity in the case of such
a metal, the heat dissipation performance may be
represented by the sheet resistivity. The sheet
resistivity is usually at least 0.05 O/?, preferably at
least 0.1 O/?, and on the other hand, it is usually at
most 0.6 O/?, preferably at most 0.5 O/?, more preferably
at most 0.4 O/?, furthermore preferably at most 0.2 O/?.
This is to guarantee particularly high heat
dissipation properties, and is necessary to suppress
recrystallization to a certain extent in a case where
competition between the formation of an amorphous phase
and the recrystallization is remarkable in the formation
of amorphous marks, as in the recording layer to be used
for the optical information recording medium. In order
to control the thermal conductivity of the reflective
layer itself or to improve the corrosion resistance, e.g.
Ta, Ti, Cr, Mo, Mg, V, Nb, Zr or Si may be added in a
small amount to the above metal. The addition amount is
usually at least 0.01 atomic% and at most 20 atomic%. An
aluminum alloy containing at least one of Ta and Ti in an
amount of at most 15 atomic%, particularly an alloy of
AlaTa1-a (O=a=O.15) is excellent in corrosion resistance,
and is a particularly preferred reflective layer material
with a view to improving the reliability of the optical
information recording medium.
Particularly in a case where the film thickness of
the second protective layer is at least 40 nm and at most
50 nm, the amount of the added element contained is
preferably at most 2 atomic% so as to make the reflective
layer have a high thermal conductivity.
Particularly preferred as the material of the
reflective layer is one containing Ag as the main
component. "Containing Ag as the main component" means
that Ag is contained in an amount of at least 50 atomic%
based on the entire reflective layer. The content of Ag
based on the entire reflective layer is preferably at
least 70 atomic%, more preferably at least 80 atomic%,
furthermore preferably at least 90 atomic%, particularly
preferably at least 95 atomic%. Most preferred with a
view to increasing the heat dissipation properties is to
employ pure Ag as the material of the reflective layer.
The reason why it is preferred that Ag is contained
as the main component is as follows. Namely, recording
is carried out again on recording marks which are stored
for a long time, such a phenomenon may take place in some
cases that the recrystallization speed of the phase-
change recording layer is high only at the first
recording immediately after the storage. The reason why
such a phenomenon takes place is not clear, but is
supposed to be because the size of the amorphous marks
formed by the first recording immediately after the
storage is smaller than the desired size of the marks due
to increase in the recrystallization speed of the
recording layer immediately after the storage.
Accordingly, in a case where such a phenomenon takes
place, Ag having extremely high heat dissipation
properties may be used for the reflective layer to
increase the cooling rate of the recording layer, whereby
recrystallization of the recording layer at the first
recording immediately after the storage can be suppressed
and the size of the amorphous marks can be maintained to
the desired size.
A Ag alloy containing one member of Mg, Ti, Au, Cu,
Pd, Pt, Zn, Cr, Si, Ge, Bi and a rare earth element in an
amount of at least 0.01 atomic% and at most 10 atomic% in
Ag also has a high reflectivity and a high thermal
conductivity, is excellent in heat resistance and is
preferred.
The film thickness of the reflective layer is
usually at least 10 nm so that the incident laser beam is
completely reflected so that there is no transmitted
light, and it is preferably at least 20 nm, more
preferably at least 40 nm. Further, when it is too
thick, there is no change in the heat dissipation effect,
the productivity is unnecessarily deteriorated, and the
cracks are likely to occur, and accordingly it is usually
at most 500 nm. However, it is preferably at most 400
nm, more preferably at most 300 nm.
The recording layer, the protective layer and the
reflective layer are formed usually by e.g. a sputtering
method.
It is preferred to carry out deposition in an in-
line apparatus having a recording layer target, a
protective layer target and, if necessary, a reflective
layer material target provided in the same vacuum
chamber, with a view to preventing oxidation or
contamination among the respective layers. Further, it
is excellent in view of the productivity also.
(E) Protective coating layer (covering layer)
It is preferred to form a protective coating layer
comprising a ultraviolet-curing resin or a thermosetting
resin on the outermost surface side of the optical
information recording medium, so as to prevent direct
contact with the air or to prevent scars by the contact
with foreign materials. The protective coating layer has
a thickness of usually from 1 urn to several hundred urn.
Further, a dielectric protective layer having high
hardness may further be formed, or a resin layer may
further be formed thereon.
(Initial crystallization method of optical information
recording medium)
The recording layer is formed usually by a physical
vapor deposition method in vacuum such as a sputtering
method. However, in a state immediately after the
deposition (as-deposited state), the recording layer is
usually amorphous, and therefore, it is preferred to
crystallize the recording layer to form a non-recorded or
erased state. This operation is referred to as
initialization (or initial crystallization). As the
initial crystallization operation, a method such as oven
annealing in a solid phase at a temperature of at least
the crystallization temperature (usually from 150 to
3 00°C) and at most the melting point, annealing under
irradiation with a light energy of e.g. a laser beam or a
flash lamp beam or melt initialization may, for example,
be mentioned. In the present invention, among the above
initial crystallization operations, it is preferred to
employ melt initialization, since a phase-change
recording material with a small formation of crystal
nuclei is employed.
In the melt initialization, if the recrystallization
speed is too slow, there will be a time until the thermal
equilibrium is reached, whereby other crystalline phases
may be formed in some cases. Accordingly, it is
preferred to increase the cooling rate to some extent.
Further, if the recording layer is held in a melted state
for a long time, the recording layer may flow, a thin
film such as the protective layer may peel off by the
stress, or e.g. the resin substrate may deform, thus
leading to destruction of the medium, such being
unfavorable.
For example, the time for maintaining the
temperature at a level of at least the melting point is
preferably usually at most 10 us, preferably at most 1
US.
Further, for the melt initialization, it is
preferred to employ a laser beam. It is particularly
preferred to carry out initial crystallization by using
an oval laser beam having its minor axis substantially in
parallel with the scanning direction (hereinafter, this
initialization method may sometimes be referred to as
"bulk erasing"). In such a case, the length of the major
axis is usually from 10 to 1000 µm, and the length of the
minor axis is usually from 0.1 to 5 urn.
Here, the lengths of the major axis and the minor
axis of the beam are defined from the half value width in
a case where the light energy intensity distribution
within the beam is measured. With respect to the beam
shape also, the minor axis length is preferably at most 5
urn, more preferably at most 2 -µm so as to easily realize
local heating and rapid cooling in the minor axis
direction.
As the laser beam source, various types may be used
including, for example, a semiconductor laser and a gas
laser. The power of the laser beam is usually from about
10 0 mW to about 10 W. Further, another light source may
be used so long as a power density and a beam shape at
the same level can be obtained. Specifically, a Xe lamp
laser beam may, for example, be mentioned.
In the initialization by bulk erasing, when a disk-
form optical information recording medium is used for
example, the minor axis direction of an oval beam is
brought substantially into line with the circumferential
direction, and by rotating the disk, scanning is carried
out in the minor axis direction, while moving the beam in
the major axis (radial) direction every full circle (one
rotation), whereby initialization can be carried out over
the entire surface. By doing this, a polycrystalline
structure aligned in a specific direction relative to the
focused laser beam for recording/retrieving scanned along
the track in the circumferential direction can be
realized.
The moving distance in the radial direction per one
revolution is preferably set to be shorter than the major
axis of the beam, so that the irradiated regions overlap,
and the same radial position will be irradiated a
plurality of times with the laser beam. As a result,
initialization can certainly be carried out, and at the
same time, it is possible to avoid non-uniformity of the
initial crystallization state attributable to the energy
distribution (usually from 10 to 2 0%) in the radial
direction of the beam. On the other hand, if the moving
distance is too short, undesirable crystalline phases
tend to be formed. Accordingly, the moving distance in
the radial direction is usually set to be at least 1/2 of
the major axis of the beam. Further, the scanning speed
of the initialization energy beam is usually within a
range of from 3 to 20 m/s.
Whether or not at least the optical information
recording medium of the present invention can be obtained
by melt initialization can be judged by determining
whether or not the reflectivity Rl in the non-recorded
state after initialization is substantially equal to the
reflectivity R2 in the erased state by recrystallization
after recording of amorphous marks is carried out by a
practical focused laser beam for recording (for example,
a focused laser beam having a diameter of the beam of
about 1 µm) . Here, R2 is the reflectivity at the erased
portion after recording 10 times.
Accordingly, the optical information recording
medium of the present invention preferably satisfies the
following relational expression (3) where the
reflectivity at the non-recorded portion after initial
crystallization is Rl and the reflectivity at the erased
portion after recording 10 times is R2:
AR=2|Rl-R2|/(Rl+R2)xl00(%)=10 (3)
The reason why the reflectivity R2 at the erased
portion after recording 10 times is taken as the judgment
index is that when recording is carried out 10 times, the
influence of the reflectivity in a crystalline state
which may remain in a non-recorded state if recording is
carried out only once, can be removed, and the entire
surface of the optical information recording medium can
be made to be in a state where it is recrystallized by
recording and erasing at least once. On the other hand,
if the number of recording is excessively higher than 10
times, factors other than the change in the crystalline
structure of the recording layer, such as microscopic
deformation of the recording layer due to the repeated
recording or diffusion of a foreign element from the
protective layer to the recording layer may cause a
change in the reflectivity, and accordingly it tends to
be difficult to judge whether or not the desired
crystalline state can be obtained.
In the above relational expression (3), AR is at
most 10%, and it is preferably at most 5%. When it is at
most 5%, an optical information recording medium having
lower signal noises can be obtained.
For example, of an optical information recording
medium with Rl of about 17%, R2 may be substantially
within a range of from 16 to 18%.
The above erased state may also be obtained by
irradiation with the writing power in a direct current
fashion to melt the recording layer, followed by
resolidification, without necessarily modulating the
focused recording laser beam in accordance with a
practical recording pulse-generating method.
In order to obtain the desired initial crystalline
state of the phase-change recording material to be used
for the recording layer in the present invention, it is
particularly important to set the scanning speed of the
initialization energy beam relative to the recording
layer plane. Basically, it is important that the
crystalline state after initial crystallization is
similar to the crystalline state at the erased portion
after recording, and accordingly, the scanning speed is
preferably in the vicinity of the relative scanning
linear velocity of the focused laser beam to the
recording layer face when practical recording is carried
out by using a focused laser beam. Specifically, the
initialization energy beam is scanned at a linear
velocity of from about 2 0 to about 80% of the maximum
linear velocity when recording is carried out on the
optical information recording medium.
The maximum linear velocity for recording is, for
example, a linear velocity when the erase ratio becomes
at least 2 0 dB at the time of irradiation with an erasing
power Pe in a direct current fashion at that linear
velocity.
The erase ratio is defined as the difference between
the carrier level of signals of the amorphous marks
recorded substantially at a single frequency and the
carrier level after erasing by direct current irradiation
of Pe. Measurement of the erase ratio is carried out as
follows for example. Firstly, under recording conditions
under which adequate signal characteristics (i.e. such
characteristics that e.g. the reflectivity and the signal
amplitude or the jitter satisfy specified values) are
obtained, a condition with a high frequency is selected
among modified signals to be recorded, recording is
carried out 10 times at a single frequency to form
amorphous marks, and the carrier level (C.L. at
recording) is measured. Then, the direct current
irradiation is carried out once on the amorphous marks
while changing the erasing power Pe, and the carrier
level at this time (C.L. after erasing) is measured, to
calculate the difference between C.L. at recording and
C.L. after erasing, i.e. the erase ratio. When the power
Pe of the direct current irradiation is changed, the
erase ratio tends to increase once, decrease and then
increase again in general. Here, the first peak value of
the erase ratio observed when the power Pe starts being
increased is taken as the erase ratio of the sample in
this case.
With respect to the scanning speed of the
initialization energy beam, if the initialization energy
beam is scanned at a speed lower than about 2 0% of the
above defined maximum linear velocity, phase separation
may occur and a single phase is less likely to be
obtained, or even if a single phase is obtained,
crystallites may grow particularly in the initialization
beam scanning direction and become giant, or aligned in
an unfavorable direction. Preferably, the initialization
energy beam is scanned at a speed of at least 30% of the
recordable maximum linear velocity.
On the other hand, if the initialization energy beam
is scanned in a speed equal to the recordable maximum
linear velocity i.e. at a rate higher than about 80% of
that, a region once melted by the initial scanning tends
to be formed into an amorphous state again, such being
unfavorable. This is because when the scanning linear
velocity is high, the cooling rate of the melted portion
tends to be high, and the time for resolidification tends
to be short. With a focused recording laser beam having
a diameter of about 1 micron, recrystallization by
crystal growth from the crystalline region at the
periphery of the melted region can be completed in a
short time. However, in a case where scanning is carried
out with an initialization oval laser beam, the melted
region area in the major axis direction tends to be
large, and accordingly it is necessary that
recrystallization during resolidification is carried out
over the entire melted region by lowering the scanning
linear velocity than that at the time of practical
recording. From such a viewpoint, the scanning linear
velocity of the initial energy beam is preferably at most
70% of the recording maximum linear velocity, more
preferably at most 60%, most preferably lower than 50%.
The optical information recording medium of the
present invention has such characteristics that when
initial crystallization is carried out by irradiation
with a laser beam, it is possible to increase the moving
speed of the medium relative to the laser beam. This
makes it possible to carry out initial crystallization in
a short time, and is preferred in view of improvement of
the productivity and the cost reduction.
(Recording and retrieving method of optical information
recording medium)
The recording/retrieving laser beam to be used for
the optical information recording medium of the present
invention is usually a laser beam such as a semiconductor
laser or a gas laser, and its wavelength is usually from
3 00 to 800 nm, preferably from about 3 50 to about 800 run.
Particularly, in order to achieve a high areal density of
at least 1 Gbit/inch2, the focused laser beam diameter is
required to be small, and it is desirable to obtain a
focused laser beam by using a blue to red laser beam
having a wavelength of from 350 to 680 nm and an object
lens having a numerical aperture NA of at least 0.5.
In the present invention, as mentioned above, it is
preferred that the amorphous state corresponds to
recording marks. Further, in the present invention, it
is effective to record information by the mark length
modulation system. This is particularly remarkable at
the time of the mark length recording with a shortest
mark length of at most 4 µm, particularly at most 1 µm.
When the recording mark is formed, recording may be
carried out by a conventional system of modulating the
writing power into two levels of a high level (writing
power) and a low level (erasing power), however, in the
present invention, it is particularly preferred to employ
a recording method by a system of modulating the writing
power into at least three levels, e.g. by providing an
off-pulse, the power in which is adequately lower than
the erasing power when the recording mark is formed as
follows.
Fig. 2 is schematic views illustrating the power
pattern of the recording laser beam in the recording
method of an optical information recording medium. When
an amorphous mark which is mark length-modulated into a
length nT (wherein T is the reference clock period, and n
is the mark length possible in the mark length modulation
recording and is an integer), the amorphous mark is
divided into m=n-k (provided that k is an integer of at
least 0) recording pulses, each recording pulse width is
aiT (l=i=m), and an off-pulse (cooling pulse) section
with a time of biT (l=i=m) accompanies each recording
pulse. With respect to the divided recording pulse in
Fig. 2, description of the reference clock period T is
omitted in view of understandability of the figure.
Namely, in Fig. 2, a part which should be described as
aiT is described simply as ai for example. Here, it is
preferred that ai=bi, or ai=bi-1 (2=i=m or m-1). åai+åbi is
usually n, but it may be åai+åbi=n+j (j is a constant
which satisfies -2=j=2) so as to obtain an accurate nT
mark.
At the time of recording, irradiation with a
recording laser beam with an erasing power Pe which may
crystallize the amorphous state is carried out between
marks. Further, at aiT (i=l to m) , irradiation with a
recording laser beam with a writing power Pw sufficient
to melt the recording layer is carried out, and at a time
biT (l=i=m-l) , irradiation with the recording laser beam
with a bias power (cooling power, off-pulse power) Pb
which satisfies Pb out.
The power Pb of the recording laser beam irradiated
in a time with a period bmT is usually Pb Pb=l/2Pe, similar to the period biT (l=i=m-l), but it may
be Pb By employing the above recording method, the power
margin or the recording linear velocity margin can be
widened. This effect is particularly remarkable when the
bias power Pb is set to be adequately low so that
Pb=l/2Pe.
In Fig. 2, the switching period (ai + bi)T or (bi-1+ai)T
of the recording pulse (section aiT) and the off-pulse
(section ßiT) is set to be substantially the same as T,
that is, (ai+ßi) or (bi-1+ai) is set to be substantially 1.
However, it is possible to set the switching period to be
larger than IT, and particularly, it is possible to set
it to be 2T or 3T.
The above recording system is a system particularly
suitable for an optical information recording medium
wherein the phase-change recording material of the
present invention is used for the recording layer. In
the phase-change recording material of the present
invention, as described above, the number of crystal
nuclei in the amorphous marks is small, and
recrystallization (erasure of the amorphous marks) is
carried out mainly by the crystal growth from the
crystalline region at the periphery of the amorphous
marks. Accordingly, in high linear velocity recording,
the crystallization speed is increased by increasing the
crystal growth rate. This is one of the characteristics
of the phase-change recording material of the present
invention containing Sb as the main component, and
particularly, the crystal growth rate can be selectively
increased by increasing the Sb amount and decreasing Ge
and Te. Such a composition adjustment promotes
recrystallization of the amorphous marks from the
peripheral crystalline portion and at the same time,
increases the crystal growth rate at the time of melting
and resolidification. If the recrystallization speed
from the periphery of the amorphous mark is increased
above a certain level, recrystallization from the
peripheral portion of the melted region proceeds at the
time of resolidification of the melted region formed for
amorphous mark recording. Accordingly, the region which
is originally to be formed into an amorphous phase tends
to be recrystallized without being formed into an
amorphous phase. Accordingly, it is important to set the
bias power Pb to be adequately low, or to adequately
secure the cooling section by making ai=bi or ai=bi-1
(2=i=m or m-1) .
Further, if the linear velocity at the time of
recording increases, the clock period is shortened,
whereby the off-pulse section is shortened, and the
cooling effect tends to be impaired. In such a case, it
is effective to divide the recording pulse at the time of
nT mark recording, to set the cooling section by the off-
pulse to be at least 1 nsec, more preferably at least 5
nsec by the real time.
[2-2] Application of information recording medium of the
present invention other than optical information
recording medium
The information recording medium of the present
invention can be used as an optical information recording
mediµm, since reversible phase-change recording at least
by irradiation with laser beam is possible, as described
above. However, the rewritable information recording
medium used in the present invention can be applied, for
example, to phase-change recording by applying an
electric current to a microscopic region. Explanation
will be made below with respect to this point.
Fig. 3 is a schematic view illustrating the
temperature history (curve a) at the time of amorphous
mark recording, and the temperature history (curve b) at
the time of erasing by recrystallization. At the time of
recording, the temperature of the recording layer is
increased to at least the melting point Tm in a short
time by heating with an electric current at a high
voltage and with a short pulse or a high power level
laser beam, and after the electric current pulse or laser
beam irradiation is turned off, the recording layer is
rapidly cooled by heat dissipation to the periphery, and
formed into an amorphous phase. When the cooling rate of
the temperature at the time t0 from the melting point Tm
to the crystallization temperature Tg is higher than the
critical cooling rate for formation of an amorphous
phase, the recording layer is formed into an amorphous
phase. On the other hand, at the time of erasing, the
recording layer is heated to at least the crystallization
temperature Tg and at most about the melting point Tm, by
application of a relatively low voltage or irradiation
with a laser energy at a low power level, and maintained
for at least a certain time, whereby recrystallization of
the amorphous marks proceeds in a substantially solid
phase state. Namely, if the holding time T1 is adequate,
the crystallization will be completed.
Here, regardless of the state of the recording layer
before application of the energy for recording or
erasing, the recording layer is formed into an amorphous
phase when the temperature history of the curve a is
imparted to the recording layer, and the recording layer
is crystallized when the temperature history of the curve
b is imparted to the recording layer.
The reason why the rewritable information recording
medium of the present invention may be used for phase-
change recording by applying an electric current to the
microscopic region, not only as an optical information
recording mediµm, is as follows. Namely, it is the
temperature history as shown in Fig. 3 that causes a
reversible phase change, and the energy source which
causes such a temperature history may be either a focused
laser beam or an electric current heating (Joule heat by
conducting).
The change in the resistivity accompanying the phase
change between the crystalline phase and the amorphous
phase of the phase-change recording material used in the
present invention, is adequately equal to the change in
the resistivity by at least two orders of magnitude, as
obtained by a GeTe-Sb2Te3 pseudo binary alloy which is
being developed as a non-volatile memory at present,
particularly a Ge2Sb2Te5 stoichiometrical composition
alloy (J. Appl. Phys., vol. 87, pages 4130 to 4133,
2000) . In fact, when the resistivity in an amorphous
state in an as-deposited state, and the resistivity after
crystallization by annealing, of a rewritable information
recording medium using a phase-change recording material
containing a composition represented by the above formula
(1) as the main component, were respectively measured,
whereupon changes by at least three orders of magnitude
were confirmed. It is considered that the amorphous and
crystalline states obtained by formation into an
amorphous phase and the crystallization by current pulses
are slightly different from the above amorphous state in
an as-deposited state and the above crystalline state by
annealing, respectively. However, it is expected that
also in a case where the phase-change recording material
used in the present invention is subjected to phase
change by current pulses, a large change in the
resistivity by a level of two orders of magnitude can
adequately occur, since the above change in the
resistivity by at least three orders of magnitude can be
obtained.
Fig. 4 is a cross-sectional view illustrating the
structure of one cell of such a non-volatile memory. In
Fig. 4, a voltage is applied between an upper electrode 1
and a lower electrode 2, and an electric current is
applied to a phase-change recording layer 3 containing a
phase-change recording material (hereinafter sometimes
referred to simply as a phase-change recording layer 3)
and a heater portion 4. The phase-change recording layer
3 is covered with an insulant 10 such as SiO2. Further,
the phase-change recording layer 3 is crystallized in the
initial state. In this case, initial crystallization is
carried out by heating the entire system of Fig. 4 to the
crystallization temperature (usually from about 100 to
about 300°C) of the recording layer. In formation of an
integrated circuit, the temperature increase to such an
extent is commonly carried out.
In Fig. 4, a particularly narrow portion 4 (heater
portion) functions as a local heater, since heat is
likely to generate by the Joule heat by application of an
electric current between the upper electrode 1 and the
lower electrode 2. A reversibly changeable portion 5
adjacent thereto is locally heated and formed into an
amorphous phase via the temperature history as shown by
the curve a in Fig. 3, and recrystallized via the
temperature history as shown by the curve b in Fig. 3.
As the reading, a low electric current is applied to
such an extent that the heat generation at the heater
portion 4 can be ignored, and the voltage difference
between the upper and lower electrodes is read. Here,
there is also a difference in the electric capacity
between the crystalline and amorphous states, and
accordingly the difference in the electric capacity may
be detected.
Practically, a further integrated memory has been
proposed by employing a semiconductor integrated circuit
formation technology (U.S. Patent 6,314,014), however,
its basic structure is as shown in Fig. 4, and when the
phase-change recording material used in the present
invention is incorporated in the phase-change recording
layer 3, the same function can be realized.
Here, as the energy source which causes the
temperature change as shown in Fig. 3, an electron beam
may also be mentioned. As an example of a recording
device employing an electron beam, a method wherein a
phase-change recording material is locally irradiated
with an electron beam radiated by a field emitter to
cause a phase change, as disclosed in U.S. Patent
5,557,59 6 may be mentioned.
The present invention is not limited to the above
embodiments. The above embodiments are examples, and any
one having substantially the same structure as the
technical idea as disclosed in the scope of the present
invention and having the same effects is included in the
present invention.
EXAMPLES
Now, the present invention will be explained with
reference to Examples wherein the phase-change recording
material to be used in the present invention is applied
to an optical information recording medium. However, the
present invention is by no means restricted to the
application to an optical information recording medium
within a range not to exceed the gist of the present
invention.
In the following Examples, an optical information
recording medium may be referred to simply as "a disk",
"an optical disk", "a phase-change type optical disk"
etc. in some cases.
EXAMPLES 1 to 6 and COMPARATIVE EXAMPLES 1 to 4
For measurement of the composition of the phase-
change recording material used for the recording layer of
an optical information recording mediµm, an acid
dissolution ICP-AES (Inductively Coupled Plasma-Atomic
Emission Spectrometry) and a fluorescent X-ray analyzer
were used. With respect to the acid dissolution ICP-AES,
JY 38 S manufactured by JOBIN YVON was used as an
analyzer, and the recording layer was dissolved in dil-
HNO3 and quantitative determination was carried out by a
matrix matching calibration method. As the fluorescent
X-ray analyzer, RIX3001 manufactured by Rigaku Denki
Kogyo K.K. was used.
Measurement of the disk characteristics was carried
out by means of DDU1000 manufactured by Pulstec.
Industrial Co., Ltd., by applying focusing servo and
tracking servo to the groove at a retrieving power of 0.8
mW. This apparatus is an optical disk tester having a
pickup with NA of 0.5 and a laser wavelength of 780 nm.
On a disk-shape polycarbonate substrate having a
diameter of 120 mm and a thickness of 1.2 mm, having
guide grooves with a groove width of 0.5 µm, a groove
depth of 40 nm and a groove ßiTch of 1.6 µm, first to
fifth layers were formed in order by a sputtering method
as follows. The first layer is a (ZnS)80(SiO2)20
protective layer, the second layer is a Ge-In-Sb-Sn-Te
recording layer, the third layer is a (ZnS)80(SiO2)20
protective layer, the fourth layer is a Ta or GeN
interfacial layer, and the fifth layer is a Ag reflective
layer (200 nm) . The fourth layer is a thin interfacial
layer to prevent diffusion of S into the Ag reflective
layer, and there is substantially no difference in the
disk characteristics whether Ta or GeN is employed. A
protective layer comprising an ultraviolet-curing resin
was further formed on these layers to prepare a phase-
change type optical disk. The film thicknesses of the
respective layers and the values x, y, z and w when the
recording layer composition is represented by
Gex(InwSn1-w)yTe2Sb1-x-y-z are shown in Table 2. For the
fourth layer, GeN was employed only for the disks of
Comparative Examples 2 and 3, and Ta was employed for the
other disks. The respective disks have slightly
different film thicknesses of the respective layers since
the reflectivity, the signal amplitude, the recording
sensitivity, the repeated recording durability etc. were
adjusted, however, it is considered that the differences
do not have significant influences over the experimental
results. Further, other than the disks of Comparative
Examples 1 and 4 on which the initial crystallization or
erasure of the recording could not favorably be carried
out, the recording layer composition was adjusted to
obtain a crystallization speed suitable for the recording
conditions as mentioned hereinafter.
Initial crystallization was tried on each of these
disks as follows.
As a laser beam for initial crystallization, a laser
beam having a wavelength of 810 nm and a power of 800 mW
and having a shape with a width of about 1 mm and a
length of about 7 5 mm was employed. While rotating the
disk at 12 m/s, the disk was irradiated with the above
laser beam so that the major axis of the laser beam was
perpendicular to the guide grooves formed on the above
substrate. Further, the laser beam was continuously
moved in a radius direction of the disk with a feed
amount of 50 mm per rotation of the disk to try initial
crystallization.
Uniform initial crystallization could be achieved on
the disks other than the disk of Comparative Example 4.
However, crystallization could not be achieved on the
disk of Comparative Example 4 under the above conditions.
Initial crystallization was tried similarly at a linear
velocity of 2 m/s at a laser power of from 400 mW to 1000
mW, however, no uniform crystalline state could be
obtained. It is considered to be because the
crystallization speed was too slow. Accordingly, it is
considered that use of the disk of Comparative Example 4
as a phase-change optical disk is substantially
difficult.
Although initial crystallization could be achieved
on the disk of Comparative Example 1, the reflectivity
was so low as about 11%. There was no change in the
reflectivity even after recording and erasing were
carried out about 10 times. When the value of y-z is
small, the reflectivity and the signal amplitude are
small, and the use as the phase-change optical disk is
difficult. Also in a case where a part of or the entire
Sn is replaced by In, the relation between the value y-z
and the reflectivity shows the similar tendency.
Each disk was subjected to an environment resistance
test (accelerated test) of holding it in an environment
of 105°C for 3 hours, and the crystalline state
reflectivity was measured before and after the test. The
accelerated test is considered to correspond to a long
term storage of the medium. The results are shown in
Table 2. The reflectivity tends to decrease by the
accelerated test with respect to every disk, however, the
degree of the decrease varies depend on the disks. It is
found that the degree of the decrease in the reflectivity
by the accelerated test is correlated with ((In content)
-(Te content)) i.e. the value wxy-z. The rate of
decrease in the reflectivity by the accelerated test
(shown in the section "rate of decrease in reflectivity
after accelerated test" in Table 2) is defined by
((reflectivity before the accelerated test)-(reflectivity
after the accelerated test))/(reflectivity before the
accelerated test), and wxy-z is required to be at most
about 0.1 if the rate of decrease is to be suppressed
lower than about 0.15. Needless to say, the rate of
decrease is preferably as low as possible.
On each of the disks of Examples 1 to 6, before the
above accelerated test was carried out, EFM random
signals were recorded at a linear velocity of 28.8 m/s as
mentioned hereinafter by means of the above optical disk
tester, and then the above accelerated test was carried
out, to measure the disk characteristics as mentioned
hereinafter before and after the accelerated test. The
pulse strategy, and the writing power Pw and the erasing
power Pe were selected so that the jitter characteristics
would be as good as possible on each disk.
On each of the disks of Examples 1 to 5, recording
was carried out as follows. Marks with lengths of from
3T to 1it (T is a reference clock period and is 9.6 nsec)
contained in the EFM signal were formed by irradiation
with pulse rows of the following laser pulses in series.
3T: A pulse with a power Pw and a length 1.4T, a
pulse with a power Pb and a length 0.85T.
4T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 0.4T.
5T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.45T, a pulse with a power
Pw and a length 1.4T, a pulse with a power Pb and a
length 0.4T.
6T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 0.4T.
7T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.45T, a pulse with a power Pw and a length 1.4T,
a pulse with a power Pb and a length 0.4T.
8T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 0.4T.
9T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.45T, a pulse with a
power Pw and a length 1.4T, a pulse with a power Pb and a
length 0.4T.
10T:A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 0.4T
1it:A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 1.45T, a pulse with a power Pw and a length 1.4T,
a pulse with a power Pb and a length 0.4T.
Between the pulse rows for mark formation,
irradiation with an erasing power Pe was carried out, and
Pb=0.8 mW. The writing power Pw and the erasing power Pe
are shown in Table 2. Overwriting was carried out ten
times.
On the disk of Example 6, recording was carried out
as follows. Marks with lengths of from 3T to 1it (T is a
reference clock period and is 9.6 nsec) contained in the
EFM signal were formed by irradiation with pulse rows of
the following laser pulses in series.
3T: A pulse with a power Pw and a length 1.8T, a
pulse with a power Pb and a length 1.1T.
4T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 0.4T.
5T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.45T, a pulse with a power
Pw and a length 1.4T, a pulse with a power Pb and a
length 0.4T.
6T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 0.4T.
7T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.45T, a pulse with a power Pw and a length 1.4T,
a pulse with a power Pb and a length 0.4T.
8T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 0.4T.
9T: A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.45T, a pulse with a
power Pw and a length 1.4T, a pulse with a power Pb and a
length 0.4T.
10T:A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 0.4T.
1it:A pulse with a power Pw and a length 1T, a pulse
with a power Pb and a length 1.1T, a pulse with a power
Pw and a length 0.9T, a pulse with a power Pb and a
length 1.1T, a pulse with a power Pw and a length 0.9T, a
pulse with a power Pb and a length 1.1T, a pulse with a
power Pw and a length 0.9T, a pulse with a power Pb and a
length 1.45T, a pulse with a power Pw and a length 1.4T,
a pulse with a power Pb and a length 0.4T.
Between the pulse rows for mark formation,
irradiation with an erasing power Pe was carried out, and
Pb=0.8 mW. The writing power Pw and the erasing power Pe
are shown in Table 2. Further, the position of the
irradiation with 3T mark formation pulses was shifted
forward (the irradiation time was adversed from the
original) by 0.2T from the original starting position of
the 3T mark length signal in the EFM random signal, and
the position of irradiation with 4T mark formation pulses
was shifted forward by 0.05T from the original starting
position of the 4T mark length signal in the EFM random
signal. By doing this, the marks to be formed are close
to the original random signals. Overwriting was carried
out ten times.
The recorded portion of each disk was retrieved at a
linear velocity of 1.2 m/s to evaluate the
characteristics of the recording signals. The evaluated
items were the jitter of 3T spaces and the crystalline
state reflectivity. The results are shown in Table 2.
As the jitter of 3T spaces, a value of at most 40 ns
could be obtained, and this characteristic is good enough
for practical application. Particularly, with the disks
of Examples 1 to 5, a value of at most 3 0 ns could be
obtained, such being favorable. The disk of Example 6 is
slightly poor in the jitter characteristics, and this is
considered to be because the Sn content is high.
Each of the disks was subjected to the above
accelerated test, and then the portion recorded before
the accelerated test was retrieved to measure the jitter
of 3T spaces again. The results are shown in Table 2.
On every disk, as the jitter of 3T spaces, a value of at
most 40 ns could be obtained, and this characteristic is
good enough for practical application. Particularly, on
the disks of Examples 1, 2, 4 and 5, a value of at most
3 0 ns could be obtained, such being favorable. On these
disks, the amorphous marks are adequately stable. On the
disk of Example 3, deterioration of the jitter value by
the accelerated test was slightly observed. In the
waveform observation by an oscilloscope, it is considered
that crystallization of the 3T mark was in progress. The
amorphous marks are particularly stable when Ge is
contained.
Then, an operation to erase the signals recorded
before the accelerated test, was carried out after the
accelerated test, and whether or not insufficiently
erased marks are present, was confirmed by observation by
oscilloscope. In a case where unerased marks are shown,
there is a fear that the signal quality when overwriting
is carried out after the recorded medium is stored for a
long term, may not be adequately excellent. The erasure
operation is to irradiate each disk with a DC light with
an erasing power Pe as shown in Table 2 once. As a
result, on the disks of Examples 4 and 5, unerased marks
were observed, whereas on the disks of Examples 1, 2 and
3, favorable erasure condition was observed. it is
considered that the excellent erasure is achieved since
the Ge content is low.
The recorded portion of a disk substantially the
same as that of Example 4 was observed by a transmission
electron microscope (TEM), whereupon it was confirmed
that amorphous state marks were recorded in the
crystalline state. Accordingly, it is thought that
amorphous state marks are recorded in the crystalline
state on the disks of all Examples on which recording was
carried out.
COMPARATIVE EXAMPLE 5
A disk of Comparative Example 5 was prepared as
follows.
On a disk-shape polycarbonate substrate having a
diameter of 120 mm and a thickness of 1.2 mm and having
guide grooves with a groove width of 0.5 µm, a groove
depth of 40 nm and a groove ßitch of 1.6 µm, first to
fifth layers were formed in order by a sputtering method
as follows. The first layer is a (ZnS)80(SiO2)20
protective layer, the second layer is a recording layer,
the third layer is a (ZnS)80(SiO2)20 protective layer, the
fourth layer is a GeN interfacial layer, and the fifth
layer is a Ag reflective layer. A protective layer
comprising an ultraviolet-curing resin was further formed
on these layers to prepare a phase-change type optical
disk. The film thicknesses of the respective layers and
the values x, y, z and w when the recording layer
composition is represented by Gex(InwSn1-w)yTezSb1-x-y-z are
shown in Table 2. Then, initial crystallization under
the same conditions as in Example 1 was carried out.
By means of a disk tester having a pickup with NA of
0.5 and a laser wavelength of 780 ran, of the disk of
Example 1 and the disk of Comparative Example: 5, the
repeated overwriting durability was measured.
The conditions for evaluation of the repeated
overwriting durability are as follows.
Namely, EFM random signals were recorded on each
disk at a recording linear velocity of 28.8 m/s. The
recording pulses employed for recording were the same as
in Example 1, the writing power Pw was 33 mW, and the
erasing power Pe was 9 mW.
Retrieving was carried out at a linear velocity of
1.2 m/s. The jitter of 3T spaces after overwriting ten
times was 25.6 ns with respect to the disk of Example 1
and 27.1 ns with respect to the disk of Comparative
Example 5. The jitter of 3T spaces after overwriting
2000 times was 32.1 ns with respect to the disk of
Example 1 and 58.4 ns with respect to the disk of
Comparative Example 5, and the disk of Comparative
Example 5 was poor in the repeated recording durability.
The main cause of the jitter deterioration of the
disk of Comparative Example 5 is considered to be a
decrease in the crystallization speed due to the repeated
overwriting, thus leading to incomplete erasure of the
marks. On the other hand, of the disk of Example 1
containing Te, the decrease in the crystallization speed
due to the repeated recording was suppressed.
REFERENCE EXAMPLE 1
A disk of Reference Example 1 was prepared as
follows.
On a disk-shape polycarbonate substrate having a
diameter of 120 mm and a thickness of 1.2 mm and having
guide grooves with a groove width of 0.5 µm, a groove
depth of 40 nm and a groove pitch of 1.6 µm, first to
fifth layers were formed in order by a sputtering method
as follows. The first layer is a (ZnS)80(SiO2)20
protective layer, the second layer is a recording layer,
the third layer is a (ZnS) 80 (SiO2)20 protective layer, the
fourth layer is a Ta interfacial layer, and the fifth
layer is a Ag reflective layer. A protective layer
comprising an ultraviolet-curing resin was further formed
on these layers to prepare a phase-change type optical
disk. The film thicknesses of the respective layers and
the values x, y, z and w when the recording layer
composition is represented by Gex(InwSn1-w)yTezSb1-x-y-z are
shown in Table 2. Then, initial crystallization was
carried out under the same conditions as in Example 1.
The disk of Reference Example 1 was subjected to an
environment resistance test (accelerated test) of holding
it in an environment of 10 5°C for 3 hours, and the
crystalline state reflectivity was measured before and
after the test. The crystalline state reflectivities
before and after the accelerated test were 27.8% and
23.4%, respectively. When the rate of decrease in the
reflectivity by the accelerated test is defined as
((reflectivity before the accelerated test)-(reflectivity
after the accelerated test))/(reflectivity before the
accelerated test), the rate of decrease was 0.158.
A graph obtained by plotting the rate of decrease in
the reflectivity after the accelerated test (a value
defined by ((reflectivity before the accelerated test)-
(reflectivity after the accelerated test))/(reflectivity
before the accelerated test) and is a data shown in "rate
of decrease in reflectivity after accelerated test" in
Table 2) relative to the (In-Te) amount of the disks of
Examples 1 to 6, Comparative Examples 2 and 3 and
Reference Example 1, is shown in Fig. 7. it can be seen
from Fig. 7 that the decrease in the reflectivity when
accelerated is suppressed to be within 0.15 (15%) when
In-Te EXAMPLES 7 to 12 and COMPARATIVE EXAMPLE 6
A polycarbonate resin substrate having a thickness
of 0.6 mm and a track pitch of 0.74 mm was formed by
injection molding and employed for the following
experimental examples. Of the grooves formed on the
substrate, the groove width was about 0.31 mm and the
groove depth was about 28 nm. The groove shape was
obtained by an optical diffraction method of U-groove
approximation by means of a He-Cd laser beam having a
wavelength of 441.6 nm.
Then, on the substrate, a (ZnS)80(SiO2)20 protective
layer of 65 nm, a Y2O2S layer of 2 nm, a Ge7In6Sb56Sn24Te7
recording layer of 12 nm, a Y2O2S layer of 2 nm, a
(ZnS)80(Si02)20 protective layer of 12 nm, a Ta
interfacial layer of 2 nm, a Ag reflective layer of 200
nm and an ultraviolet-curing resin layer of about 4 nm
were formed in this order. The Ta layer is an
interfacial layer to prevent diffusion of S into the Ag
reflective layer.
Formation of the respective layers was carried out
by sequential deposition by a sputtering method on the
above substrate without breaking the vacuum. However,
the ultraviolet-curing resin layer was coated by a spin
coating method. Then, a similar substrate having a
thickness of 0.6 mm on which no film was formed was
bonded by means of an adhesive so that the above
recording layer side faced the inside (Example 7).
Similarly, on the above substrate, a (ZnS)80(SiO2)20
protective layer of 60 nm, a Y2O2S layer of 2 nm, a
Ge7ln6Sb56Sn24Te7 recording layer of 12 nm, a Y2O2S layer of
14 nm, a Ta interfacial layer of 2 nm, a Ag reflective
layer of 200 nm and an ultraviolet-curing resin layer of
about 4 mm were formed in this order. The Ta layer is an
interfacial layer to prevent diffusion of S into the Ag
reflective layer.
Formation of the respective layers was carried out
by sequential deposition by a sputtering method on the
above substrate without breaking the vacuum. However,
the ultraviolet-curing resin layer was coated by a spin
coating method. Then, a similar substrate having a
thickness of 0.6 mm on which no film was formed was
bonded by means of an adhesive so that the above
recording layer side faced inside (Example 8).
Similarly, on the above substrate, a (ZnS) 8o (SiO2) 20
protective layer of 7 0 nm, a Ge7In6Sb56Sn24Te7 recording
layer of 13 nm, a (ZnS)80(SiO2) 20 protective layer of 14
nm, a Ta interfacial layer of 2 nm, a Ag reflective layer
of 200 nm and an ultraviolet-curing resin layer of about
4 mm were formed in this order. The Ta layer is an
interfacial layer to prevent diffusion of S into the Ag
reflective layer.
Formation of the respective layers was carried out
by sequential deposition by a sputtering method on the
above substrate without breaking the vacuum. However,
the ultraviolet-curing resin layer was coated by a spin
coating method. Then, a similar substrate having a
thickness of 0.6 mm on which no film was formed was
bonded by means of an adhesive so that the above
recording layer side faced inside (Example 9).
Similarly, a disk employing a GeN layer instead of
the Y2O2S layer in Example 7 was prepared (Example 10).
Similarly, a disk employing a ZnO layer instead of
the Y2O2S layer in Example 7 was prepared (Example 11).
Similarly, a disk employing a (ZnS)80 (CeC)20 layer
instead of the Y2O2S layer in Example 7 was prepared
(Example 12).
Similarly, a disk employing a Ge5Sb72Te23 layer
instead of the Ge7In6Sb56Sn24Te7 layer in Example 7 was
prepared (Comparative Example 6).
With respect to the thickness of each layer, the
deposition rate was estimated, and then the thickness was
controlled by the sputtering time. The composition of
the recording layer was determined by correcting the
fluorescent intensities of the respective elements
obtained by a fluorescent X-ray analysis by the absolute
composition separately obtained by a chemical analysis
(atomic absorption spectrometry).
Then, initial crystallization was carried out. As
the laser beam for the initial crystallization, a laser
beam having a wavelength of 810 ran and focused into an
oval shape having a major axis of about 7 5 urn and a minor
axis of about 1 mm was employed. While rotating the
disk, the disk was irradiated with the above laser beam
so that the major axis of the laser beam would be
perpendicular to the guide grooves formed on the above
substrate, and the above laser beam was continuously
moved in a radius direction of the disk with a feed
amount of 50 mm per rotation of the disk to carry out
initial crystallization.
For the disks of Examples 7 and 9 to 12, the linear
velocity was 30 m/s and the laser power was 1500 mW, for
the disk of Example 8, the linear velocity was 30 m/s and
the laser power was 1800 mW, and for the disk of
Comparative Example 6, the linear velocity was 3 m/s and
the laser power was 500 mW.
Recording/retrieving evaluation was carried out by
means of DDU1000 tester manufactured by Pulstec.
Industrial Co., Ltd. (wavelength: about 650 nm, NA=0.65,
spot shape: a circular of about 0.86 mm with an
intensity of 1/e2) . On the basis of the reference linear
velocity of 3.49 m/s of DVD being 1-time velocity,
recording characteristics at 10-times velocity were
evaluated.
The reference clock period of data at each linear
velocity was one inversely proportionated at each linear
velocity against the reference clock period of 3 8.2 nsec
of data at 1-time velocity.
Unless otherwise specified, retrieving was carried
out at 1-time velocity. The output signal from DDU1000
was passed through a high frequency-passing filter having
a cutoff lies between 5 and 20 kHz, whereupon the jitter
was measured by a time interval analyzer (manufactured by
Yokogawa Electric Corporation). The retrieving power Pr
was 0.6 mW.
Formation of a logic level to control the recording
pulse division method was carried out by means of an
optional signal generator (AWG710, manufactured by Sony
Tektronix Co.). From the above signal generator, logic
signals at ECL level were input as gate signals against a
laser driver of the above tester.
EFM+ random data were overwritten 2000 times at a
linear velocity of 10-times velocity on each of the disks
of Examples 7 to 12, and the data to clock jitter
(hereinafter one normalized by the reference clock period
T and represented by a % value will be simply referred to
as jitter) of the recorded data was measured.
The pulse rows for the respective mark length
recording were set as follows. The laser irradiation
time for recording a nT mark was divided in the order of
a1T, ß1T, a2T, (a2T, ..., aiT, ßiT,..., amT bmT(m is the
pulse division number and T is the reference clock
period), and in the time at ait(l=i=m), irradiation with
a recording laser beam with a writing power Pw was
carried out, and in the time at biT (l=i=m), irradiation
with a recording laser beam with a bias power Pb was
carried out. These values were selected so that
favorable jitter value would be obtained on each disk,
and they were as shown in Table 3 on the disks of
Examples 7 and 9 to 12, and they were as shown in Table 4
on the disk of Example 8. for marks of some lengths, the
timing of irradiation with the pulse row was delayed for
a certain time from the original starting time of said
mark length in the EFM+ signal, and this time was shown
in the section "delay time". A case where the
irradiation timing was delayed was represented by + and a
case where it was advanced was represented by -. The
value was normalized by the clock period T. The mark
formed by providing the delay time is close to the ideal
EFM+ random signal, and the jitter is excellent. At the
space between marks (the portion other than the portion
as disclosed in Table), irradiation with an erasing power
Pe was carried out. For the disks of Examples 7 and 10
to 12, Pw was 23 mW, Pb was 0.5 mW and Pe was 6.6 mW.
For the disk of Example 8, Pw was 28 mW, Pb was 0.5 mW
and Pe was 8 mW. For the disk of Example 9, Pw was 23
mW, Pb was 0.5 mW and Pe was 6.2 mW. As the laser power,
values which were considered to be optimum for the
respective disks were selected.
The results of the repeated durability test of the
disks of Examples 7 to 10 are shown in Fig. 8. In Fig.
8, the horizontal axis illustrates the number of
overwriting cycle. Actually, the first recording is
recording on a disk in a non-recorded initial crystalline
state, and the second and the subsequent recordings are
overwriting (hereinafter the same applies in Figs. 9, 10
and 12) . In each Example, deterioration of the jitter is
at most about 2% up to 1000 times, such being excellent.
Of the disk of Example 9, the jitter value increased to
12.5% by overwriting 2000 times, however, of the disks of
Examples 7 and 8, the jitter value was at most 10%, and
deterioration by repeated recording was slight. Namely,
when Y2O2S is provided in contact with the Ge-In-Sb-Sn-Te
type recording layer, the repeated recording durability
tends to be significantly improved. Of the disk of
Example 10 also, the jitter value after overwriting 2 0 00
times was at most 10%, and the repeated recording
durability was improved. On the other hand, the disks of
Examples 11 and 12, which are not shown in Fig. 8, were
inferior in the repeated recording durability to the disk
of Example 9, however, they are stable during overwriting
at least about several hundred times and are adequately
practical. Further, it is possible to stabilize the
jitter at least 1000 times by further optimizing the
protective layer or the layer structure on these disks.
Then, the signal amplitude after overwriting 10
times of each of the disks of Examples 7 and 10 was
measured. In either case, Pw was 23 mW, Pb was 0.5 mW
and Pe was 6.6 mW. When the signal amplitude was defined
as ((reflectivity at the space between marks)-
(reflectivity at the 14T mark portion)), the values of
the signal amplitude were 0.151 and 0.144 in Examples 7
and 10, respectively, and there was a difference.
Namely, it is found that the signal amplitude is high and
is excellent when Y2O2S is employed than when GeN is
employed, for the Ge-In-Sb-Sn-Te type recording layer.
These values are obtained as a result of
recording/retrieving with an optimum angle between the
laser head and the disk. it is considered that the
difference in the signal amplitude has a significant
influence over the signal quality e.g. at the time of
recording under severer conditions.
Then, each of the disks of Examples 7 and 8 was
subjected to an environment resistance test of holding it
in an environment of 100°C for 1 hour (hereinafter
referred to as environment resistance test 1). The
results of measurement of the repeated recording
durability before and after the environment resistance
test 1 are shown in Figs. 9 and 10. "Archival" in Figs.
9 and 10 represents the result when signals repeatedly
recorded predetermined times in a repeated recording
durability test before the environment resistance test 1,
were only retrieved after the environment resistance test
1. it can be seen in the disks of Examples 7 and 8, that
there was no problem in the stability of the amorphous
mark and the archival change of the repeated recording
durability.
The disks of Examples 7 and 8 and Comparative
Example 6 were subjected to an environment resistance
test of holding them in an environment at a temperature
of 80°C at a humidity of 85%RH for 90 hours (hereinafter
referred to as environment resistance test 2). No film
peeling occurred on the disks of Examples 7 and 8,
however, film peeling was observed on the disk of
Comparative Example 6. With respect to the disk of
Comparative Example 6, particularly when the portion
irradiated with the laser beam was observed by an
oscilloscope after the environment resistance test 2,
there observed a large number of portions where the
reflectivity decreased, the cause of which was considered
to be due to film peeling. Specifically, when
irradiation with a DC laser beam of 8 mW was carried out
at a linear velocity of 4-times velocity, a large number
of portions at which the reflectivity decreased appeared.
Such did not occur on the disks of Examples 7 and 8 at
all. Namely, in a case where Y2O2S was provided in
contact with a conventional SbTe eutectic type
composition material, there is a problem in the adhesion
properties between layers in some cases, however, in a
case where Y2O2S is provided in contact with the Ge-In-
Sb-Sn-Te type material, there is no problem in the
adhesion properties between the layers. The disk of
Example 8 was subjected to an environment resistance test
at the same temperature and humidity as the environment
resistance test 2 up to 250 hours, and no problem such as
film peeling occurred. Then, the same measurement as in
the above environment resistance test 1 was carried out
with respect to the disk of Example 8, whereupon there
was substantially no difference as compared with the case
of the environment resistance test 1.
EXAMPLES 13 and 14
A polycarbonate resin substrate having a thickness
of 0.6 mm and a track pitch of 0.74 mm was formed by
injection molding and employed for the following
experimental examples. Of the groove formed on the
substrate, the groove width was about 0.31 µm, and the
groove depth was about 2 8 nm. The groove shape was
obtained by an optical diffraction method by U-groove
approximation by means of a He-Cd laser beam having a
wavelength of 441.6 nm.
Then, on the substrate, a (ZnS)80(SiO2)20 protective
layer of 40 nm, a (Y2O2S)90(ZnO) 10 layer of 2 nm, a
Ge7In6Sb56Sn24Te7 recording layer of 10 nm, a
(Y2O2S)90(ZnO)10 layer of 14 nm, a Ta interfacial layer of
2 nm, a Ag reflective layer of 200 nm and an ultraviolet-
curing resin layer of about 4 mm were formed in this
order. The Ta layer is an interfacial layer to prevent
diffusion of S into the Ag reflective layer.
Formation of the respective layers was carried out
by sequential deposition by a sputtering method on the
substrate without breaking the vacuum. However, the
ultraviolet-curing resin layer was coated by a spin
coating method. Then, a similar substrate having a
thickness of 0.6 mm on which no film was formed was
bonded by means of an adhesive so that the above
recording layer side faced inside (Example 13).
Similarly, on the above substrate, a (ZnS)80(SiO2)20
protective layer of 60 nm, a (Y2O2S)90(ZnO)10 layer of 2
nm, a Ge7In6Sb56Sn24Te7 recording layer of 12 nm, a
(Y2O2S)90(ZnO)10 layer of 14 nm, a Ta interfacial layer of
2 nm, a Ag reflective layer of 200 nm and an ultraviolet-
curing resin layer of about 4 mm were formed in this
order. Then, a similar substrate having a thickness of
0.6 mm on which no film was formed was bonded by means of
an adhesive so that the recording layer side faced inside
(Example 14).
With respect to the film thickness of each layer,
the deposition rate was measured, and then the thickness
was controlled by the sputtering time. The composition
of the recording layer was determined by correcting the
fluorescent intensities of the respective elements
obtained by a fluorescent X-ray analysis by the absolute
composition separately obtained by a chemical analysis
(atomic absorption spectrometry).
Then, initial crystallization was carried out. As
the laser beam for the initial crystallization, a laser
beam having a wavelength of 810 nm and a power of 1800 mW
and focused into an oval shape having a major axis of
about 7 5 urn and a minor axis of about 1 mm was employed.
While rotating the disk at 30 m/s, the disk was
irradiated with the above laser beam so that the major
axis of the laser beam would be perpendicular to the
guide grooves formed on the above substrate, and the
above laser beam was continuously moved in a radius
direction of the disk with a feed amount of 50 mm per
rotation of the disk to carry out initial
crystallization.
Recording/retrieving evaluation was carried out by
means of DDU1000 tester manufactured by Pulstec.
Industrial Co., Ltd. (wavelength: about 650 nm, NA=0.65,
spot shape: a circular of 0.86 mm with an intensity of
1/e2) . On the basis of the reference linear velocity of
3.49 m/s of DVD being 1-time velocity, recording
characteristics at 10-times velocity were evaluated.
The reference clock period of data at each linear
velocity was one inversely proportionated at each linear
velocity to the reference clock period of 38.2 nsec of
data at 1-time velocity.
Unless otherwise specified, retrieving was carried
out at 1-time velocity. The output signal from DDU1000
was passed through a high frequency-passing filter having
a cutoff lies between 5 and 20 kHz, whereupon the jitter
was measured by a time interval analyzer (manufactured by
Yokogawa Electric Corporation). The retrieving power Pr
was 0.6 mW.
Formation of a logic level to control the recording
pulse division method was carried out by means of an
optional signal generator (AWG710, manufactured by Sony
Tektronix Co.). From the above signal generator, logic
signals at ECL level were input as gate signals against a
laser driver of the above tester.
Each of the disks of Examples 13 and 14 was
subjected to an environment resistance test 1 of holding
it in an environment of 100°C for 1 hour to measure the
recording characteristics before and after the
environment resistance test 1. EFM+ random data were
recorded at a linear velocity of 10-times velocity, and
the jitter etc. of the recorded data was measured.
The pulse rows for the respective mark length
recording were set as follows. The light irradiation
time to record the nT mark was divided in order of a1T,
ß1T, a2T, b2T,..., a1T, b1T, ..., amT, bmT (m is the pulse
division number and T is the reference clock period),
irradiation with a recording laser beam with a writing
power Pw was carried out at the time of ait (1=i=m), and
irradiation with a recording laser beam with a bias power
Pb was carried out at the time of biT (1=i=m) . These
values were set as shown in Table 5. For marks of some
lengths, the timing of irradiation with the pulse row was
delayed for a certain time from the original starting
time of said mark length in the EFM+ signal, and this
time is shown in the section "delay time". A case where
the irradiation timing was delayed was represented by +,
and a case where it was advanced was represented by -.
The value was normalized by the clock period T. The mark
formed by providing the delay time is close to the ideal
EFM+ random signal, and the jitter is excellent. At the
space between marks (the portion other than the portion
shown in Table), irradiation with an erasing power Pe was
carried out.
The jitter characteristics when overwriting was
carried out twice after the above environment resistant
test 1, were measured by changing the writing power Pw.
Pb was set to 0.5 mW, and Pe was set to 8 mW. The
results are shown in Fig. 11. On the disk of Example 13,
there is a power with which the jitter was at most 10%,
however, on the disk of Example 14, the jitter would not
be at most 10%. By overwriting up to about 1000 times
before and after the environment resistance test 1, the
jitter most deteriorates at the second recording (shelf
second recording) in the repeated overwriting test after
the environment resistance test 1, and the jitter once
decreases when the overwriting is carried out repeatedly
(Fig. 12 as disclosed hereinafter), and accordingly it is
preferred that the jitter after the second recording is
suppressed low. Accordingly, it can be said that the
disk of Example 13 has a further higher performance than
the disk of Example 14.
Further, with respect to the disk of Example 13,
when overwriting was carried out after the environment
resistance test 1 on the signals recorded before the
environment resistance test 1, the deterioration of the
jitter at the first overwriting (archival second
recording) was similarly suppressed low. it can be said
j that such a disk has a high reliability particularly for
long term use.
Further, the signal intensities of the disks of
Examples 13 and 14 after overwriting ten times before the
environment resistance test 1 were compared. At Pw of 28
mW, Pe of 8 mW and Pb of 0.5 mW, the signal amplitudes
i.e. ((reflectivity between marks)-(reflectivity at mark
portion)) were 0.161 in Example 13 and 0.161 in Example
14, and were the same. The signal intensity becomes low
only by making the recording layer thin, however, by
making the recording layer thin at the same time by
making the incident side protective layer thin, the
recording characteristics after the environment
resistance test 1 could be improved without reducing the
signal intensity.
Further, the repeated recording durability up to
2000 times of the disk of Example 13 at Pw of 28 mW, Pe
of 8 mW and Pb of 0.5 mW is shown in Fig. 12. The jitter
is at most 10% at every overwriting cycle, and it is
found that high reliability in the repeated overwriting
in a long term use can be obtained. Further, the portion
once recorded before the environment resistance test 1
was retrieved after the environment resistance test 1,
whereupon the jitter was 7% and was not deteriorated at
all. Namely, the storage stability of the amorphous mark
is also sufficient.
Then, the reflectivity at a portion on which
overwriting was carried out ten times before the above
environment resistance test 1 was measured before and
after the environment resistance test 1. As a result,
with respect to the disk of Example 13, the
reflectivities were 0.234 and 0.229, respectively. On
the other hand, with respect to the disk of Example 14,
the reflectivities were 0.246 and 0.234, respectively.
When the rate of decrease in the reflectivity by the
environment resistance test 1 is defined as
((reflectivity before the environment resistance test 1)-
(reflectivity after the environment resistance test
1))/(reflectivity before the environment resistance test
1), the rate of decrease in the reflectivity was about
0.021 in Example 13 or about 0.049 in Example 14, and the
rate of decrease in the reflectivity was lower in Example
13. Namely, it is found that the rate of decrease in the
reflectivity by the environment resistance test 1 becomes
low by making the recording layer thin.
EXAMPLE 15
The following experiment was carried out to show
possibility of recording by a change in the electric
resistance on the phase-change recording material used in
the present invention.
Namely, on a polycarbonate substrate having a
diameter of 120 mm, an amorphous film of Ge-In-Sn-Te-Sb
(Gex(InwSn1-w)yTezSb1-x-y-z wherein w=0.189, x=0.056, y=0.301
and z=0.073) having a film thickness of 50 nm was
prepared by sputtering.
The resistivity of the above amorphous film was
measured, and the amorphous film was crystallized to
measure the resistivity of the film after the
crystallization.
For initial crystallization, a laser beam having a
wavelength of 810 nm and a power of 1040 mW and having a
shape with a width of about 1 mm and a length of about 75
mm was employed. While rotating the Ge-In-Sn-Te-Sb
amorphous film formed on the above substrate at a linear
velocity of 12 m/s, the above amorphous film was
irradiated with the above laser beam so that the major
axis of the above laser beam would be perpendicular to
the guide grooves formed on the above substrate.
Further, the above laser beam was continuously moved in a
radius direction with a feed amount of 50 mm per one
rotation to carry out initial crystallization.
For measurement of the resistivity, a resistivity
measurement device Loresta MP (MCP-T3 50) manufactured by
Dia Instruments Co., Ltd. was used.
The resistivity before the crystallization was
1.36X10-1 ?cm. The resistivity after the crystallization
was 0.95xl0~4 Qcm. From this result, it was found that
there is a change in the resistivity by almost three
orders of magnitude between the amorphous state and the
crystalline state. Accordingly, it was found that the
phase-change recording material used in the present
invention provides a large difference in the resistivity
by phase change between the amorphous state and the
crystalline state, and is applicable to a rewritable type
information recording medium on which recording is
carried out by the change in the electric resistance.
EXAMPLE 16
A polycarbonate resin substrate having a thickness
of 0.6 mm and a track pitch of 0.74 urn was formed by
injection molding and employed for the following
experiment example. Of the grooves formed on the
substrate, the groove width was about 0.31 mm and the
groove depth was about 28 nm. The groove shape was
obtained by an optical diffraction method by U-groove
approximation by means of a He-Cd laser beam having a
wavelength of 441.6 nm.
Then, on the substrate, a (ZnS)80(SiO2)20 protective
layer of 65 nm, a Y2O2S layer of 2 nm, a
Ge5In8.5Sb52Sn24Te10.5 recording layer of 15 nm, a Y2O2S
layer of 17 nm, a Mo interfacial layer of 2 nm, a Ag
reflective layer of 200 nm and an ultraviolet-curing
resin layer of about 4 pa were formed in this order. The
Mo layer is an interfacial layer to prevent diffusion of
S into the Ag reflective layer.
Formation of the respective layers was carried out
by sequential deposition by a sputtering method without
breaking the vacuum. However, the ultraviolet-curing
resin layer was coated by a spin coating method. Then, a
similar substrate having a thickness of 0.6 mm on which
no film was deposited was bonded by means of an adhesive
so that the above recording layer side faced inside.
With respect to the thickness of each layer, the
deposition rate was measured, and then the thickness was
controlled by the sputtering time. The recording layer
composition was the composition of the sputtering target.
Then, initial crystallization was carried out. As
the laser beam for the initial crystallization, a laser
beam having a wavelength of 810 nm and a power of 1200 mW
and focused into an oval shape having a major axis of
about 75 mm and a minor axis of about 1 urn was employed.
While rotating the disk at 16 m/s, the disk was
irradiated with the above laser beam so that the major
axis of the laser beam would be perpendicular to the
guide grooves formed on the above substrate:, and the
above laser beam was continuously moved in a radius
direction of the disk with a feed amount of 50 mm per one
rotation of the disk to carry out the initial
crystallization.
Recording/retrieving evaluation was carried out by
means of ODU-1000 tester manufactured by Pulstec.
Industrial Co., Ltd. (wavelength: about 650 nm, NA=0.65,
spot shape: a circular of 0.86 mm with an intensity of
1/e2) . On the basis of the reference linear velocity of
3.49 m/s of DVD being 1-time velocity, recording
characteristics at 8-times velocity were evaluated.
The reference clock period of data at each linear
velocity was one inversely proportionated at each linear
velocity to the reference clock period of 38.2 nsec of
data at 1-time velocity.
Unless otherwise specified, retrieving was carried
out at 1-time velocity. The output signal from ODU-1000
was passed through a high frequency-passing filter having
a cutoff lies between 5 to 2 0 kHz, whereupon the jitter
was measured by a time interval analyzer (manufactured by
Yokogawa Electric Corporation). The retrieving power Pr
was 0.6 mW.
Formation of a logic level to control the recording
pulse division method was carried out by means of an
optional signal generator (AWG710, manufactured by Sony
Tektronix Co.). From the above signal generator, logic
signals at ECL level were input as gate signals against a
laser driver of the above tester.
On the disk of Example 16, EFM+ random data was
overwritten 10 times at a linear velocity of 8-times
velocity, and the jitter of said recording data was
measured.
The pulse rows for the respective mark, length
recording were set as follows. The light irradiation
time to record the nT mark was divided in order of a1T,
ß1T, a2T, b2T, ..., aiT, biT, ..., amT, bmT (m is the pulse
division number and T is the reference clock period),
irradiation with a recording laser beam with a writing
power Pw was carried out at the time of ait (1=i=m) , and
irradiation with a recording laser beam with a bias power
Pb was carried out at the time of bit (l=i=m) . These
values were set as shown in Table 6. For marks of some
lengths, the timing of irradiation with the pulse row was
delayed for a certain time from the original starting
time of said mark length in the EFM+ signal, and this
time is shown in the section "delay time". A case where
the irradiation timing was delayed was represented by +,
and a case where it was advanced was represented by -.
The value was normalized by the clock period T. The mark
formed by providing the delay time is close: to the ideal
EFM+ random signal, and the jitter is excellent. At the
space between marks (portion other than the portion
disclosed in Table), irradiation with an erasing power Pe
was carried out. Pe was 7.6 mW, and Pb was 0 mW.
The results are shown in Fig. 13. A power range in
which the jitter is at most 10% is present, and with such
characteristics, the disk can be practically applied.
INDUSTRIAL APPLICABILitY
According to the present invention, a phase-change
recording material on which high velocity
recording/erasing is possible, which provides excellent
recording signal characteristics such as jitter
characteristics, which provides a high storage stability
of the recording signals, and with which the archival
change of the recording signal quality (such as decrease
in the reflectivity) due to the long term storage is
small, and an information recording medium employing the
above material, can be obtained. Further, excellent
recording signal characteristics can be obtained even if
overwriting is carried out after the recorded medium is
stored for a long time.
The present invention has been described in detail
with reference to specific embodiments, but it should be
apparent to those skilled in the art that various changes
and modifications can be made without departing from the
intension and the scope of the present invention.
Further, this application is based on a Japanese
Patent Application No 2003-125803 (filed on April 30,
2003), and its entirety is hereby included by reference.
WE CLAIM :
1. A phase-change recording material characterized by containing a composition
represented by the following formula (1) as the main component:
Gex(InwSn1-w)yTezSb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge content, the In content, the
Sn content, and the Te content, and x, y, z and w representing atomic ratios, satisfy
the following (i) to (vi):
(i) 0=x=0.3
(ii) 0.07=y-z
(iii) wxy-z=0.1
(iv) 0 (v) (l-w)xy=0.35
(vi) 0.35=1-x-y-z)
2. The phase-change recording material as claimed in claim 1, wherein in the
formula (1), x further satisfies 0 3. The phase-change recording material as claimed in claim 1 or 2, wherein in the
formula (1), x further satisfies x =0.1
4. The phase-change recording material as claimed in any one of claims 1 to 3,
wherein in the formula (1), w further satisfies 0 5. The phase-change recording material as claimed in any one of claims 1 to 4,
wherein in the formula (1), z further satisfies 0.1 6. The phase-change recording material as claimed in any one of claims 1 to 5,
wherein of the above information recording material, the crystalline state corresponds
to a non-recorded state, and the amorphous state corresponds to a recorded state.
7. An information recording medium having a recording layer, wherein the above
recording layer contains a composition represented by the following formula (1) as the
main component:
Gex(InwSn1-w)yTe2Sb1-x-y-z (1)
(wherein the Sb content is higher than any one of the Ge content, the In content, the
Sn content and the Te content, and x, y, z and w representing atomic ratios, satisfy the
following (i) to (vi):
(i) 0 = x=0.3
(ii) 0.07 =y-z
(iii) wxy-z=0.1
(iv) 0 (v) (l-w)xy=0.35
(vi) 0.35=1-x-y-z)
8. The information recording medium as claimed in claim 7, wherein in the
formula (1), x further satisfies 0 9. The information recording medium as claimed in claim 7 or 8, wherein in the
formula (1), x further satisfies x=0.1.
10. The information recording medium as claimed in any one of claims 7 to 9.
wherein in the formula (1), w further satisfies 0 11. The information recording medium as claimed in any one of Claims 7 to 10,
wherein in the formula (1), z further satisfies 0.1 12. The information recording medium as claimed in any one of claims 7 to 11,
wherein of the above information recording mediµm, the crystalline state corresponds
to a non-recorded state, and the amorphous state corresponds to a recorded state.
13. The information recording medium as claimed in any one of claims 7 to 12,
wherein the information recording medium is an optical information recording
mediµm, on which recording is carried out by a laser beam.
14. The information recording medium as claimed in claim 13, wherein the optical
information recording medium has a protective layer A in contact with the recording
layer, and the protective layer A contains a metal oxysulfide and/or a metal nitride.
15. The information recording medium as claimed in claim 14, wherein the metal
oxysulfide is a oxysulfide of yttriµm, and the metal nitride is a nitride of an alloy
containing germanium as the main component.
16. The information recording medium as claimed in claim 14 or 15, wherein the
protective layer A is formed in contact with each side of the recording layer.
17. The information recording medium as claimed in any one of claims 14 to 16,
wherein the above protective layer A is formed in contact with the side of the
recording layer from which a laser beam enters, and the above protective layer A has
maximum thickness of 50 nm.
18. The information recording medium as claimed in any one of claims 14 to 16,
wherein the protective layer A is formed in contact with the side of the recording layer
from which a laser beam enters, and further, a protective layer B is formed on the side
opposite to the above recording layer in contact with the protective layer A, and the
total thickness of the thickness of the protective layer A and the thickness of the
protective layer B is 50 nm at the maximum.
19. The information recording medium as claimed in any one of claims 14 to 18,
wherein the recording layer has a thickness of 5 nm to 15 nm.
20. The information recording medium as claimed in any one of claims 13 to 19,
wherein the optical information recording medium further has a reflective layer, and
the reflective layer contains Ag as the main component.
A phase-change recording material on which high
velocity recording/erasing is possible, which provides
excellent recording signal characteristics, which
provides a high storage stability of the recording
signals, with which the change in the reflectivity of the
recorded signals is small even after a long term storage,
and which provides excellent recording signal
characteristics even if overwriting is carried out again,
and an information recording medium employing the above
material, are provided.
it is characterized by containing as the main
component a composition represented by
Gex(InwSn1-w)yTezSb1-x-y-z (wherein the Sb content is higher
than any one of the Ge content, the In content, the Sn
content and the Te content, and x, y, z and w
representing atomicity ratios satisfy (i) 0=x=0.3, (ii)
0.07=y-z, (iii) wxy-z=0.l, (iv) 0 (vi) 0.35=l-x-y-z).

Documents:

625-KOLNP-2005-CORRESPONDENCE.pdf

625-KOLNP-2005-FORM 27.pdf

625-KOLNP-2005-FORM-27.pdf

625-kolnp-2005-granted-abstract.pdf

625-kolnp-2005-granted-assignment.pdf

625-kolnp-2005-granted-claims.pdf

625-kolnp-2005-granted-correspondence.pdf

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

625-kolnp-2005-granted-drawings.pdf

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

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

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

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

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

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

625-kolnp-2005-granted-gpa.pdf

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

625-kolnp-2005-granted-specification.pdf


Patent Number 225651
Indian Patent Application Number 625/KOLNP/2005
PG Journal Number 47/2008
Publication Date 21-Nov-2008
Grant Date 19-Nov-2008
Date of Filing 11-Apr-2005
Name of Patentee MITSUBISHI CHEMICAL CORPORATION
Applicant Address 33-8, SHIBA 5-CHOME, MINATO-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 OHNO, TAKASHI C/O MITSUBISHI KAGAKU MEDIA CORPORATION LTD., 31-19, SHIBA 5-CHOME, MINATO-KU, TOKYO 1080014
2 HORIE, MICHIKAZU C/O MITSUBISHI KAGAKU MEDIA CORPORATION LTD., 31-19, SHIBA 5-CHOME, MINATO-KU, TOKYO 1080014
PCT International Classification Number B41M 5/26, G11B 7/24
PCT International Application Number PCT/JP2004/006112
PCT International Filing date 2004-04-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-125803 2003-04-30 Japan