JP3379256B2 - Optical information recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical information recording medium capable of recording, erasing and reproducing information at high speed and high density by irradiation with laser light or the like.

[0002]

2. Description of the Related Art In recent years, an optical disk using a laser beam has been developed as a recording medium that meets the demands for increasing the amount of information and increasing the recording and reproducing density and speed. Optical disks are classified into a write-once type that allows recording only once and a rewritable type that allows recording / erasing as many times as desired.

Examples of the rewritable optical disk include a magneto-optical recording medium utilizing a magneto-optical effect and a phase change medium utilizing a reversible change in crystal state. The phase change medium is
Recording / erasing is possible by changing the power of the laser beam without the need for an external magnetic field. Further, there is an advantage that it is possible to perform one-beam overwriting in which erasing and re-recording are simultaneously performed with a single beam.

In the one-beam overwritable phase change recording method, it is general that the recording film is made amorphous to form a recording bit and is crystallized to erase. A chalcogen-based alloy thin film is often used as a recording layer material used in such a phase change recording method.

For example, Ge-Te system, Ge-Te-Sb
System, In-Sb-Te system, Ge-Sn-Te system alloy thin film, and the like. A write-once type phase change medium can be realized by using almost the same material and layer structure as the rewritable type. In this case, since there is no reversibility, information can be recorded and stored for a longer period of time, and in principle, it can be stored almost permanently.

When the phase change medium is used as the write-once type, unlike the perforated type, there is no swelling called a rim around the bit, so that the signal quality is excellent, and since an air gap is not required above the recording layer, it has an air sandwich structure. It has the advantage of not having to. Generally, in a rewritable phase change recording medium, two different laser light powers are used to realize different crystal states.

This method will be described by taking as an example the case of performing recording / erasing in an erased / initial state in which an amorphous bit and crystallized. Crystallization is performed by heating the recording layer to a temperature sufficiently higher than the crystallization temperature of the recording layer and lower than the melting point. In this case, the cooling layer is sandwiched between dielectric layers or a long elliptical beam is used in the moving direction of the beam so that the crystallization is sufficiently slow.

On the other hand, the amorphization is performed by heating the recording layer to a temperature higher than the melting point and quenching it. in this case,
The dielectric layer also has a function as a heat dissipation layer for obtaining a sufficient cooling rate (supercooling rate). In addition, in order to prevent deformation of the recording layer due to melting and volume change in the heating / cooling process, thermal damage to the plastic substrate, and deterioration of the recording layer due to moisture as described above, A protective layer consisting of a body layer is important.

The protective layer material is such that it is optically transparent to laser light, has a high melting point / softening point / decomposition temperature, is easy to form, and has suitable thermal conductivity. Selected from the perspective. Examples of the protective layer having sufficient heat resistance and mechanical strength include a dielectric thin film such as metal oxide or nitride.

Since the dielectric thin film and the plastic substrate differ greatly in the coefficient of thermal expansion and elastic properties, they may be peeled off from the substrate to cause pinholes and cracks during repeated recording and erasing. Further, the plastic substrate is liable to warp due to humidity, which may also cause peeling of the protective film.

On the other hand, ZnS is used as a new dielectric protective layer.
It has been proposed that the main component is, and SiO ₂ or Y ₂ O ₃ is mixed. These composite compound protective films are superior in adhesion to chalcogenide alloy thin films such as GeTeSb, which are often used as recording layers, as compared with pure oxide or nitride dielectric films.

Therefore, in addition to the durability against repeated overwriting, the film peeling in the accelerated test is small, and the reliability of the phase change medium is further improved.

[0013]

However, the composite compound does not always exhibit good properties when simply mixed. Depending on the composition range and the physical properties of the composite film, the reliability may be lowered rather than the case where individual pure compounds are used.

Conventionally, oxides, nitrides, fluorides, etc. are added to ZnS, ZnSe, etc., which are compounds containing chalcogenide elements.
Although many proposals have been made for protective films mixed with carbides, etc., only some of them describe the optimum composition range.Even if a mixture of such compositions is used, it is not always possible to obtain a pure compound alone from the original pure compound. No excellent characteristics were obtained than the protective layer.

This is because the physical properties of the above-mentioned composite material are greatly different from those of the compounds constituting the composite material, and changes in the physical properties due to the manufacturing method and other factors were unpredictable. For example, a sputtering method is widely used for forming a protective layer made of the above-mentioned composite compound. However, the composite compound protection which is naturally obtained when the composite target is used and when the individual targets are simultaneously sputtered. The physical properties of the film are different.

It is a well-known fact that even in the same manufacturing method, the physical properties change due to the pressure during sputtering. In the presence of such variations in the physical properties of the protective film, how to find a composite protective film suitable for a phase change medium has been an issue.

[0017]

The optical information recording medium of the present invention is an optical information recording medium having at least a phase transition type optical recording layer and a dielectric layer on a substrate, wherein the dielectric layer is It is characterized by containing at least a chalcogen compound, a rare earth fluoride and a metal oxide. As the chalcogen compound, it is preferable to use at least one selected from the group consisting of ZnS, ZnSe and ZnTe.

As a rare earth fluoride, PmF₃, SmF₃,
EuF₃, GdF₃, TbF, DyF ₃, LaF₃, CaF
₃, PrF₃And NdF₃At least one selected from the group of
It is preferred to use seeds. SiO as oxide₂, T
a₂O_Five, ZrO₂And Y₂O₃At least one selected from the group of
It is preferable to use one kind.

The dielectric layer is preferably formed by using a composite sputtering target composed of a mixture of a plurality of compounds forming the dielectric. Next, the structure of the optical recording medium according to the present invention will be described. The optical recording medium of the present invention usually has at least a structure of substrate / dielectric layer / recording layer / dielectric layer / reflection layer, and the substrate is made of a transparent resin such as polycarbonate, acryl or polyolefin, or glass. Etc. can be used.

On the surface of the substrate, a dielectric satisfying the above characteristics is
Usually, the thickness is set to 100 to 5000Å. When the thickness of the dielectric layer is less than 100 Å, the effect of preventing the deformation of the substrate and the recording film is insufficient and does not serve as a protective layer. If it exceeds 5000 Å, the internal stress of the dielectric layer itself and the difference in elastic characteristics from the substrate become remarkable, and cracks are likely to occur.

In the present invention, a mixture of two or more different compounds is used in the dielectric layer. That is, it contains at least a chalcogen compound, a rare earth fluoride and a metal oxide. Chalcogen refers to the four elements of sulfur, selenium, tellurium and polonium. The chalcogen compound is preferably Zn
At least one selected from the group of S, ZnSe and ZnTe is used. The content of the chalcogen compound in the dielectric layer is preferably about 50 to 90 mol%.

The rare earth fluoride is preferably PmF.
It is at least one selected from the group of ₃ , SmF ₃ , EuF ₃ , GdF ₃ , TbF ₃ and DyF ₃ . The content of rare earth fluoride in the dielectric layer is preferably about 5 to 40 mol%. The metal oxide is preferably SiO ₂ , Ta ₂ O ₅ ,
It is at least one selected from the group of ZrO ₂ and Y ₂ O ₃ . The content of the metal oxide in the dielectric layer is 5 to 40 mo.
About 1% is desirable.

The dielectric layer may have a main component (50 mol% or more, preferably 80 mol% or more) in total of the chalcogen compound, the rare earth fluoride and the metal oxide, and may be mixed with another dielectric. . Si as another dielectric
_{O 2, ZrO 2, BaO,} B 2 O 3 and the like. When another dielectric is mixed in the dielectric layer, it is necessary that the heat resistance at 1000 ° C. or higher and the optical characteristics are maintained.

The heat resistance of 1000 ° C. or higher means that the melting point is 10.
It means that no decomposition occurs even if heated to 1000 ° C while keeping the temperature above 00 ° C. The optical characteristic means that the light absorption coefficient is 0.02 or less at a thickness of 500 Å. The film density of the dielectric layer is preferably 80% or more of the theoretical density.

The theoretical density of the film is represented by the following formula, and is an integrated value of the density of each constituent compound in the bulk state and the molar content of the constituent compound. Theoretical density = Σ {(density of constituent compound in bulk state) × (molar content of constituent compound)} By setting the density of the mixture dielectric layer in this way, durability against repeated recording and aging can be significantly improved. it can.

The film density can be controlled by adjusting the degree of vacuum during sputtering. Decrease the vacuum degree (decrease the argon gas pressure) to increase the film density.
The degree of vacuum is usually 1 Pa or less, preferably about 0.8 to 0.1. The dielectric layer is
It is preferable to use a composite sputtering target composed of a mixture of a plurality of compounds forming the film.

This is because a sputtering method is generally widely used in forming a dielectric layer made of the above-mentioned composite compound. However, the composite target is used in comparison with the simultaneous sputtering using the individual compound targets. In addition, the resulting composite compound protective film is excellent in uniformity of the constituent elements, and thus the properties as a protective film are also excellent, which is preferable.

The recording layer of the medium of the present invention is a phase change type recording layer, and the thickness thereof is preferably in the range of 100Å to 1000Å. If the thickness of the recording layer is less than 100Å, it is difficult to obtain sufficient contrast, and the crystallization speed tends to be slow, which makes it difficult to erase the recording in a short time. While 10
If it exceeds 00Å, it is difficult to obtain optical contrast and cracks are likely to occur, which is not preferable.

The thicknesses of the recording layer and the dielectric layer should be such that the absorption efficiency of laser light is good and the amplitude of the recording signal, that is, the contrast between the recorded state and the unrecorded state is large, taking into consideration the interference effect associated with the multilayer structure. To be chosen. For the recording layer, a ternary compound such as GeSbTe or InSbTe is selected as an overwritable material. These three
0.1 to 10 atomic% Sn, In, Pb, A in the original compound
s, Se, Si, Bi, Au, Ti, Cu, Ag, P
It is also effective to add one or more elements out of t, Pd, Co, Ni and the like to improve the crystallization rate, optical constants and oxidation resistance.

An optical reflection layer and a hard coat layer for preventing thermal deformation are provided on the outer protection layer (protection layer not on the substrate side). The optical reflection layer is preferably a substance having a high reflectance, and Au is preferably used. , Ag, Cu, Al, etc. are used. This reflective layer has the effect of promoting the diffusion of the thermal energy absorbed by the recording layer, so that Ta, Ti,
It is preferable to add a small amount of Cr, Mo, Mg, V, Nb, Zr or the like.

The recording layer, the dielectric layer and the reflective layer are formed by a sputtering method or the like. It is desirable to form a film by an in-line apparatus in which the target for the recording film, the target for the protective film, and if necessary, the target for the reflective layer material are installed in the same vacuum chamber in order to prevent oxidation and contamination between the layers. It is also excellent in terms of productivity.

[0032]

The present invention will be described in detail with reference to the following examples. Example 1 As a dielectric layer material, powders of ZnS, SmF ₃ and SiO ₂ were adjusted and mixed in a molar ratio of 80:10:10, and a composite sintered body target was obtained by a hot pressing method.

Dielectric layer / on polycarbonate resin substrate
A recording layer / dielectric layer / reflection layer was provided to prepare a four-layer recording medium. The thickness of each layer is the lower dielectric layer 1800Å,
Recording layer 300Å, upper dielectric layer 300Å, reflective layer 100
It was 0Å. The composition of the recording layer is Ge _(22.2) Sb _(22.2) Te
_(55.6) .

An Al alloy was used for the reflective layer. The dielectric layer is A
A film was formed by high frequency (13.56 MHz) sputtering with an r gas pressure of 0.7 Pa. Film density is 3.3g / cc
And was 84% of the theoretical density. The recording layer and the reflective layer were formed by DC sputtering under Ar gas pressure of 0.7 Pa.

Further, an ultraviolet curable resin having a thickness of about 4 μm was provided. This disk was further initialized by using an Ar ion laser, that is, the recording layer was crystallized, and the dynamic characteristics of the disk were evaluated under the following conditions. 4MHz, duty 50% while rotating at a linear velocity of 10m / s
The pulsed light was used to repeatedly overwrite with a recording power of 13 mW and a base power of 7.5 mW, and the C / N ratio was measured each time a predetermined number of times was reached. As shown in FIG. 1, after repeating 10,000 times, the decrease in C / N was about 2 dB compared with the 10th time, and the decrease in C / N after 100,000 times was about 5 dB compared with the 10th time. there were.

Comparative Example 1 ZnS and SmF ₃ as protective layer materials in Example 1
A disk was prepared in the same manner as above except that the one whose molar ratio was 40:60 was used, and the same dynamic characteristic evaluation was performed. As a result, as shown in FIG. 2, the C / N reduction was about 5 dB after 1,000 cycles compared to the 10th cycle. The film density was 5.9 g / cc, which was 95% of the theoretical density.

Example 2 A disk was prepared in the same manner except that the protective layer material of Example 1 was mixed with 10 mol% of ZrO _2, and the same dynamic characteristics were evaluated. The results were almost the same as in Example 1.

[0038]

EFFECT OF THE INVENTION By using the optical recording medium of the present invention, recording and erasing can be repeated many times, and it is effective in many practical applications of this type of recording / erasing medium.

[Brief description of drawings]

FIG. 1 is a graph showing changes in C / N in an example.

FIG. 2 is a graph showing changes in C / N in a comparative example.

[Explanation of symbols]

1 Graph of Example 1 2 Graph of Comparative Example 1

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G11B 7/24

Claims (6)

(57) [Claims] 1. A phase transition type optical recording layer on a substrate,
An optical information recording medium provided with a dielectric layer, wherein the dielectric layer contains at least a chalcogen compound, a rare earth fluoride and a metal oxide. 2. The chalcogen compound is ZnS or ZnSe.
The optical information recording medium according to claim 1, wherein the optical information recording medium is at least one selected from the group consisting of ZnTe and ZnTe. 3. The rare earth fluoride is PmF ₃ , SmF ₃ or E.
uF ₃ , GdF ₃ , TbF ₃ , DyF ₃ , LaF ₃ , Ca
F _3, PrF _3, and the optical information recording medium according to claim 1 or 2 is at least one selected from the group consisting of NdF _3. 4. The metal oxide is SiO ₂ , Ta ₂ O ₅ , Zr.
4. The optical information recording medium according to claim 1, which is at least one selected from the group consisting of O ₂ and Y ₂ O ₃ . 5. An optical information recording medium according to any one of claims 1 to 4 film density of the dielectric layer, characterized in that at least 80% of theoretical density. 6. The dielectric layer according to claim 1, characterized in that the target consists of a mixture is a film formed by sputtering of a plurality of compounds constituting the dielectric 乃
6. The optical information recording medium according to any one of items 5 to 5 .