JP4836910B2 - Optical information recording medium, recording / reproducing method and recording / reproducing apparatus - Google Patents

Description

  The present invention relates to an optical information recording medium capable of recording and reproducing an information signal with high signal quality by irradiating a thin film formed on a substrate with a high energy light beam such as a laser beam, and recording and reproducing. The present invention relates to a method and a recording / reproducing apparatus.

Research and development has been actively conducted on a recording medium in which a thin film is formed on a transparent substrate and an information signal is recorded / reproduced by irradiating the thin film with a laser beam focused on a minute spot. As a recordable type recording medium, a material in which a metal element or the like is dispersed with an oxide as a base material on a substrate, for example, a TeO _x (0 <x <2) recording thin film that is a mixture of Te and TeO ₂ is used. What was formed is known (for example, refer to Patent Document 1). From this recording medium, a large change in reflectance can be obtained by irradiation with a reproducing light beam.

The TeO _x recording thin film can be irradiated with laser light in the amorphous state after the film formation without performing an initialization process such as laser annealing to form a crystal recording mark. Since this is an irreversible process and cannot be corrected or erased by overwriting, a medium using this recording thin film can be used as a recording medium that can only be additionally written. In the TeO _x recording thin film, it takes some time until the signal is saturated after recording, that is, until the crystallization by laser light irradiation in the recording thin film proceeds sufficiently. For this reason, a medium using this recording thin film is not suitable as a medium requiring high-speed response, such as a computer data file for recording data on a disk and verifying the data after one rotation. Is appropriate. In order to compensate for this drawback, it has been proposed to add Pd, Au, or the like as a third element to TeO _x (see, for example, Patent Documents 2, 3, and 4). Pd and Au are considered to have a function of promoting the crystal growth of Te in the TeO _x recording thin film when irradiated with laser light, whereby the crystal grains of Te and Te—Pd alloy or Te—Au alloy are formed at high speed. Generate with Pd and Au have high oxidation resistance and do not impair the high moisture resistance of the TeO _x recording thin film.

Also, as a basic means to increase the amount of information that can be handled per medium, the laser beam spot diameter can be reduced by shortening the wavelength of the laser beam or increasing the numerical aperture of the objective lens that collects the laser beam. Generally, a method of improving the recording surface density by reducing the recording density is used. Furthermore, a multilayer structure medium in which a plurality of information layers are laminated has been put into practical use in recent years. In order to cope with such high-density recording and multi-layer recording, a recording medium in which the composition and film thickness of a recording material in which Pd, Au, etc. are added to TeO _x has been proposed (for example, see Patent Document 5). Further, the recording density is increased by an optical enhancement effect obtained by adding a reflective layer and an effect of suppressing thermal interference between marks due to cooling (for example, see Patent Document 6).
JP 50-46317 A JP 60-203490 A JP-A-61-68296 JP-A-62-88152 International Publication No. 98/09823 (pages 20-23, Fig. 4) JP 2002-251778 A

  When performing high-density recording as described above, particularly recording using a blue-violet laser, the recording layer (recording thin film) may not be suitable for high-density recording. This is because the recording layer may be damaged in some cases due to the heat load due to laser heating, and the quality of the recording signal may deteriorate due to an increase in noise or the like. In order to prevent this, it is effective to provide a protective layer made of a material such as a dielectric. The performance of the protective layer is as follows: (1) High heat resistance, protecting the recording layer from thermal damage, (2) Good adhesion to adjacent materials such as the recording layer, and peeling even under high temperature and high humidity conditions (3) It has high transparency and an appropriate refractive index, enhances the optical change of the recording layer, (4) itself is thermally stable, high temperature and high It is required that the particle size and composition distribution do not fluctuate even in wet conditions. Particularly in a write-once recording medium, it is very important to have high storage reliability as well as high density recording. Even if sufficient signal quality is obtained at the time of recording, for example, when left in a high temperature or high humidity environment, the influence of thermal damage that did not affect immediately after recording becomes obvious and noise Can also rise.

  In addition, a protection made of a material such as a dielectric to prevent the recording layer from being damaged due to a heat load caused by laser heating as described above and the quality of the recording signal from being deteriorated due to an increase in noise or the like. As a means other than providing a layer, it is also effective to provide a layer with high heat dissipation such as metal. By using a material having an appropriate optical constant in the same layer to have a reflection function, that is, a reflection layer, the optical interference effect is used to increase the light absorption rate of the recording layer and improve the recording sensitivity. Furthermore, it is common to enhance optical changes in the recording layer. The reflective layer is also required to have high heat resistance, adhesion to adjacent layers, and high storage reliability.

  An object of the present invention is to provide an optical information recording medium having good signal quality in high-density recording and high storage reliability. Another object of the present invention is to provide a recording / reproducing method and a recording / reproducing apparatus for such an optical information recording medium.

  In the optical information recording medium of the present invention, at least one information layer provided on the transparent substrate includes a protective layer and a write-once recording layer arranged in order from the transparent substrate side, , Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O, and the protective layer includes Cr— It contains at least one selected from O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O. When the total of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%, the total number ratio of Cr, Zn, Ga, In, Sn, Sb, Bi, and Te in the protective layer is 70. It is at least atomic percent.

  The optical information recording medium recording / reproducing method of the present invention is a method for recording / reproducing information by irradiating the optical information recording medium of the present invention with a light beam having a wavelength of 450 nm or less.

  The recording / reproducing apparatus for the optical information recording medium of the present invention comprises a recording / reproducing unit that records and reproduces information by irradiating the optical information recording medium of the present invention with a light beam having a wavelength of 450 nm or less; And a detection unit for detecting reflected light from the target information recording medium.

  According to the present invention, it is possible to provide an optical information recording medium with good signal quality in high-density recording and high storage reliability, and a recording / reproducing method and recording / reproducing apparatus thereof.

  In the optical information recording medium of the present invention, at least one information layer is provided on a transparent substrate. This information layer includes a protective layer and a write-once recording layer. In this information layer, the protective layer and the recording layer are arranged in this order from the transparent substrate side. The optical information recording medium of the present invention has a configuration in which a light beam such as a laser beam is incident from the transparent substrate side. The recording layer contains at least one selected from Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O. The protective layer contains at least one selected from Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O. When the total of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%, the total number ratio of Cr, Zn, Ga, In, Sn, Sb, Bi and Te in the protective layer is 70 atoms. % Or more.

  Note that in this specification, the material represented by “element-O” is a material containing the element and oxygen (O) as components, and a compound containing the element and oxygen (O), It includes oxides of the elements, oxygen deficient in the oxides of the elements, and the like.

  Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings. In addition, the following description is an example of this invention and this invention is not limited by these.

(Embodiment 1)
1 to 3 are partial sectional views of structural examples of the optical information recording medium of the present invention. In addition, the same code | symbol may be attached | subjected to the structure which has the same function, and the description may be abbreviate | omitted.

  In the optical information recording medium shown in FIG. 1, at least a protective layer 2, a recording layer 3, an intermediate layer 4 and a reflective layer 5 are arranged in this order on a transparent substrate 1. In this example, the information layer is constituted by the protective layer 2, the recording layer 3, the intermediate layer 4, and the reflective layer 5 arranged in order from the transparent substrate 1, but the information layer is formed from only the protective layer 2 and the recording layer 3. It may be configured. Further, both the intermediate layer 4 and the reflective layer 5 disposed on the opposite side of the protective layer 2 with respect to the recording layer 3 may be provided, or only one of them may be provided. Information is recorded / reproduced on the optical information recording medium by converging and irradiating laser light 6 with an objective lens 7 from the transparent substrate 1 side.

  Further, like the optical information recording medium shown in FIG. 2, a buffer layer 8 is provided between the protective layer 2 and the recording layer 3, and a protective substrate 9 is reflected on the opposite side of the intermediate layer 4 with respect to the reflective layer 5. An upper protective layer 10 may be provided between the layer 5 and the protective substrate 9. The buffer layer 8, the protective substrate 9, and the upper protective layer 10 can be provided as necessary.

  In addition, as in the optical information recording medium shown in FIG. 3, the first information layer 12 to the nth information layer 13 (where n is the nth layer) between the transparent substrate 1 and the protective substrate 9 via the separation layer 11. N number of information layers may be provided. At that time, at least one of the n information layers has the same structure (multilayer thin film structure) as the information layer shown in FIG. 1 or 2 in order from the side closer to the transparent substrate 1. have. For each information layer of the optical information recording medium, laser light 6 is condensed onto the predetermined information layer by the objective lens 7 from the transparent substrate 1 side and irradiated to record and reproduce information. In the case where the optical information recording medium of the present invention includes n information layers, as described above, at least one of the n information layers is disposed on the transparent substrate 1 side (laser light incident). The configuration of the other information layers is not limited as long as the configuration includes the protective layer 2 and the recording layer 3 arranged in order from the side). Therefore, a rewritable information layer or a read-only information layer can be used as another information layer. In this case, information that is recorded only once and does not need to be erased, and information that is to be rewritten or information that is read-only can coexist on a single medium, which is highly convenient and can be applied to various applications. A possible optical information recording medium can be provided.

  The recording layer 3 is formed of a write-once recording material, and is selected from Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O. At least one of them is included as a base material. In addition to these base materials, the recording layer 3 has Te, Sb, Bi, Ge, Sn, Ga, In, Pd, Au, Pt, Any one or more elements of Ni, Ag, and Cu can be added. When Te-O is used as the base material, for example, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ru, Rh One or more elements selected from Pd, Ag, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Bi can be added. In particular, when Te—O is used as the base material, at least one selected from Pd and Au is suitable as the additive element.

  In addition to the above components, the recording layer 3 further contains other components (elements) for the purpose of adjusting the crystallization speed, thermal conductivity, optical constants, etc., or improving heat resistance or moisture resistance. It may be. Examples of other elements contained in the recording layer 3 include one or more elements selected from non-metallic elements such as N, F, C, S, and B. These elements can be appropriately added to the recording layer 3 as necessary. The atomic ratio is 20 atomic% or less when the total of all the atoms contained in the recording layer 3 is 100 atomic%. Is preferable, and 10 atomic% or less is more preferable.

  The film thickness of the recording layer 3 is preferably 2 nm or more and 70 nm or less, and more preferably 4 nm or more and 40 nm or less. If the thickness of the recording layer 3 is thinner than the above, a sufficient reflectance and a change in reflectance cannot be obtained, and the C / N ratio may be lowered. If the thickness of the recording layer 3 is larger than the above, the thermal diffusion in the thin film surface of the recording layer 3 becomes relatively large, so that the outline of the recording mark becomes unclear and the C / N ratio becomes low in high density recording. May end up.

  The protective layer 2 contains at least one selected from Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O. Each of the above components contained in the protective layer 2 does not have to be a compound composition, and may be a composition lacking oxygen (O), for example. In order to improve the adhesion to the recording layer 3, a composition in which oxygen is deficient can be used. When the total of all atoms other than oxygen atoms contained in the protective layer 2 is 100 atomic%, the total number of atomic ratios of Cr, Zn, Ga, In, Sn, Sb, Bi, and Te in the protective layer 2 is 70 Atomic% or more (preferably 90 atomic% or more, more preferably 100 atomic%). In addition, the protective layer 2 can contain material components (for example, N, F, C, S, B, etc.) other than the above as long as the original function is not impaired.

  This protective layer 2 in combination with the recording layer 3 described above (1) has high heat resistance and protects the recording layer 3 from thermal damage, and (2) an adjacent material such as the recording layer 3 Good adhesion, and does not cause peeling, corrosion or diffusion even under high temperature and high humidity conditions, and (3) has high transparency and an appropriate refractive index, and enhances optical changes in the recording layer 3. (4) It itself is thermally stable and satisfies all the conditions that the particle size and composition distribution do not change even at high temperature and high humidity.

  Among the materials for the protective layer 2, Zn—O, Te—O, and Sn—O are preferably used. Therefore, when the protective layer 2 includes at least one selected from Zn—O, Te—O, and Sn—O, and the total of all atoms other than oxygen atoms contained in the protective layer 2 is 100 atomic%. The total number of Zn, Te and Sn in the protective layer 2 preferably occupies 30 atomic% or more.

  A group consisting of Zn—O, Te—O and Sn—O is a first component group, and a group consisting of Cr—O, Sb—O, Bi—O, In—O and Ga—O is a second component group. In this case, it is preferable that the protective layer 2 contains at least one selected from the first component group and at least one selected from the second component group. At this time, when the total of all atoms other than oxygen atoms contained in the protective layer 2 is 100 atomic%, the total atomic ratio of Zn, Te and Sn in the protective layer 2 is 33 atomic% or more and 96 atomic%. The total number of Cr, Sb, Bi, In, and Ga atoms is preferably 4 atomic% or more and 67 atomic% or less. Among these, it is more preferable that Zn—O is included as one type selected from the first component group, and Cr—O is included as one type selected from the second component group. In this case, the atomic ratio of Zn is preferably 33 atomic% to 96 atomic%, and the atomic ratio of Cr is 4 atomic% to 67 atomic% (preferably less than 50 atomic%, more preferably less than 34 atomic%). Is preferred.

  Moreover, the protective layer 2 may contain sulfur (S) as a component. Adhering the protective layer 2 containing S to the recording layer 3 is not particularly problematic because of high adhesion, but peeling, corrosion, diffusion, and the like may occur when adjacent to the transparent substrate 1 made of a resin material. For this reason, when the sum of all atoms other than oxygen atoms contained in the protective layer 2 is 100 atomic%, the ratio of the number of S atoms in the protective layer 2 is desirably 2 atomic% or less.

In addition, the protective layer 2 is not necessarily in contact with the recording layer 3, and a buffer layer is provided as necessary in order to prevent peeling or the like caused by film stress of both layers or an expansion / contraction imbalance during heating or humidification. 8 (see FIG. 2) may be interposed. For example, the adhesion can be further improved by providing the buffer layer 8 formed using various dielectric materials, particularly sulfides, carbides, and the like. For example, it is preferable to insert a buffer layer 8 formed using ZnS or a material mixed with SiO _{2 and the} like based on ZnS between the protective layer 2 and the recording layer 3.

  The material of the reflective layer 5 can be a metal such as Ag, Au, Al, or Cu, or an alloy based on these metals. Among them, an Ag alloy having a particularly high reflectance is preferable. The additive element to Ag is not particularly limited. For example, Pd, Pt, Ni, Ru, Au, Cu, Zn, Al, Ga, In, Si, which have a high effect of preventing aggregation and reducing the particle size in a small amount. Ge, Sn, Sb, Bi, Ca, Mg, Y, Nd, Sm, Ti, Cr, O, N, F, C, S, B, etc. are suitable, and among them, Pd, Cu, Bi, Nd, Y Ga is more effective, and one or more of these elements can be used. In order not to impair the high thermal conductivity and reflectance of Ag while exhibiting such an effect, the ratio of the number of atoms of the additive element is relative to the entire reflective layer 5 (of all atoms contained in the reflective layer 5). When the total is 100 atomic%), it is preferably from 0.01 atomic% to 10 atomic%, and more preferably from 0.05 atomic% to 5 atomic%.

  Examples of the material of the intermediate layer 4 include oxides such as Y, Ce, Ti, Zr, Nb, Ta, Co, Zn, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te, Ti, Zr, Nb, Ta, Cr, Mo, W, B, Al, Ga, In, Si, Ge, Sn, Pb, and other nitrides, Ti, Zr, Nb, Ta, Cr, Mo, W, and Si carbides, Zn And sulfides such as Cd, selenides or tellurides, fluorides such as rare earths such as Mg, Ca and La, simple substances such as C, Si and Ge, or a mixture thereof. However, when the reflective layer 5 contains Ag or an Ag alloy, it is preferable to use a material that does not contain sulfides, since if the sulfide is used for the intermediate layer 4, corrosion may occur. It is also possible to use the same material as the protective layer 2 for the intermediate layer 4. The thickness of the intermediate layer 4 is preferably 2 nm or more and 40 nm or less, and more preferably 5 nm or more and 20 nm or less.

  As the material of the upper protective layer 10, the materials mentioned as the material of the intermediate layer 4 can be used, but it is not necessary to be the same material as that of the intermediate layer 4. It is preferable to use a material containing no sulfide. The upper protective layer 10 may be formed of the same material as the protective layer 2 or the intermediate layer 4. The thickness of the upper protective layer 10 is preferably 2 nm or more and 80 nm or less, and more preferably 5 nm or more and 50 nm or less.

  Each of the above thin films can be formed by a vapor phase thin film deposition method such as a vacuum evaporation method, a sputtering method, an ion plating method, a CVD (Chemical Vapor Deposition) method, an MBE (Molecular Beam Epitaxy) method, or the like. Each of the above thin films is formed by a method such as Auger electron spectroscopy, X-ray photoelectron spectroscopy, or secondary ion mass spectrometry (for example, “Thin Film Handbook” edited by the Society of Applied Physics / Thin Film / Surface Physics Society) Company, 1991, etc.), it is possible to examine the material and composition of each layer. In the present embodiment, it was confirmed that the composition of the target material of each layer and the composition of the actually formed thin film were substantially equivalent. However, depending on the film forming apparatus, film forming conditions, target manufacturing method, and the like, the target material composition may differ from the actually formed thin film composition. In such a case, it is preferable to obtain a correction coefficient for correcting the composition deviation in advance from an empirical rule and to determine the target material composition so that a thin film having a desired composition can be obtained.

  Laser light is incident on the optical information recording medium of the present invention from the transparent substrate side. Therefore, the material of the transparent substrate 1 is preferably substantially transparent at the wavelength of the laser beam 6, and is a polycarbonate resin, polymethyl methacrylate resin, polyolefin resin, norbornene resin, ultraviolet curable resin, glass, or a combination thereof as appropriate. Can be used. Further, the thickness of the transparent substrate 1 is not particularly limited, but a thickness of about 0.01 to 1.5 mm can be used. For example, when the numerical aperture NA of the objective lens 5 is about 0.6 to 0.7. When the numerical aperture NA is about 0.8 to 0.9, the thickness is preferably about 0.03 to 0.2 mm. When the transparent substrate 1 is as thin as 0.3 mm or less, for example, the above-mentioned resin in the form of a sheet is pasted on the information layer, or an ultraviolet curable resin is applied by spin coating and cured by ultraviolet irradiation. Thus, the transparent substrate 1 can be produced.

  The protective substrate 9 is a substrate disposed on the side opposite to the laser beam incident side in the medium. As the material of the protective substrate 9, the same materials as those described as the material of the transparent substrate 1 can be used. However, the material may be different from that of the transparent substrate 1, and may not necessarily be transparent at the wavelength of the laser light 6. . Moreover, the thickness of the protective substrate 9 is not particularly limited, but a thickness of about 0.01 to 3.0 mm can be used.

  As the separation layer 11, an ultraviolet curable resin or the like can be used. The thickness of the separation layer 11 is at least the numerical aperture NA of the objective lens 7 so that crosstalk from other layers is reduced when reproducing any one of the first information layer 12 to the n-th information layer 13. It is necessary that the thickness be equal to or greater than the focal depth determined from the wavelength λ of the laser light 6, and it is also necessary that the thickness be within a range where all the information layers can be condensed. For example, the thickness of the separation layer 11 must be at least 10 μm to 100 μm when λ = 660 nm and NA = 0.6, and at least 5 μm to 50 μm when λ = 405 nm and NA = 0.85. It is. However, if an optical system or technique capable of reducing crosstalk between layers is developed, the thickness of the separation layer 11 may be made thinner than the above.

  Also, two optical information recording media as shown in FIGS. 2 and 3 are bonded to each other with the respective protective substrates 9 facing each other to form a double-sided structure, so that the amount of information that can be stored per medium is obtained. Can be further doubled.

  When the optical information recording medium of the present embodiment is manufactured, the protective substrate 9 may be formed or bonded after the thin films and the separation layer 11 are sequentially formed on the transparent substrate 1. The transparent substrate 1 may be formed or bonded after sequentially forming each thin film on the protective substrate 9. In particular, the latter is suitable when the numerical aperture NA of the objective lens 7 is as large as 0.8 or more and the transparent substrate 1 is as thin as 0.2 mm or less. In that case, the concave / convex patterns such as grooves and address signals, which are grooves for guiding the laser beam 6, are formed on the surfaces of the protective substrate 9 and the separation layer 11, that is, those having a desired concave / convex pattern formed in advance such as a stamper. It is formed by being transferred. At that time, especially when the layer thickness is thin as in the case of the separation layer 11 and a commonly used injection method is difficult, the 2P method (photo-polymerization method) can be used.

  FIG. 4 shows a schematic diagram of an example of the minimum necessary apparatus configuration for a recording / reproducing apparatus that performs recording / reproducing of the optical information recording medium of the present invention. In this apparatus, at least a recording / reproducing unit for recording / reproducing information by irradiating the optical information recording medium 17 with a laser beam 6 having a wavelength of 450 nm or less, and a reflected light from the optical information recording medium 17 are detected. And a photo detector (detection unit) 18. In the present embodiment, the recording / reproducing unit includes a laser diode 14 that emits laser light 6 having a wavelength of 450 nm or less, a half mirror 15, and an objective lens 7. The laser beam 6 emitted from the laser diode 14 is focused on an optical information recording medium 17 rotated by a motor 16 through a half mirror 15 and an objective lens 7. Information reproduction is performed by causing reflected light from the optical information recording medium 17 to enter the photodetector 18 and detecting a signal. The optical information recording medium 17 is the medium of the present embodiment shown in FIGS.

  When recording an information signal, the intensity of the laser beam 6 is modulated between a plurality of power levels. In order to modulate the intensity of the laser beam 6, it is preferable to modulate the drive current of the semiconductor laser, or it is possible to use means such as an electro-optic modulator or an acousto-optic modulator. A single rectangular pulse having a peak power P1 may be used for the mark forming portion. However, in the case of forming a long mark in particular, it is shown in FIG. 5 for the purpose of eliminating excessive heat and making the mark width uniform. As described above, a recording pulse train composed of a plurality of pulse trains modulated between the peak power P1 and the bottom power P3 (where P1> P3) may be used. Further, a cooling section with cooling power P4 may be provided after the last pulse. For a portion where no mark is formed, the bias power P2 (where P1> P2) is kept constant.

  Here, each pattern such as the length of the mark to be recorded and the length of the space before and after the mark causes irregularities in the mark edge position, which may cause an increase in jitter. In the recording / reproducing method of the optical information recording medium of the present invention, in order to prevent this and improve the jitter, the position or length of each pulse of the pulse train is set as necessary so that the edge position is aligned for each pattern. Can be adjusted and compensated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, a following example does not limit this invention.

Example 1
In this example, an optical information recording medium provided with two information layers (first information layer and second information layer) was produced. In this embodiment, the first information layer arranged on the transparent substrate side corresponds to the information layer in the optical information recording medium of the present invention.

A protective substrate made of polycarbonate resin having a diameter of about 12 cm, a thickness of about 1.1 mm, a groove pitch of 0.32 μm, and a groove depth of about 20 nm was used. On the surface of the protective substrate on which the groove is formed, a reflective layer made of Ag ₉₈ Pd ₁ Cu ₁ and having a thickness of 60 nm, (ZnO) ₈₀ (Cr ₂ O ₃ ) ₅ (In ₂ O ₃ ) is formed as the second information layer. Sputtering is used to form each of an intermediate layer made of _{15 with a} thickness of 10 nm, a recording layer made of Te ₃₆ O ₅₄ Pd _{10 with a} thickness of 24 nm, and a protective layer made of (ZnO) ₈₀ (Cr ₂ O ₃ ) _{20 with a} thickness of 20 nm. Were stacked in this order. On the surface of the second information layer, the same groove pattern as that of the protective substrate was transferred by the 2P method using an ultraviolet curable resin to form a separation layer having a thickness of about 25 μm. On the surface of this separation layer, as a first information layer, a 10 nm-thick reflective film made of Ag ₉₈ Pd ₁ Cu ₁ , a film made of (ZnO) ₈₀ (Cr ₂ O ₃ ) ₅ (In ₂ O ₃ ) ₁₅ Each thin film of an intermediate layer having a thickness of 10 nm, a recording layer having a thickness of 12 nm made of Te ₃₆ O ₅₄ Pd _10, and a protective layer having a thickness of 15 nm made of various materials was laminated in this order by a sputtering method. A transparent substrate having a thickness of 75 μm was formed on the surface of the first information layer using an ultraviolet curable resin.

As an embodiment of the present invention, the protective layer of the first information layer is ZnO, SnO ₂ , TeO ₂ , (ZnO) ₈₀ (Cr ₂ O ₃ ) ₂₀ , (ZnO) ₈₀ (Sb ₂ O ₃ ) ₂₀ , (ZnO). ₈₀ (Bi ₂ O ₃ ) ₂₀ , (SnO ₂ ) ₇₀ (In ₂ O ₃ ) ₃₀ , (SnO ₂ ) ₇₀ (Ga ₂ O ₃ ) ₃₀ , (TeO ₂ ) ₈₀ (Cr ₂ O ₃ ) ₂₀ , (ZnO ) Disks 1 to 12 using ₈₀ (Cr ₂ O ₃ ) ₅ (In ₂ O ₃ ) ₁₅ , (ZnO) ₅₀ (TeO ₂ ) ₅₀ and (SnO ₂ ) ₅₀ (TeO ₂ ) ₅₀ were prepared and compared. For example, (ZnO) ₅₀ (SiO ₂ ) ₅₀ , (TiO ₂ ) ₅₀ (Cr ₂ O ₃ ) ₅₀ , Si ₃ N ₄ , SiO ₂ , (ZnS) ₅₀ (SiO ₂ ) _{50 is used for} the protective layer of the first information layer. , (ZnS) ₈₀ (Cr ₂ O ₃ ) ₂₀ were used to produce disks 13 to 18, respectively.

  Using the optical system having a wavelength of 405 nm and a lens numerical aperture of 0.85 for the groove of each disk, that is, between the groove and the groove between the grooves, the linear velocity 4 While rotating at .9 m / s, a single signal with a frequency of 16.5 MHz was recorded by irradiating with laser light.

  When recording a signal, a single pulse having a power level P1 and a width of 6 ns was used, and P2, P3, P4 and the reproduction power were all 0.7 mW.

  Under this condition, a signal was recorded once on an unrecorded track, and the C / N ratio of a single signal was measured with a spectrum analyzer. Measurement was performed by arbitrarily changing P1, and a value 1.25 times the power at which the amplitude was 3 dB lower than the maximum value was set as the set power. After measuring the C / N ratio (pre-acceleration C / N ratio) at the set power of each disk, each disk was held for 100 hours at a temperature of 90 ° C. and a relative humidity of 80% in order to confirm storage reliability. The C / N ratio (C / N ratio after acceleration) was measured again. The results of the first information layer are shown in Table 1. Table 1 also shows the number of atoms of Cr, Zn, Ga, In, Sn, Sb, Bi, and Te in the protective layer when the total of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%. The total percentage (atomic%) is also shown.

  According to Table 1, all of the disks 1 to 12 according to the examples of the present invention have a sufficiently high C / N ratio before acceleration, a small decrease after acceleration, and good storage reliability. On the other hand, the disks 13 to 18 of the comparative examples differ in material composition from those of the present invention, but all of the results show that the decrease after acceleration is large and the storage reliability is insufficient.

  Similarly, in the case of the second information layer, an experiment for comparing the protective layer material was performed, and in the case of the second information layer, a single information layer having only the second information layer in which the thickness of the transparent substrate was 100 μm. In this case, the recording layer was made of Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, or Bi—O. The superiority or inferiority of the storage reliability between the materials and compositions of the layers did not change.

  As described above, since the optical information recording medium of the present invention has good signal quality in high-density recording and high storage reliability, it is a medium that stores data that can be digitized such as video, music, and information. Useful as.

It is sectional drawing which shows one structural example of the optical information recording medium of this invention. It is sectional drawing which shows another structural example of the optical information recording medium of this invention. It is sectional drawing which shows another example of a structure of the optical information recording medium of this invention. It is the schematic which shows an example of the recording / reproducing apparatus of the optical information recording medium of this invention. It is a recording pulse waveform used for recording / reproducing of the optical information recording medium of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Protective layer 3 Recording layer 4 Intermediate layer 5 Reflective layer 6 Laser light 7 Objective lens 8 Buffer layer 9 Protective substrate 10 Upper protective layer 11 Separation layer 12 First information layer 13 nth information layer 14 Laser diode 15 Half mirror 16 Motor 17 Optical information recording medium 18 Photo detector (detection unit)

Claims (14)

At least one information layer provided on the transparent substrate includes a protective layer and a write-once recording layer arranged in order from the transparent substrate side,
The recording layer includes at least one selected from Cr—O, Zn—O, Ga—O, In—O, Sn—O, Sb—O, Bi—O, and Te—O,
The protective layer contains Zn—O and at least one selected from Cr—O, Sb—O, Bi—O, In—O, and Ga—O, except for oxygen atoms contained in the protective layer In the protective layer, the atomic ratio of Zn is 33 atomic% or more and 96 atomic% or less, and the number of Cr, Sb, Bi, In, and Ga atoms in the protective layer is 100 atomic%. An optical information recording medium having a total ratio of 4 atomic% to 67 atomic% . When the protective layer contains Zn—O and Cr—O, and the total of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%, the atomic ratio of Zn in the protective layer is 33 atoms. 2. The optical information recording medium according to claim 1 , wherein the optical information recording medium is not less than 96% and not more than 96%, and the atomic ratio of Cr is not less than 4% and not more than 67%. When the total number of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%, the atomic ratio of Zn in the protective layer is 33 atomic% to 96 atomic%, and Cr atoms The optical information recording medium according to claim 2 , wherein the number ratio is 4 atom% or more and less than 50 atom%. The protective layer further contains S, and when the total of all atoms other than oxygen atoms contained in the protective layer is 100 atomic%, the atomic ratio of S in the protective layer is 2 atomic% or less. Item 4. The optical information recording medium according to any one of Items 1 to 3 . Said information layer, further comprising a buffer layer disposed between the protective layer and the recording layer, the optical information recording medium according to any one of claims 1-4. The recording layer comprises a Te-O, the optical information recording medium according to any one of claims 1-5. The optical information recording medium according to claim 6 , wherein the recording layer further includes at least one selected from Pd and Au. Further comprising a protective substrate disposed opposite the transparent substrate with respect to the information layer, the optical information recording medium according to any one of claims 1-7. Wherein the information layer groove is provided, the pitch of the grooves is 1μm or less, the optical information recording medium according to any one of claims 1-8. On the transparent substrate, there are provided n information layers of a first information layer to an nth information layer (where n is an integer of 2 or more), and at least one piece of information from the first information layer to the nth information layer layer, including the transparent substrate side the protective layer and the recording layer are disposed in order from the optical information recording medium according to any one of claims 1-9. Said information layer, further comprising a reflective layer disposed on the opposite side of the protective layer to the recording layer, the optical information recording medium according to any one of claims 1-10. Said information layer, further comprising an intermediate layer disposed on the opposite side of the protective layer to the recording layer, the optical information recording medium according to any one of claims 1 to 11. 13. A recording / reproducing method for an optical information recording medium, wherein information is recorded / reproduced by irradiating the optical information recording medium according to any one of claims 1 to 12 with a light beam having a wavelength of 450 nm or less. A recording / reproducing unit that records and reproduces information by irradiating the optical information recording medium according to any one of claims 1 to 12 with a light beam having a wavelength of 450 nm or less, and from the optical information recording medium A recording / reproducing apparatus for an optical information recording medium, comprising at least a detection unit for detecting reflected light.

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