WO2021117470A1 - Couche d'enregistrement pour support d'enregistrement d'informations optique, support d'enregistrement d'informations optique, et cible de pulvérisation cathodique - Google Patents

Couche d'enregistrement pour support d'enregistrement d'informations optique, support d'enregistrement d'informations optique, et cible de pulvérisation cathodique Download PDF

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WO2021117470A1
WO2021117470A1 PCT/JP2020/043470 JP2020043470W WO2021117470A1 WO 2021117470 A1 WO2021117470 A1 WO 2021117470A1 JP 2020043470 W JP2020043470 W JP 2020043470W WO 2021117470 A1 WO2021117470 A1 WO 2021117470A1
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optical information
oxide
recording medium
information recording
layer
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PCT/JP2020/043470
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English (en)
Japanese (ja)
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功兵 西山
田内　裕基
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株式会社神戸製鋼所
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2407—Tracks or pits; Shape, structure or physical properties thereof
    • G11B7/24073—Tracks
    • G11B7/24082—Meandering
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2433—Metals or elements of Groups 13, 14, 15 or 16 of the Periodic Table, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2578—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers

Definitions

  • the present invention relates to a recording layer for an optical information recording medium, an optical information recording medium, and a sputtering target.
  • large-capacity optical discs have been commercialized.
  • the recording methods for write-once optical discs are mainly phase change methods that change the phase of the recording layer, interlayer reaction methods that react multiple recording layers, decomposition methods that decompose the compounds that make up the recording layer, and recording layers. It is roughly classified into a drilling method in which recording marks such as holes and pits are locally formed.
  • a recording layer of an optical information recording medium constituting this large-capacity optical disc As a recording layer of an optical information recording medium constituting this large-capacity optical disc, a recording layer containing Mn oxide has been proposed (see JP-A-2012-139876).
  • this recording layer is irradiated with laser light, heated Mn oxide by the laser beam, it decomposed to release oxygen (O 2 gas), so bubbles are generated in the laser irradiated portion. As a result, the film shape changes and a recording mark is formed. That is, this recording layer is classified into a write-once type drilling method.
  • the modulation degree is excellent enough to secure the signal amplitude necessary for reproducing the recorded signal, and the reading signal can be read.
  • a recording layer having a high C / N ratio Carrier to Noise ratio, which is an output ratio to the background noise level, is realized.
  • the power of the laser beam reaching the recording layer fluctuates due to the thickness of the recording layer and the in-plane non-uniformity due to individual differences during mass production. Therefore, in addition to the basic characteristics such as the degree of modulation and the C / N ratio, the recording layer is unlikely to deteriorate the signal characteristics of the recorded signal even when the power of the laser beam to be recorded fluctuates from the optimum value. Desired.
  • the present invention has been made based on the above circumstances, and is excellent in basic characteristics such as modulation degree and C / N ratio, and is also excellent in power margin.
  • An object of the present invention is to provide an optical information recording medium using a recording layer and to provide a sputtering target for forming the recording layer for the optical information recording medium.
  • the present inventors have appropriately controlled the atomic number ratio of Mn, including Sn oxide or Ta oxide together with W oxide in addition to Mn oxide.
  • the present invention was completed by finding that the power margin can be improved.
  • recording marks are formed by the generation of bubbles by laser irradiation, but Sn oxide or Ta oxide is further added together with W oxide, and the atomic number ratio of Mn is appropriately adjusted.
  • the present inventors consider that the power margin is improved as a result of changing the mechanical properties of the recording layer and making it easier to stabilize the morphology of the bubbles by controlling the recording layer.
  • the invention made to solve the above problems is a recording layer for an optical information recording medium capable of recording an information signal by irradiation with laser light, and is a Sn oxide or Ta oxidation together with a Mn oxide and a W oxide. It has a metal oxide containing a substance, and the ratio of the number of atoms of Mn to the total number of atoms of the metal elements constituting the metal oxide is 3 atm% or more and 40 atm% or less.
  • the recording layer for the optical information recording medium uses an irreversible recording method by generating bubbles due to laser irradiation of Mn oxide, it is excellent in basic characteristics such as modulation degree and C / N ratio. Further, the recording layer for an optical information recording medium contains Sn oxide or Ta oxide together with W oxide in addition to Mn oxide as a metal oxide, and the atomic number ratio of Mn is controlled within the above range. .. Therefore, the bubbles generated by laser irradiation of the Mn oxide of the recording layer for the optical information recording medium are easily stabilized by the W oxide and the Sn oxide or the Ta oxide, and the power margin is improved. Therefore, the recording layer for the optical information recording medium is excellent in basic characteristics such as the degree of modulation and the C / N ratio, and is also excellent in the power margin.
  • the ratio of the number of atoms of W to the total number of atoms of the metal elements constituting the metal oxide is preferably 10 atm% or more and 65 atm% or less.
  • the ratio of the number of atoms of Sn or Ta to the total number of atoms of the metal elements constituting the metal oxide is preferably 5 atm% or more.
  • the metal oxide may contain Sn oxide and Ta oxide, and the ratio of the total atomic number of Sn and Ta to the total atomic number of the metal elements constituting the metal oxide is preferably 5 atm% or more.
  • the metal oxide further contains Zn oxide.
  • Zn oxide in the metal oxide, the power margin can be further improved.
  • Another invention made to solve the above problems includes a recording layer for an optical information recording medium of the present invention and a protective layer laminated on the front surface and the back surface of the recording layer for an optical information recording medium, and the above protection is provided.
  • the optical information recording medium includes the recording layer for the optical information recording medium of the present invention, it is excellent in basic characteristics such as modulation degree and C / N ratio, and is also excellent in power margin. Further, since the protective layer of the optical information recording medium is a dielectric material, the signal strength can be increased and the basic characteristics thereof can be further improved.
  • a sputtering target for forming a recording layer for an optical information recording medium capable of recording an information signal by irradiation with a laser beam, wherein at least Mn and metal elements are used. It contains Sn or Ta together with W, and the ratio of the number of atoms of Mn to the total number of atoms of the metal elements is 3 atm% or more and 40 atm% or less.
  • the sputtering target contains Sn or Ta together with at least Mn and W as metal elements, and the ratio of the number of atoms of Mn to the total number of atoms of the metal elements is within the above range.
  • the sputtering target is used as a sputtering target for forming a recording layer for an optical information recording medium while oxidizing a contained metal element, so that in addition to Mn oxide as a metal oxide, Sn oxide together with W oxide.
  • it contains Ta oxide, and the atomic number ratio of Mn can be easily controlled within the above range. Therefore, by using the sputtering target, it is possible to easily manufacture a recording layer for an optical information recording medium which is excellent in basic characteristics such as a degree of modulation and a C / N ratio and also has an excellent power margin.
  • the ratio of the number of atoms of W to the total number of atoms of the metal elements is preferably 10 atm% or more and 65 atm% or less.
  • the ratio of the number of atoms of Sn or Ta to the total number of atoms of the metal elements is preferably 5 atm% or more.
  • the recording layer for an optical information recording medium and the optical information recording medium of the present invention are excellent in basic characteristics such as modulation degree and C / N ratio, and are also excellent in power margin.
  • FIG. 1 is a schematic side view showing a layer structure of an optical information recording medium according to an embodiment of the present invention.
  • FIG. 2 is a graph showing a measurement example of the degree of modulation in the examples.
  • FIG. 3 is a graph showing a measurement example of jitter in the examples.
  • the optical information recording medium shown in FIG. 1 is laminated on the front surface and the back surface of a substrate 1, a recording layer 2 for an optical information recording medium, which is itself an embodiment of the present invention, and a recording layer 2 for an optical information recording medium.
  • a protective layer 3 and a light transmitting layer 4 are provided. Further, the protective layer 3 on the back surface side of the recording layer 2 for the optical information recording medium is laminated on the substrate 1, and the light transmitting layer 4 is laminated on the protective layer 3 on the front surface side of the recording layer 2 for the optical information recording medium. .. That is, in the optical information recording medium, the substrate 1, the protective layer 3, the optical information recording medium recording layer 2, the protective layer 3, and the light transmitting layer 4 are laminated in this order from the bottom.
  • the optical information recording medium can be used as, for example, a CD, DVD, BD, or the like.
  • a blue laser light having a wavelength of 380 nm or more and 450 nm or less, preferably about 405 nm is irradiated to the recording layer 2 for the optical information recording medium to obtain data. Recording and playback can be performed.
  • the power of the laser beam used at this time is practically 5 mW or more and 15 mW or less.
  • the substrate 1 is a member for ensuring the strength of the optical information recording medium.
  • the shape of the substrate 1 is appropriately determined according to the standard of the optical information recording medium and the like.
  • the substrate 1 has a disk shape with an outer diameter of 120 mm, and irregularities (grooves) as wobbling grooves are formed on the surface on the side where the protective layer 3 is laminated.
  • Examples of the material of the substrate 1 include polycarbonate, norbornene-based resin, cyclic olefin-based copolymer, and amorphous polyolefin.
  • the upper limit of the average thickness of the substrate 1 is preferably 1.2 mm, more preferably 1.1 mm. If the average thickness of the substrate 1 is less than the above lower limit, the strength of the optical information recording medium may be insufficient. On the contrary, if the average thickness of the substrate 1 exceeds the above upper limit, it may not conform to the standard of, for example, a large-capacity optical disc.
  • the recording layer 2 for an optical information recording medium is a recording layer for an optical information recording medium capable of recording an information signal by irradiation with a laser beam.
  • the recording layer 2 for an optical information recording medium has a metal oxide containing Sn oxide or Ta oxide together with Mn oxide and W oxide.
  • the recording layer 2 for an optical information recording medium is a write-once type recording layer of a perforation type.
  • the Mn oxide When the recording layer 2 for an optical information recording medium is irradiated with a laser beam, the Mn oxide is heated and decomposed by the laser beam to release oxygen (O 2 gas) so that bubbles are generated in the laser-irradiated portion. become. As a result, the shape of the recording layer 2 for the optical information recording medium changes, and a recording mark is formed. In the portion where the bubbles are generated and the recording mark is formed, the transmittance is increased (the reflectance is decreased) as compared with the portion where the bubbles are not generated (that is, the portion where the recording mark is not formed). It is considered that the recording layer 2 for the optical information recording medium can increase the degree of modulation.
  • the recording layer 2 for the optical information recording medium contains Mn oxide, the light absorption rate can be increased, so that the energy of the laser beam can be efficiently converted into heat energy at the time of writing. Therefore, the recording layer 2 for the optical information recording medium can improve the recording sensitivity.
  • the form of the Mn oxide is not particularly limited as long as it exists as a normal state, and is an oxide composed of only Mn and oxygen (O) such as MnO, Mn 3 O 4 , Mn 2 O 3 , and Mn O 2. It may be a composite oxide containing other metals such as W, Zn, and Sn.
  • the lower limit of the ratio of the number of atoms of Mn to the total number of atoms of the metal elements constituting the metal oxide is 3 atm%, more preferably 10 atm%.
  • the upper limit of the Mn atom number ratio is 40 atm%, more preferably 35 atm%. If the ratio of the number of atoms of Mn is less than the above lower limit, the effect of improving the degree of modulation and the recording sensitivity of the recording layer 2 for the optical information recording medium may be insufficient. On the contrary, when the atomic number ratio of Mn exceeds the upper limit, the atomic number of W, Sn or Ta is relatively reduced, so that the effect of improving the power margin may be insufficient.
  • the recording layer 2 for the optical information recording medium preferably does not contain the metal Mn. Oxidation and decomposition of the metal Mn are likely to proceed, and when the recording layer 2 for the optical information recording medium contains the metal Mn, the durability of the recording layer 2 for the optical information recording medium and the durability of the optical information recording medium are deteriorated. It may be lowered.
  • the specific "does not contain a metal element” means that the specific metal element is intentionally not contained, and the metal element inevitably contained may exist.
  • the content of the metal element inevitably contained in the recording layer 2 for the optical information recording medium is about 100 mass ppm or less in the recording layer 2 for the optical information recording medium. That is, "does not contain metal Mn” means that metal Mn is not intentionally contained, and therefore the content of metal Mn in the recording layer 2 for the optical information recording medium is 100 mass ppm or less.
  • the recording layer 2 for an optical information recording medium contains a Sn oxide or a Ta oxide together with a W oxide as a metal oxide in addition to the Mn oxide.
  • the W oxide and the Sn oxide or the Ta oxide stabilize the bubbles generated by irradiating the Mn oxide of the recording layer 2 for the optical information recording medium with the laser, and improve the power margin.
  • the metal oxide further contains a Zn oxide. By including Zn oxide in the metal oxide, the power margin can be further improved.
  • the form of the W oxide, Sn oxide, Ta oxide and Zn oxide may be an oxide bonded only to oxygen (O), and is a composite containing other metal elements. It may be an oxide.
  • the lower limit of the ratio of the number of atoms of W to the total number of atoms of the metal elements constituting the metal oxide is preferably 10 atm%, more preferably 15 atm%.
  • the upper limit of the atomic number ratio of W 65 atm% is preferable, and 50 atm% is more preferable. If the atomic number ratio of W is less than the lower limit, the power margin may decrease. On the contrary, when the atomic number ratio of W exceeds the upper limit, the atomic number ratio of Sn or Ta is relatively decreased, so that the jitter characteristic is deteriorated and a reading error may easily occur.
  • the lower limit of the ratio of the number of atoms of Sn or Ta to the total number of atoms of the metal elements constituting the metal oxide is preferably 5 atm%, more preferably 10 atm%.
  • the upper limit of the atomic number ratio of Sn or Ta 60 atm% is preferable, and 50 atm% is more preferable. If the atomic number ratio of Sn or Ta is less than the above lower limit, the jitter characteristic may be deteriorated and a reading error may easily occur. On the contrary, when the atomic number ratio of Sn or Ta exceeds the upper limit, the atomic number ratio of W is relatively decreased, so that the power margin may be decreased.
  • the lower limit of the atomic number ratio of W to the atomic number of Sn or Ta constituting the metal oxide 0.3 is preferable, and 0.4 is more preferable.
  • the upper limit of the atomic number ratio of W to the atomic number of Sn or Ta 12 is preferable, and 10 is more preferable. If the atomic number ratio of W to the atomic number of Sn or Ta is less than the lower limit, the power margin may decrease. On the contrary, when the atomic number ratio of W to the atomic number of Sn or Ta exceeds the upper limit, the atomic number ratio of Sn or Ta is relatively lowered, so that the jitter characteristic is lowered and a reading error is likely to occur. There is a risk.
  • the lower limit of the ratio of the number of Zn atoms to the total number of atoms of the metal elements constituting the metal oxide is preferably 5 atm%, more preferably 10 atm%.
  • the upper limit of the atomic number ratio of Zn 70 atm% is preferable, 50 atm% is more preferable, and 40 atm% is further more preferable. If the ratio of the number of atoms of Zn is less than the above lower limit, the effect of improving the power margin may be insufficient due to the Zn oxide. On the contrary, when the atomic number ratio of Zn exceeds the upper limit, the atomic number of W, Sn or Ta is relatively reduced, so that the power margin may be lowered.
  • the metal oxide may contain oxides other than Mn oxide, W oxide, Sn oxide, Ta oxide and Zn oxide.
  • examples of such a metal oxide include In oxide and Cu oxide.
  • the metal oxide does not contain oxides other than Mn oxide, W oxide, Sn oxide, Ta oxide and Zn oxide.
  • metal oxides other than Mn oxide it is preferable that the metal constituting these oxides is not contained as a simple substance of the metal element. Above all, it is more preferable that all the metal elements contained in the recording layer 2 for the optical information recording medium are oxidized.
  • metal In, metal Zn, metal Ta, metal Cu, metal Sn, etc. may deprive other oxides of oxygen and oxidize, which may deteriorate the characteristics of the recording layer 2 for the optical information recording medium. ..
  • the lower limit of the average thickness of the optical information recording medium recording layer 2 is set as the lower limit. 2 nm is preferable, 5 nm is more preferable, and 10 nm is further preferable.
  • the upper limit of the average thickness of the recording layer 2 for the optical information recording medium is preferably 50 nm, more preferably 40 nm, and even more preferably 15 nm. If the average thickness of the recording layer 2 for the optical information recording medium is less than the above lower limit, the number of Mn atoms in the thickness direction of the recording layer 2 for the optical information recording medium decreases, so that the recording mark is sufficiently formed.
  • the degree of modulation may be insufficient.
  • the recording layer 2 for the optical information recording medium exceeds the above upper limit, the recording layer 2 for the optical information recording medium becomes unnecessarily thick, so that the recording layer 2 for the optical information recording medium is formed. It takes a long time to reduce the productivity, and the laser power required for recording may become too large.
  • the recording layer 2 for an optical information recording medium uses an irreversible recording method by generating bubbles accompanying laser irradiation of Mn oxide, it is excellent in basic characteristics such as modulation degree and C / N ratio. Further, the recording layer 2 for an optical information recording medium contains a Sn oxide or a Ta oxide together with a W oxide in addition to the Mn oxide as a metal oxide, and the atomic number ratio of Mn constitutes the metal oxide. It is controlled to be 3 atm% or more and 40 atm% or less with respect to the total number of atoms of the elements.
  • the bubbles generated by laser irradiation of the Mn oxide of the recording layer 2 for the optical information recording medium are easily stabilized by the W oxide and the Sn oxide or the Ta oxide, and the power margin is improved. Therefore, the recording layer 2 for the optical information recording medium is excellent in basic characteristics such as the degree of modulation and the C / N ratio, and is also excellent in the power margin.
  • the protective layer 3 is a dielectric. Oxygen bubbles are generated in the recording layer 2 for the optical information recording medium by laser irradiation, but the dielectric prevents the bubbles from escaping, and the reflectance of the recording layer 2 for the optical information recording medium is lowered. Suppress. Therefore, when the optical information recording medium includes a dielectric as the protective layer 3, it becomes easy to secure the degree of modulation of the optical information recording medium recording layer 2.
  • Examples of the material of the dielectric material constituting the protective layer 3 include oxides such as Si, Al, In, Zn, Zr, Ti, Nb, Ta, Cr and Sn, Si, Al, In, Ge, Cr and Nb.
  • Known dielectrics such as nitrides such as Mo and Ti, Zn sulfides, carbides such as Cr, Si, Al, Ti, Zr and Ta, and fluorides such as Mg, Ca and La can be mentioned.
  • In 2 O 3 which is an oxide of In, is preferable from the viewpoint of productivity of the optical information recording medium and recording sensitivity.
  • these dielectrics may be mixed and used.
  • the upper limit of the average thickness of the protective layer 3 is preferably 30 nm, more preferably 25 nm. If the average thickness of the protective layer 3 is less than the above lower limit, the effect of preventing the escape of bubbles generated when the recording layer 2 for the optical information recording medium is irradiated with the laser may be insufficient. On the contrary, when the average thickness of the protective layer 3 exceeds the above upper limit, light interference is likely to occur, and bubbles are less likely to be generated in the recording layer 2 for the optical information recording medium. Recording sensitivity may decrease.
  • the light transmitting layer 4 smoothes the surface of the optical information recording medium to facilitate the incident of laser light, and prevents corrosion of the protective layer 3 and the recording layer 2 for the optical information recording medium.
  • the material of the light transmitting layer 4 a material having a high transmittance for the laser light for recording / reproduction and a small light absorption rate is selected.
  • the material of the light transmitting layer 4 for example, polycarbonate, ultraviolet curable resin, or the like can be used.
  • the lower limit of the average thickness of the light transmitting layer 4 is preferably 0.01 mm, more preferably 0.015 mm.
  • the upper limit of the average thickness of the light transmitting layer 4 is preferably 0.2 mm, more preferably 0.15 mm. If the average thickness of the light transmitting layer 4 is less than the above lower limit, the corrosion prevention effect on the protective layer 3 and the recording layer 2 for the optical information recording medium may be insufficient. On the contrary, if the average thickness of the light transmitting layer 4 exceeds the above upper limit, the NA (numerical aperture) becomes too small, and there is a possibility that fine recording marks cannot be recorded.
  • the optical information recording medium is manufactured including, for example, a substrate preparation step, a back surface side protective layer laminating step, a recording layer laminating step for an optical information recording medium, a front surface side protective layer laminating step, and a light transmitting layer laminating step. It can be manufactured by the method.
  • the substrate preparation step the substrate 1 having irregularities as wobbling grooves formed on the surface on the side where the protective layer 3 is laminated is prepared.
  • Such a substrate 1 can be formed by transferring the uneven shape of the wobbling groove for tracking from the mastering master by injection molding or the like.
  • the protective layer 3 is laminated on the surface of the substrate 1 prepared in the substrate preparation step.
  • a known film forming method such as a sputtering method can be used by using a sputtering target having the same composition as the dielectric constituting the protective layer 3.
  • the optical information recording medium recording layer 2 is laminated on the front surface side of the laminate in which the substrate 1 and the protective layer 3 are laminated after the back surface side protective layer laminating step.
  • the recording layer 2 for an optical information recording medium contains Sn oxide or Ta oxide together with Mn oxide and W oxide as metal oxides.
  • a sputtering method By using the sputtering method, it is easy to ensure the uniformity of the thickness of the recording layer 2 for the optical information recording medium.
  • a sputtering target for forming the recording layer 2 for the optical information recording medium a sputtering target containing Sn or Ta together with at least Mn and W as metal elements is used.
  • the lower limit of the ratio of the number of atoms of Mn to the total number of atoms of the metal elements is 3 atm%, more preferably 10 atm%.
  • the upper limit of the Mn atom number ratio is 40 atm%, more preferably 35 atm%.
  • the sputtering target is used as a sputtering target for forming the recording layer 2 for an optical information recording medium while oxidizing the contained metal element.
  • a metal oxide in addition to Mn oxide, W oxide and Sn oxidation It contains a substance or Ta oxide, and the atomic number ratio of Mn can be easily controlled within the above range. Therefore, by using the sputtering target, it is possible to easily manufacture the recording layer 2 for an optical information recording medium, which is excellent in basic characteristics such as the degree of modulation and the C / N ratio and is also excellent in the power margin.
  • the lower limit of the ratio of the number of atoms of W to the total number of atoms of the metal elements 10 atm% is preferable, and 15 atm% is more preferable.
  • the upper limit of the atomic number ratio of W 65 atm% is preferable, and 50 atm% is more preferable. If the atomic number ratio of W is less than the lower limit, the power margin of the recording layer 2 for an optical information recording medium manufactured by using the sputtering target may decrease.
  • the atomic number ratio of W exceeds the upper limit, the atomic number ratio of Sn or Ta decreases relatively, so that the jitter of the recording layer 2 for the optical information recording medium manufactured by using the sputtering target The characteristics may deteriorate and reading errors may occur easily.
  • the lower limit of the ratio of the number of atoms of Sn or Ta to the total number of atoms of the metal elements 5 atm% is preferable, and 10 atm% is more preferable.
  • the upper limit of the atomic number ratio of Sn or Ta 60 atm% is preferable, and 50 atm% is more preferable. If the atomic number ratio of Sn or Ta is less than the above lower limit, the jitter characteristic of the recording layer 2 for an optical information recording medium manufactured by using the sputtering target may be deteriorated, and a reading error may easily occur. On the contrary, when the atomic number ratio of Sn or Ta exceeds the upper limit, the atomic number ratio of W relatively decreases, so that the power of the recording layer 2 for the optical information recording medium manufactured by using the sputtering target Margin may decrease.
  • the recording layer 2 for the optical information recording medium is formed by a sputtering method
  • reactive sputtering oxygen is supplied to promote oxidation while sputtering is performed on the sputtering target.
  • Oxygen is supplied by using an atmospheric gas obtained by diluting oxygen gas with an inert gas (for example, Ar gas).
  • the lower limit of the oxygen flow rate ratio to the Ar flow rate in the atmospheric gas is preferably 0.5 and more preferably 1.
  • 5 is preferable as the upper limit of the oxygen flow rate ratio. If the oxygen flow rate ratio is less than the above lower limit, the oxidation of the metal becomes insufficient, and the metal element tends to remain in the recording layer 2 for the optical information recording medium, so that the durability of the optical information recording medium is lowered. There is a risk.
  • sputtering conditions can be determined by a conventional method.
  • the gas pressure is 0.1 Pa or more and 1 Pa or less
  • the sputtering power is 0.2 W / cm 2 or more and 20 W / cm 2 or less
  • the substrate temperature is room temperature. (20 ° C. or higher and 30 ° C. or lower).
  • the protective layer 3 is further laminated on the surface side of the laminated body in which the optical information recording medium recording layer 2 is laminated in the optical information recording medium recording layer laminating step.
  • This front surface side protective layer laminating step can be performed in the same manner as the back surface side protective layer laminating step.
  • the light transmitting layer 4 is further laminated on the surface side of the laminated body in which the protective layer 3 on the surface side is laminated in the surface side protective layer laminating step.
  • the method for laminating the light transmitting layer 4 a known method can be used depending on the characteristics of the material used.
  • an ultraviolet curable resin when used as the light transmitting layer 4, it can be formed by applying an ultraviolet curable resin composition by spin coating or the like and then irradiating with light.
  • the optical information recording medium includes the recording layer 2 for the optical information recording medium of the present invention, it is excellent in basic characteristics such as modulation degree and C / N ratio, and is also excellent in power margin. Further, in the optical information recording medium, since the protective layer 3 is a dielectric material, the signal strength can be increased and the basic characteristics thereof can be further improved.
  • the recording layer for an optical information recording medium is a recording layer for an optical information recording medium capable of recording an information signal by irradiation with a laser beam.
  • the recording layer for an optical information recording medium has a metal oxide containing an Mn oxide, a W oxide, a Ta oxide, and a Sn oxide, and is Mn with respect to the total number of atoms of the metal elements constituting the metal oxide.
  • the atomic number ratio of is 3 atm% or more and 40 atm% or less.
  • the optical information recording medium recording layer can be used in place of the optical information recording medium recording layer 2 of the optical information recording medium shown in FIG.
  • Mn oxide Since the Mn oxide is the same as the recording layer 2 for the optical information recording medium shown in FIG. 1, detailed description thereof will be omitted.
  • the recording layer for an optical information recording medium contains W oxide, Ta oxide, and Sn oxide in addition to Mn oxide as metal oxides.
  • the W oxide, Ta oxide and Sn oxide stabilize the bubbles generated by laser irradiation of the Mn oxide of the recording layer for the optical information recording medium and improve the power margin.
  • the metal oxide further contains a Zn oxide. By including Zn oxide in the metal oxide, the power margin can be further improved.
  • the form of the W oxide, Ta oxide, Sn oxide and Zn oxide may be an oxide bonded only to oxygen (O), and is a composite containing other metal elements. It may be an oxide. Further, since the W oxide and the Zn oxide are the same as the recording layer 2 for the optical information recording medium shown in FIG. 1, the following description will be omitted.
  • the lower limit of the ratio of the total number of atoms of Ta and Sn to the total number of atoms of the metal elements constituting the metal oxide is preferably 5 atm%, more preferably 10 atm%.
  • the upper limit of the total atomic number ratio of Ta and Sn 60 atm% is preferable, and 50 atm% is more preferable. If the total atomic number ratio of Ta and Sn is less than the above lower limit, the jitter characteristic may be deteriorated and a reading error may easily occur. On the contrary, when the total atomic number ratio of Ta and Sn exceeds the upper limit, the atomic number ratio of W is relatively lowered, so that the power margin may be lowered.
  • the lower limit of the atomic number ratio of Sn to the atomic number of Ta constituting the metal oxide 0.7 is preferable, and 0.8 is more preferable.
  • the upper limit of the atomic number ratio of Sn to the atomic number of Ta 1.3 is preferable, and 1.2 is more preferable.
  • the lower limit of the atomic number ratio of W to the total atomic number of Ta and Sn constituting the metal oxide 0.3 is preferable, and 0.4 is more preferable.
  • the upper limit of the atomic number ratio of W to the total atomic number of Ta and Sn 12 is preferable, and 10 is more preferable. If the ratio of the number of atoms of W to the total number of atoms of Ta and Sn is less than the above lower limit, the power margin may decrease. On the contrary, when the atomic number ratio of W to the total atomic number of Ta and Sn exceeds the upper limit, the ratio of the total atomic number of Ta and Sn is relatively lowered, so that the jitter characteristic is lowered and a reading error occurs. It may be easier.
  • the recording layer for an optical information recording medium containing Ta oxide and Sn oxide is also excellent in basic characteristics such as modulation degree and C / N ratio as in the recording layer 2 for an optical information recording medium shown in FIG. 1, and has a power margin. And excellent in jitter characteristics.
  • the optical information recording medium in which the protective layer is laminated on the front surface and the back surface of the recording layer for the optical information recording medium has been described, but in the recording layer for the optical information recording medium, the protective layer is laminated on only one surface. It may or may not have such a protective layer.
  • the optical information recording medium does not have a protective layer, it is preferable to provide a metal reflective layer on the back surface of the recording layer for the optical information recording medium. By providing the reflective layer in this way, the signal strength can be increased.
  • the metal constituting this reflective layer include metals such as Ag, Au, Cu, Al, Ni, Cr, and Ti, and alloys thereof.
  • the lower limit of the average thickness of the recording layer for an optical information recording medium is preferably 10 nm, more preferably 20 nm, and more preferably 30 nm. Is even more preferable.
  • the upper limit of the average thickness of the recording layer for an optical information recording medium is preferably 60 nm, more preferably 50 nm, and even more preferably 45 nm. If the average thickness of the recording layer for the optical information recording medium is less than the above lower limit, the reflectance required for reading the irradiated laser beam may not be obtained.
  • the recording layer for the optical information recording medium when the average thickness of the recording layer for the optical information recording medium exceeds the above upper limit, the recording layer for the optical information recording medium becomes unnecessarily thick, so that it takes time to form the recording layer for the optical information recording medium, and the production There is a risk that the property will deteriorate and the laser power required for recording will become too large.
  • the optical information recording medium may be provided with an optical adjustment layer such as an oxide, a nitride, or a sulfide on the front surface side or the back surface side of the optical information recording medium recording layer.
  • an optical adjustment layer such as an oxide, a nitride, or a sulfide on the front surface side or the back surface side of the optical information recording medium recording layer.
  • a single-layer optical information recording medium in which one recording layer for an optical information recording medium and one light transmission layer are formed has been described, but two or more recording layers for an optical information recording medium and light transmission have been described. It can also be a multi-layered optical information recording medium having layers.
  • a recording layer group composed of a recording layer for an optical information recording medium and an optical adjustment layer and a protective layer laminated as needed is formed on the optical information recording medium via a transparent intermediate layer. Stacked in the thickness direction.
  • a transparent intermediate layer for example, a transparent resin such as an ultraviolet curable resin or polycarbonate can be used.
  • the layer on which information is recorded is selected by adjusting the focal position of the laser in the thickness direction during laser irradiation, and multi-layer recording is realized.
  • the thickness of the transparent intermediate layer is appropriately determined so that crosstalk does not occur between the recording layers arranged in the upper and lower layers.
  • Sn or Ta is contained as a metal element together with at least Mn and W as a sputtering target for forming a recording layer for an optical information recording medium, and the ratio of the number of atoms of Mn to the total number of atoms of the metal element is 3 atm%.
  • a recording layer for an optical information recording medium can also be formed by using another sputtering target.
  • metal Sn or metal Ta can be used together with a simple substance metal Mn and metal W.
  • Sn oxide or Ta oxide may be used together with Mn oxide and W oxide as a simple substance, or a mixture of the above-mentioned metal target and oxide target may be used.
  • Example 1 As a substrate for the optical information recording medium, a polycarbonate substrate (diameter 120 mm, average thickness 1.1 mm, track pitch 0.32 ⁇ m, groove depth about 33 nm) was prepared.
  • the back surface side protective layer, the optical information recording medium recording layer (hereinafter, also simply referred to as “recording layer”), and the front surface side protective layer were laminated in this order on this substrate.
  • the front surface side protective layer and the back surface side protective layer were formed by a conventional DC magnetron sputtering method.
  • the material of the protective layer was a metal oxide containing Sn, Zn and Zr in the atomic number ratios of 40 atm%, 40 atm% and 20 atm%, respectively, on both the front surface side and the back surface side, and the average thickness thereof was 14 nm.
  • the Ar flow rate was 20 sccm and the O 2 flow rate was 1 sccm.
  • metal Mn, metal Sn, and metal W were prepared as sputtering targets, and the composition was controlled by the multiple sputtering method so as to have the composition shown in Table 1.
  • the sputtering conditions at this time were an Ar flow rate of 10 sccm, an O 2 flow rate of 10 sccm, a gas pressure of 0.26 Pa, a substrate temperature of 25 ° C. (room temperature), and a sputtering power of 0.2 W / W / according to the target composition. It was adjusted with cm 2 or more 3W / cm 2 or less.
  • the average thickness of the recording layer was 32 nm.
  • the light transmitting layer was laminated on the surface of the laminated body (the surface of the surface side protective layer) laminated by the sputtering method in this way.
  • the light transmitting layer was formed by spin-coating an ultraviolet curable resin composition (“BRD-864” of Nippon Kayaku Co., Ltd.) and then irradiating with ultraviolet rays.
  • the average thickness of the light transmitting layer was 0.1 mm.
  • Examples 2 to 4 The optical information recording media of Examples 2 to 4 were obtained in the same manner as in Example 1 except that the composition of the recording layer was controlled so as to have the composition shown in Table 1.
  • Example 5 and 6 In the formation of the recording layer, the optical information recording media of Examples 5 and 6 were obtained in the same manner as in Example 1 except that the metal Zn was further prepared and controlled so as to have the composition shown in Table 1.
  • Example 7 and 8 In the formation of the recording layer, the optical information recording media of Examples 7 and 8 were used in the same manner as in Example 5, except that a metal Ta was prepared in place of the metal Sn and the composition was controlled so as to have the composition shown in Table 1. Obtained.
  • Comparative Examples 1 to 4 The optical information recording media of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the composition of the recording layer was controlled so as to have the composition shown in Table 1.
  • ⁇ Evaluation device "ODU-1000" (recording laser center wavelength: 405 nm, NA (numerical aperture): 0.85) manufactured by Pulsetech Industries, Ltd. was used to evaluate the recording signal characteristics of the optical information recording medium, and the reference clock was reproduced at 66 MHz.
  • the recording laser was irradiated, and recording and reading were performed on the optical information recording medium.
  • the recording operation is performed by RLL (Run Length Limited) (1,7) PP modulation (Parity presserve / Prohibit rmtr (repeated minimum transmission runlength)), the signal is recorded on the adjacent 5 tracks, and the signal characteristics of the center track are evaluated. did.
  • the linear velocity of the optical information recording medium was 4.92 m / s, and the laser power during reproduction was 0.7 mW.
  • This modulation degree means that the larger the value, the larger the fluctuation of the reflected light and the easier it is to read.
  • a degree of modulation of 0.5 or more were excellent in the degree of modulation.
  • ⁇ Jitter> The jitter was measured using a time interval analyzer "TA520" manufactured by Yokogawa Electric Corporation. As shown in FIG. 3, the jitter changes depending on the laser power at the time of recording, and becomes the minimum value at a certain power. This minimum value was taken as the jitter of each optical information recording medium. The results are shown in Table 1.
  • jitter As for jitter, the smaller the value, the higher the reading accuracy. Here, it was judged that the one having a jitter of 6.5% or less was excellent in the jitter.
  • the power margin was calculated by the following procedure. First, the laser power was standardized by the laser power that minimizes jitter (see FIG. 3). From the result of standardizing this laser power, a standardized laser power having a jitter of 8.5% was obtained. Since the minimum value of jitter of each optical information recording medium is less than 8.5%, there are two laser powers. Table 1 shows each as a low power side and a high power side.
  • the power margin is the value after standardization, and the lower the power side (always less than 1) is, the better it is, and the higher power side (always more than 1) is better than 1. Here, it was judged that the one having 0.85 or less on the low power side and 1.15 or more on the high power side was excellent in power margin.
  • the optical information recording media of Examples 1 to 8 having a metal oxide containing Sn oxide or Ta oxide together with Mn oxide and W oxide as a recording layer are used for optical information recording of Comparative Examples 1 to 4.
  • it is excellent in jitter and power margin, especially the power margin on the low power side, and the degree of modulation is the same.
  • the optical information recording media of Examples 5 and 6 have smaller jitter than the optical information recording media of Examples 1 to 4, and are excellent in power margin on the low power side. From this, it can be seen that the power margin can be further improved by including the Zn oxide in the metal oxide of the recording layer.
  • the recording layer for an optical information recording medium and the optical information recording medium of the present invention are excellent in basic characteristics such as modulation degree and C / N ratio, and are also excellent in power margin.
  • Substrate 2 Recording layer for optical information recording medium 3 Protective layer 4 Light transmitting layer

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Abstract

Une couche d'enregistrement pour un support d'enregistrement d'informations optique selon la présente invention est capable d'enregistrer un signal d'informations par un faisceau laser irradié sur celle-ci, et comprend un oxyde métallique comprenant un oxyde d'étain (Sn) ou un oxyde de tantale (Ta), en plus d'un oxyde de manganèse (Mn) et d'un oxyde de tungstène (W). Le rapport du nombre d'atomes de Mn au nombre total d'atomes d'éléments métalliques qui constituent l'oxyde métallique est de 3 atm % à 40 atm %. Un support d'enregistrement d'informations optique selon la présente invention comprend la couche d'enregistrement pour un support d'enregistrement d'informations optique, et une couche de protection stratifiée sur la surface avant et la surface arrière de la couche d'enregistrement pour un support d'enregistrement d'informations optique. La couche de protection est un diélectrique.
PCT/JP2020/043470 2019-12-09 2020-11-20 Couche d'enregistrement pour support d'enregistrement d'informations optique, support d'enregistrement d'informations optique, et cible de pulvérisation cathodique WO2021117470A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017159561A1 (fr) * 2016-03-14 2017-09-21 パナソニックＩｐマネジメント株式会社 Support d'enregistrement d'informations, et procédé de production de support d'enregistrement d'informations
JP2018106794A (ja) * 2012-06-04 2018-07-05 ソニー株式会社 情報記録媒体
JP2019077907A (ja) * 2017-10-23 2019-05-23 デクセリアルズ株式会社 Ｍｎ−Ｚｎ−Ｗ−Ｏ系スパッタリングターゲット及びその製造方法
JP2020045521A (ja) * 2018-09-19 2020-03-26 デクセリアルズ株式会社 Ｍｎ−Ｔａ−Ｗ−Ｃｕ−Ｏ系スパッタリングターゲット及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018106794A (ja) * 2012-06-04 2018-07-05 ソニー株式会社 情報記録媒体
WO2017159561A1 (fr) * 2016-03-14 2017-09-21 パナソニックＩｐマネジメント株式会社 Support d'enregistrement d'informations, et procédé de production de support d'enregistrement d'informations
JP2019077907A (ja) * 2017-10-23 2019-05-23 デクセリアルズ株式会社 Ｍｎ−Ｚｎ−Ｗ−Ｏ系スパッタリングターゲット及びその製造方法
JP2020045521A (ja) * 2018-09-19 2020-03-26 デクセリアルズ株式会社 Ｍｎ−Ｔａ−Ｗ−Ｃｕ−Ｏ系スパッタリングターゲット及びその製造方法

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