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WO2014168073A1 - Oxide sputtering target and method for producing same, and protective film for optical recording media - Google Patents

Oxide sputtering target and method for producing same, and protective film for optical recording media Download PDF

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Publication number
WO2014168073A1
WO2014168073A1 PCT/JP2014/059866 JP2014059866W WO2014168073A1 WO 2014168073 A1 WO2014168073 A1 WO 2014168073A1 JP 2014059866 W JP2014059866 W JP 2014059866W WO 2014168073 A1 WO2014168073 A1 WO 2014168073A1
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Prior art keywords
oxide
sputtering target
powder
sputtering
sno
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French (fr)
Japanese (ja)
Inventor
齋藤　淳
理恵 森
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to CN201480009608.9A priority Critical patent/CN105074045B/en
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C04B35/6455—Hot isostatic pressing
    • 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
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • G11B7/266—Sputtering or spin-coating layers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • 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
    • G11B2007/25705—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
    • G11B2007/25706—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 containing transition metal elements (Zn, Fe, Co, Ni, Pt)
    • 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
    • G11B2007/25705—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
    • G11B2007/2571—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 containing group 14 elements except carbon (Si, Ge, Sn, Pb)
    • 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
    • G11B2007/25705—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
    • G11B2007/25715—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 containing oxygen

Definitions

  • the present invention relates to an oxide sputtering target and a manufacturing method thereof. Specifically, the present invention relates to an oxide sputtering target for forming a protective film for an optical recording medium used for, for example, a Blu-ray Disc (registered trademark: hereinafter referred to as BD) and a manufacturing method thereof.
  • BD Blu-ray Disc
  • Patent Document 3 proposes a sputtering target mainly composed of tin oxide having a tin oxide phase as a main phase, zinc oxide, and an oxide of a trivalent or higher element.
  • tin oxide phase in the structure of this sputtering target causes nodules, which leads to generation of particles.
  • the conventional techniques have problems and problems remain.
  • the present invention has been made in view of the above-mentioned problems, and can form a film that is highly storable as a recording medium, is soft and hardly cracked, and is formed by direct current (DC) sputtering. It is an object of the present invention to provide an oxide sputtering target and a method for manufacturing the same.
  • the present inventors have conducted research on a ZnO-based sputtering target mainly composed of tin oxide (SnO 2 ), zinc oxide (ZnO), and an oxide of a trivalent or higher element, and obtained the following knowledge. It was.
  • a target production raw material to which indium oxide (In 2 O 3 ) is added as an oxide of a trivalent or higher element is pressure-sintered in a non-oxidizing atmosphere, a Zn 2 SnO 4 phase in which In is dissolved is generated, Moreover, the specific resistance of the target itself can be further reduced by the occurrence of some oxygen vacancies. Thereby, stable direct current (DC) sputtering is possible.
  • DC direct current
  • the target does not contain a sulfur component, the influence of the target component on the reflectance of the laminated reflective layer can be suppressed.
  • sputtering is performed using this sputtering target, it is possible to form a Sn—In—Zn—O quaternary oxide film which has high storage stability and is hard to break.
  • the oxide sputtering target according to the first aspect of the present invention contains Sn: 7 at% or more and In: 0.1 to 35.0 at% with respect to the total amount of metal components, and the balance is
  • the oxide sintered body is composed of Zn and unavoidable impurities and has a composition in which the Sn / Zn atomic ratio Sn / (Sn + Zn) is 0.5 or less. It has a structure having 2 SnO 4 as a main phase.
  • the oxide sputtering target according to the second aspect of the present invention contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total metal component amount, The total content of one or more of Ge and Cr: 1.0 to 30.0 at%, the balance is made of Zn and inevitable impurities, and the atomic ratio Sn / (Sn + Zn) of Sn and Zn is 0.5 or less.
  • the manufacturing method of the oxide sputtering target according to the third aspect of the present invention is the manufacturing method of the oxide sputtering target according to (1) above, and includes SnO 2 powder, In 2 O 3 powder, and ZnO.
  • the mixed powder obtained by blending and mixing with the powder is subjected to pressure firing in a vacuum or an inert gas at a temperature of 800 to 1100 ° C. for 2 to 9 hours.
  • the manufacturing method of the oxide sputtering target according to the fourth aspect of the present invention is the manufacturing method of the oxide sputtering target according to (2) above, and includes SnO 2 powder, In 2 O 3 powder, and ZnO.
  • the protective film for an optical recording medium according to the fifth aspect of the present invention is formed by sputtering using the oxide sputtering target of (1), and Sn: 7 at% or more with respect to the total metal component amount. And In: 0.1 to 35.0 at%, with the balance being Zn and inevitable impurities.
  • the protective film for an optical recording medium according to the sixth aspect of the present invention is formed by sputtering using the oxide sputtering target of (2), and Sn: 7 at% or more with respect to the total amount of metal components. And In: 0.1 to 35.0 at%, and a total of at least one of Ge and Cr: 1.0 to 30.1 at%, with the balance being Zn and inevitable impurities It is an oxide having a component composition.
  • the oxide sputtering target according to the present invention contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, with the balance being Zn and inevitable impurities. and containing atomic ratio of Sn and Zn R1: Sn / (Sn + Zn) oxide sintered body of the component compositions is 0.5 or less, and a main phase of Zn 2 SnO 4 which in is dissolved tissue Have For this reason, since the specific resistance of the target itself further decreases, stable direct current (DC) sputtering becomes possible.
  • DC direct current
  • the oxide film formed by the oxide sputtering target of the present invention is suitable as a dielectric protective film for BD using an organic dye recording layer.
  • Example of the oxide sputtering target which concerns on the Example of this invention, and the protective film for optical recording media it is the element distribution image of each element which measured the cross-sectional structure
  • XRD X-ray diffraction
  • the oxide sputtering target according to the present embodiment contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and the balance is composed of Zn and inevitable impurities,
  • the atomic ratio R1: Sn / Zn is an oxide sintered body having a component composition in which Sn / (Sn + Zn) is 0.5 or less.
  • This oxide sintered body is Zn 2 SnO 4 in which In is dissolved. With a main phase. For this reason, specific resistance is low and stable direct current (DC) sputtering is possible. Further, it is possible to form a film that is less affected by the reflectance of the film component and is soft and difficult to break, and high storage stability can be expected as a recording medium.
  • DC direct current
  • the oxide sintered body a structure having Zn 2 SnO 4 in which In having a low specific resistance is dissolved as a main phase is used, so that either or both of zinc oxide having a high specific resistance and Zn 2 SnO 4 are used.
  • the specific resistance of the sputtering target itself can be lower than that of a structure having a main phase of. As a result, abnormal discharge during sputtering and particle generation can be suppressed, and direct current (DC) sputtering can be stabilized.
  • the oxide sputtering target of this embodiment is a sputtering target for producing a dielectric protective film laminated on a recording layer formed of an organic dye in BD, for example, Sn: 7 at% or more, and In: 0.1 to 35.0 at%, the balance is composed of Zn and inevitable impurities, and the atomic composition ratio Sn / (Sn + Zn) between Sn and Zn is set to 0.5 or less. It consists of an oxide sintered body. Since an oxide sputtering target generally exhibits insulating properties, when sputtering is performed with an oxide sputtering target, radio frequency (RF) sputtering is used, and direct current (DC) sputtering is difficult to perform.
  • RF radio frequency
  • DC direct current
  • the specific resistance of the sputtering target itself be 1 ⁇ ⁇ cm or less.
  • the specific resistance is desirably 0.1 ⁇ ⁇ cm or less, and further 0.01 ⁇ ⁇ cm or less.
  • the reason why the content of In is set to 0.1 to 35.0 at% is as follows. When it is less than 0.1 at%, direct current (DC) sputtering becomes unstable, and the formed film is likely to crack. When the In content exceeds 35.0 at%, a part of indium oxide (In 2 O 3 ) in the structure may be reduced, and metal indium (In) may be eluted. If this In is eluted, In will adhere to the furnace during production, causing damage to the furnace, as well as reducing productivity due to cleaning in the furnace, and further sputtering by the eluted In. The compositional variation of the target becomes a problem.
  • the content of In is more preferably 8 to 20 at%.
  • the reason why the Sn content is 7 at% or more is that if it is less than 7 at%, the hardness (indentation hardness) of the formed film becomes 800 mgf / ⁇ m 2 or more, and it becomes hard. is there. Furthermore, regarding the Sn content, the reason why the atomic ratio R1: Sn / (Sn + Zn) between Sn and Zn is 0.5 or less is that when this ratio exceeds 0.5, there is too much Sn, This is because a large amount of tin oxide (SnO 2 ) phase remains in the structure of the sputtering target. Since the tin oxide phase can cause generation of particles and abnormal discharge during sputtering, it may be difficult to realize more stable sputtering.
  • the Sn content is desirably 46 at% or less.
  • the Sn content is more preferably 25 to 46 at%.
  • the atomic ratio R1: Sn / (Sn + Zn) of Sn and Zn is preferably 0.08 or more, and more preferably 0.3 to 0.5.
  • content atomic ratio R2: (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) shall be 0.6 or less. This is because when the ratio exceeds 0.6, many tin oxide phases, chromium oxide phases, and germanium oxide phases remain in the target structure. Since these phases cause particles and abnormal discharge, it may be difficult to realize more stable sputtering.
  • the atomic ratio R2: (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) is preferably 0.08 or more, and more preferably 0.3 to 0.6.
  • the content of Cr exceeds 30 at%, abnormal discharge increases. If the Ge content also exceeds 30 at%, abnormal discharge increases. For this reason, it is preferable that the total content of at least one of Ge and Cr is 30 at% or less.
  • the Cr or Ge content is preferably 1.0 at% or more in order to reliably suppress film peeling from the chamber. Further, a more preferable Cr content is 1 to 10 at%, and a more preferable Ge content is 1 to 10 at%.
  • the SnO 2 powder, an In 2 O 3 powder and a mixed powder obtained by mixing and blending the ZnO powder, vacuum or inert gas Medium is baked under pressure at a temperature of 800 to 1100 ° C. for 2 to 9 hours.
  • SnO 2 powder, In 2 O 3 powder, and ZnO powder are blended, and one of Cr 2 O 3 powder and GeO 2 powder is added.
  • the mixed powder obtained by blending and mixing the seeds or more is subjected to pressure firing in a vacuum or an inert gas at a temperature of 800 to 1100 ° C. for 2 to 9 hours.
  • Sn 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and a total of one or more of Ge and Cr: 1.0- 30.0 at%, the balance is made of Zn and inevitable impurities, the atomic ratio R1: Sn / (Sn + Zn) of Sn and Zn is 0.5 or less, and Sn, Cr, Ge, Zn Contained atomic ratio R2: An oxide sintered body having a composition of (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) of 0.6 or less can be produced, and the oxide sintered body has a solid solution of In. Thus, it has a structure whose main phase is Zn 2 SnO 4 . By setting it as such a structure, the specific resistance of a sputtering target can be made still lower and stable direct current (DC) sputtering becomes possible.
  • DC direct current
  • SnO 2 powder is 7 ⁇ 48mol%
  • In 2 O 3 powder is 0.1 ⁇ 20 mol%
  • the more Cr 2 O 3 powder and GeO 2 powder In some cases, the total of both is less than 33 mol%, and it is preferable to adjust so that the balance is ZnO powder.
  • the pressure baking temperature is preferably 900 to 1000 ° C.
  • the pressure baking time is preferably 3 to 5 hours.
  • a film formed by direct current (DC) sputtering using the oxide sputtering target manufactured as described above a soft and hard-to-break film can be formed.
  • a film that suppresses the influence on the reflective layer can be formed, a change in the reflectance of the reflective layer is reduced, and a recording medium having such a film has high storage stability.
  • a film formed using an oxide sputtering target is suitable as a protective film for BD using a recording layer of an organic dye.
  • Sn 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components
  • the balance is made of Zn and inevitable impurities, and Sn and Zn are contained.
  • a total of one or more of Ge and Cr 1.0 to 30.0 at%
  • the balance is made of Zn and inevitable impurities
  • the atomic ratio of Sn and Zn Sn / (Sn + Zn) Is an oxide sintered body having a composition in which the atomic ratio of Sn, Cr, Ge, Zn (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) is 0.6 or less, and In is a solid solution.
  • the weighed raw material powder and 3 times its amount (weight ratio) of zirconia balls (diameter 5 mm) were placed in a plastic container and wet mixed in a ball mill apparatus for 24 hours.
  • alcohol was used for the solvent in this case, for example.
  • the obtained mixed powder is dried and granulated, and then vacuum or vacuum is applied at 800 to 1100 ° C., preferably 900 to 1000 ° C., for 2 to 9 hours at a pressure of 100 to 500 kgf / cm 2.
  • Hot pressing was performed in an active gas atmosphere to produce the sputtering targets of Examples 1 to 8.
  • the target size was 125 mm diameter x 5 mm thickness.
  • the pressure sintering is performed by hot pressing.
  • an HIP method hot isostatic pressing method or the like may be employed.
  • Comparative Example 1 A comparative example was prepared for comparison with the examples.
  • no indium oxide (In 2 O 3 ) powder was used as the raw material powder.
  • Comparative Examples 2 to 7 the prepared oxide sputtering target was out of the composition range of the present invention.
  • oxide sputtering targets of Comparative Examples 1 to 7 were produced at the blending ratios shown in Table 1. For reference, 80 mol% of ZnS and 20 mol% of a sputtering target formed of the SiO 2 (Comparative Example 8), and was prepared sputtering target formed of ITO (Comparative Example 9).
  • Table 2 shows the results of analyzing the metal component composition by ICP (inductively coupled plasma) for the oxide sputtering targets of Examples 1 to 8 and Comparative Examples 1 to 6 manufactured as described above.
  • R1 is the atomic ratio Sn / (Sn + Zn) of Sn and Zn
  • R2 is the atomic ratio of Sn, Cr, Ge (Sn + Cr + Ge) / (Sn + Cr +). Ge + Zn).
  • each element symbol represents the content (at%), and when the element was not included, the content atomic ratio was calculated by setting the content of the element to 0 at%.
  • Sn—In—Zn—O quaternary was formed as a protective film for an optical recording medium under the following film forming conditions.
  • a system oxide film was formed to prepare oxide films of Examples 1 to 21 and Comparative Examples 1 to 9.
  • Table 3 shows the results of analyzing the metal component composition of these oxide films.
  • the content ratios R1 and R2 in Table 3 were calculated from the content (at%) of each element in the same manner as in Table 2.
  • ⁇ Density ratio measurement> The density ratio was calculated by machining the sintered body to a predetermined size, measuring the weight, obtaining the bulk density, and then dividing by the theoretical density ⁇ fn .
  • the theoretical density ⁇ fn was determined by the following formula based on the weight of the raw material.
  • ⁇ 1 is the density of In 2 O 3
  • ⁇ 2 is the density of ZnO
  • ⁇ 3 is the density of SnO 2
  • ⁇ 4 is the density of GeO 2
  • ⁇ 5 is the density of Cr 2 O 3
  • ⁇ fn is the theoretical density
  • the unit of density is g / cm 3
  • C 1 is In 2 O 3 wt%
  • C 2 is ZnO wt%
  • C 3 is SnO 2 wt%
  • C 4 is GeO 2 wt%
  • C 5 is Cr 2 O 3 wt%. is there.
  • Sample preparation The sample was wet-polished and dried using SiC-Paper (grit 180) to obtain a measurement sample for XRD. The following conditions make XRD, the shown resulting main phase, and a Zn 2 SnO 4 a (440) 2 [Theta] showing reflection in Table 4.
  • Tube Cu (CuK ⁇ 1) Tube voltage: 40kW Tube current: 40 mA Scanning range (2 ⁇ ): 5 ° -80 ° Slit size: Divergence (DS) 2/3 degrees, Scattering (SS) 2/3 degrees, Light reception (RS) 0.8mm Measurement step width: 0.02 degrees at 2 ⁇ Scan speed: 2 degrees per minute Sample stage rotation speed: 30 rpm
  • Pre-sputtering was performed under the above conditions to remove the target surface processed layer, and then the chamber was once opened to the atmosphere to clean the chamber members such as the deposition preventive plate. Thereafter, evacuation was performed again, and after evacuation, pre-sputtering for 30 minutes was performed to remove atmospheric adsorption components on the target surface, and then a film having a thickness of 100 nm was formed on a 4-inch Si wafer. A total of 25 films were formed under the same conditions, and the number of particles of 1.0 ⁇ m or more adhering to the wafer surface was measured with a commercially available foreign substance inspection apparatus for the wafers after film formation, and the average value of 25 sheets was calculated.
  • Table 4 “A” indicates that the number of particles is 20 or less, “B” indicates that the number of particles is 21 to 50, “C” indicates that the number is 51 to 200, and “D” indicates that the number of particles is 201 or more. It was written.
  • the substrate was formed with Corning 1737 glass and a target film thickness of 500 nm, and the indentation weight was set to 35 mgf, and an ultra-fine indentation hardness tester (ENTIONICS Corporation ENT- 1100a) was used for the measurement.
  • the substrate was set in a 27 ° C. apparatus, and the indentation hardness was measured after 1 hour or more had passed.
  • the average value of indentation hardness measured at 10 points is shown in Table 5 as a measured value.
  • Dye As the dye formed on the substrate, for example, as an azo dye, a compound having a coupler component having a 6-hydroxy-2-pyridone structure and a diazo component of isoxazole triazole, and the organic dye compound are arranged. And metal complex compounds composed of metal ions that are positioned. A mixed solution in which the compound having the coupler component and the diazo component was diluted to 1.0% by weight with octafluoropentanol (OFP) was formed by spin coating.
  • OFP octafluoropentanol
  • the sputtering targets of Examples 1 to 21 all have a specific resistance of 0.1 ⁇ ⁇ cm or less, can perform direct current sputtering, and have a very high number of abnormal discharges. It was confirmed that there were few. In any of Examples 1 to 21, no elution of In was observed, and it was also confirmed that Zn 2 SnO 4 in which In was dissolved was the main phase. On the other hand, in the sputtering target of Comparative Example 1, Zn 2 SnO 4 was the main phase, but it did not contain In, had a high specific resistance, and abnormal discharge occurred frequently.
  • the oxide film (protective film) formed As can be seen from the results shown in Table 5 above, when the film was formed by direct current sputtering using the sputtering targets of Examples 1 to 21. In any case, it was confirmed that a film that was soft and difficult to break and had a small change in reflectance was obtained. On the other hand, in the case of Comparative Example 1, the indentation hardness value of the film was high, and the film was cracked, so that a soft film suitable for the protective film could not be obtained. In the case of Comparative Example 3, although the film did not crack, the value of indentation hardness of the film was high, and a soft film suitable for the protective film could not be obtained.
  • the oxide sintered body constituting the sputtering target has a structure whose main phase is Zn 2 SnO 4 in which In is dissolved, so that the target itself It was confirmed that the specific resistance was further reduced and stable direct current (DC) sputtering was possible. It was also confirmed that a Sn—In—Zn—O quaternary oxide film could be formed by direct current sputtering using the oxide sputtering target of each example, and that a soft and hard-to-break film could be obtained. Therefore, the oxide film formed with the oxide sputtering target of each example is suitable as a dielectric protective film for BD using an organic dye recording layer, and has high storage stability as a recording medium. I was able to confirm that there was.
  • Example 1 a diffraction peak attributed to ZnO and a diffraction peak attributed to Zn 2 SnO 4 which is a composite oxide of SnO 2 and ZnO were detected (Powder Diffraction File No. 1). 74-2184), the presence of ZnO and Zn 2 SnO 4 phases was confirmed. In Example 1, it was confirmed that the diffraction peak of Zn 2 SnO 4 was shifted to the low angle side due to the solid solution of In.
  • XRD X-ray diffraction
  • a reflected electron image (CP) and an element distribution image showing the composition distribution of each element were observed with EPMA (FE-EPMA: field emission electron beam microanalyzer).
  • the reflected electron image and element distribution image are shown in FIG.
  • the element distribution image by EPMA is originally a color image, but is converted into a black and white image. Therefore, in FIG. 1, a light and shaded portion (a relatively white portion) is a portion where the concentration of a predetermined element is high. It has become. From these images, it can be seen that the sputtering target of Example 1 is composed of a phase of ZnO and Zn 2 SnO 4 and In is very uniformly dispersed in the Zn 2 SnO 4 phase.
  • the oxide sintered body according to this embodiment As a sputtering target, surface roughness: 5.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, particle size: 20 ⁇ m or less, more preferably 10 ⁇ m.
  • the metal impurity concentration is 0.1 atomic% or less, more preferably 0.05 atomic% or less, and the bending strength is 50 MPa or more, more preferably 100 MPa or more.
  • pressure sintering is performed by hot pressing, but as another method, a HIP method (hot isostatic pressing method) or the like may be employed.
  • an oxide sputtering target capable of forming a film having a high storage stability, soft and difficult to break, and having few particles, and capable of direct current sputtering, for forming an optical recording medium protective film.

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Abstract

An oxide sputtering target according to the present invention comprises a sintered oxide that comprises Sn in an amount of 7 at% or more and In in an amount of 0.1 to 35.0 at% both relative to the total amount of all of metal components, with the remainder made up by Zn and unavoidable impurities. In the sintered oxide, the atom content ratios of Sn to Zn, i.e., Sn/(Sn+Zn), is 0.5 or less. The sintered oxide has a structure that contains, as the main phase, Zn2SnO4 in which In exists in the form of a solid solution.

Description

酸化物スパッタリングターゲット、その製造方法及び光記録媒体用保護膜Oxide sputtering target, method for producing the same, and protective film for optical recording medium

　本発明は、酸化物スパッタリングターゲット及びその製造方法に関する。具体的には、本発明は、例えば、Blu-ray Disc（登録商標：以下、ＢＤと称す）等に用いる光記録媒体用保護膜を成膜するための酸化物スパッタリングターゲット及びその製造方法に関する。
　本願は、２０１３年４月８日に、日本に出願された特願２０１３－０８０２４７号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an oxide sputtering target and a manufacturing method thereof. Specifically, the present invention relates to an oxide sputtering target for forming a protective film for an optical recording medium used for, for example, a Blu-ray Disc (registered trademark: hereinafter referred to as BD) and a manufacturing method thereof.
This application claims priority based on Japanese Patent Application No. 2013-080247 filed in Japan on April 8, 2013, the contents of which are incorporated herein by reference.

　近年、写真や動画の高画質化に伴い、光記録媒体等へ記録する際のデジタルデータが増大し、記録媒体の高容量化が求められ、既に、高記録容量の光記録媒体として二層記録方式により５０ＧＢの容量を有したＢＤが販売されている。このＢＤに対し、今後もさらなる高容量化が望まれており、記録層の多層化による高容量化の研究が盛んに行われている。 In recent years, with the improvement of the picture quality of photographs and moving images, digital data when recording on an optical recording medium or the like has increased, and there has been a demand for an increase in the capacity of the recording medium. Depending on the system, BDs with a capacity of 50 GB are sold. In the future, it is desired to further increase the capacity of the BD, and research on increasing the capacity by increasing the number of recording layers has been actively conducted.

特開２００９－２６３７８号公報JP 2009-26378 A 特開２００５－２２８４０２号公報JP 2005-228402 A 特開２００５－１５４８２０号公報JP 2005-154820 A

　ここで、従来の技術について、上記特許文献を参照し、以下に説明する。
　有機色素を記録層として用いたタイプの記録媒体では、無機物を記録層として用いた場合と比較して、記録時のレーザー照射による記録層の変形が大きい。このため、上記特許文献１に記載されているように、その記録層と隣り合う保護層には、低い硬度が必要である。そのため、従来では、この保護層に、適度な硬度を有した膜であるＺｎＳ－ＳｉＯ２やＩＴＯが採用されている。 Here, the conventional technique will be described below with reference to the above-mentioned patent document.
In a type of recording medium using an organic dye as a recording layer, the deformation of the recording layer due to laser irradiation during recording is larger than when an inorganic substance is used as the recording layer. For this reason, as described in Patent Document 1, the protective layer adjacent to the recording layer needs to have low hardness. Therefore, conventionally, ZnS—SiO 2 or ITO, which is a film having an appropriate hardness, has been employed for the protective layer.

　しかしながら、保護層にＺｎＳ－ＳｉＯ２を採用した場合には、上記特許文献２に記載があるように、硫黄（Ｓ）が含まれている。このため、硫黄と反射膜中の金属とが反応することにより、反射膜の反射率が低下するので、保護層にＺｎＳ－ＳｉＯ２を採用した記録媒体は保存性が低いという不都合がある。また、保護層にＩＴＯを採用した場合には、スパッタリングの際にパーティクルが多く発生し、ディスクの記録特性、保存性に悪影響を与える。このため、生産設備の清掃を頻繁に行う必要があり、生産性が悪いという問題があった。さらに、上記特許文献３では、酸化スズ相を主相とした酸化スズと、酸化亜鉛と、３価以上の元素の酸化物とを主成分としたスパッタリングターゲットが提案されている。しかしながら、このスパッタリングターゲットにおける組織中の酸化スズ相がノジュールの原因となり、これがパーティクルの発生に繋がってしまうという問題があった。
　この様に、従来の技術には、問題点があり、課題が残されている。 However, when ZnS—SiO 2 is used for the protective layer, as described in Patent Document 2, sulfur (S) is contained. For this reason, the sulfur and the metal in the reflective film react to reduce the reflectance of the reflective film, so that the recording medium employing ZnS—SiO 2 for the protective layer has a disadvantage of low storage stability. In addition, when ITO is used for the protective layer, many particles are generated during sputtering, which adversely affects the recording characteristics and storability of the disc. For this reason, it is necessary to frequently clean the production equipment, and there is a problem that productivity is poor. Further, Patent Document 3 proposes a sputtering target mainly composed of tin oxide having a tin oxide phase as a main phase, zinc oxide, and an oxide of a trivalent or higher element. However, there is a problem that the tin oxide phase in the structure of this sputtering target causes nodules, which leads to generation of particles.
As described above, the conventional techniques have problems and problems remain.

　本発明は、上述の課題に鑑みてなされたもので、光記録媒体保護膜形成用として、記録媒体としての保存性が高く、柔らかく割れ難い膜を成膜可能であると共に、直流（ＤＣ）スパッタリングが可能で、かつ、パーティクルも少ない酸化物スパッタリングターゲット及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems, and can form a film that is highly storable as a recording medium, is soft and hardly cracked, and is formed by direct current (DC) sputtering. It is an object of the present invention to provide an oxide sputtering target and a method for manufacturing the same.

　本発明者らは、酸化スズ（ＳｎＯ２）と酸化亜鉛（ＺｎＯ）と３価以上の元素の酸化物とを主成分としたＺｎＯ系のスパッタリングターゲットについて研究を進めたところ、以下の知見を得た。３価以上の元素の酸化物として酸化インジウム（Ｉｎ２Ｏ３）を加えたターゲット製造原料を、非酸化性雰囲気にて加圧焼結すると、Ｉｎが固溶したＺｎ２ＳｎＯ４相が生じ、かつ若干の酸素欠損が生じることによりターゲット自体の比抵抗を一層低下させることが図れる。これにより、安定した直流（ＤＣ）スパッタリングが可能である。また、ターゲットに硫黄成分が含まれないので、積層された反射層の反射率に対するターゲット成分の影響を抑制できる。この結果、このスパッタリングターゲットを用いてスパッタリングすると、保存性が高く、しかも、柔らかく割れ難いＳｎ－Ｉｎ－Ｚｎ－Ｏ四元系酸化膜を成膜できる。 The present inventors have conducted research on a ZnO-based sputtering target mainly composed of tin oxide (SnO 2 ), zinc oxide (ZnO), and an oxide of a trivalent or higher element, and obtained the following knowledge. It was. When a target production raw material to which indium oxide (In 2 O 3 ) is added as an oxide of a trivalent or higher element is pressure-sintered in a non-oxidizing atmosphere, a Zn 2 SnO 4 phase in which In is dissolved is generated, Moreover, the specific resistance of the target itself can be further reduced by the occurrence of some oxygen vacancies. Thereby, stable direct current (DC) sputtering is possible. In addition, since the target does not contain a sulfur component, the influence of the target component on the reflectance of the laminated reflective layer can be suppressed. As a result, when sputtering is performed using this sputtering target, it is possible to form a Sn—In—Zn—O quaternary oxide film which has high storage stability and is hard to break.

　したがって、本発明は、上記知見から、前記課題を解決するために以下の構成を採用した。
（１）本発明の第一の態様に係る酸化物スパッタリングターゲットは、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である組成の酸化物焼結体であり、前記酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有することを特徴とする。
（２）本発明の第二の態様に係る酸化物スパッタリングターゲットは、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下であり、且つ、Ｓｎ、Ｃｒ，Ｇｅ、Ｚｎの含有原子比（Ｓｎ＋Ｃｒ＋Ｇｅ）／（Ｓｎ＋Ｃｒ＋Ｇｅ＋Ｚｎ）が０．６以下である組成の酸化物焼結体であり、前記酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有することを特徴とする。
（３）本発明の第三の態様に係る酸化物スパッタリングターゲットの製造方法は、前記（１）の酸化物スパッタリングターゲットの製造方法であって、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成することを特徴とする。
（４）本発明の第四の態様に係る酸化物スパッタリングターゲットの製造方法は、前記（２）の酸化物スパッタリングターゲットの製造方法であって、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し、さらに、Ｃｒ２Ｏ３粉末及びＧｅＯ２粉末のうち１種以上を配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成することを特徴とする。
（５）本発明の第五の態様に係る光記録媒体用保護膜は、前記（１）の酸化物スパッタリングターゲットを用いてスパッタリング成膜され、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなることを特徴とする。
（６）本発明の第六の態様に係る光記録媒体用保護膜は、前記（２）の酸化物スパッタリングターゲットを用いてスパッタリング成膜され、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．１ａｔ％を含有し、残部がＺｎ及び不可避不純物からなる成分組成の酸化物であることを特徴とする。 Therefore, the present invention adopts the following configuration in order to solve the above-described problems based on the above knowledge.
(1) The oxide sputtering target according to the first aspect of the present invention contains Sn: 7 at% or more and In: 0.1 to 35.0 at% with respect to the total amount of metal components, and the balance is The oxide sintered body is composed of Zn and unavoidable impurities and has a composition in which the Sn / Zn atomic ratio Sn / (Sn + Zn) is 0.5 or less. It has a structure having 2 SnO 4 as a main phase.
(2) The oxide sputtering target according to the second aspect of the present invention contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total metal component amount, The total content of one or more of Ge and Cr: 1.0 to 30.0 at%, the balance is made of Zn and inevitable impurities, and the atomic ratio Sn / (Sn + Zn) of Sn and Zn is 0.5 or less. And an oxide sintered body having a composition in which the atomic ratio of Sn, Cr, Ge, Zn (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) is 0.6 or less, and the oxide sintered body contains In. It has a structure having a main phase of solid solution Zn 2 SnO 4 .
(3) The manufacturing method of the oxide sputtering target according to the third aspect of the present invention is the manufacturing method of the oxide sputtering target according to (1) above, and includes SnO 2 powder, In 2 O 3 powder, and ZnO. The mixed powder obtained by blending and mixing with the powder is subjected to pressure firing in a vacuum or an inert gas at a temperature of 800 to 1100 ° C. for 2 to 9 hours.
(4) The manufacturing method of the oxide sputtering target according to the fourth aspect of the present invention is the manufacturing method of the oxide sputtering target according to (2) above, and includes SnO 2 powder, In 2 O 3 powder, and ZnO. the powder was blended, further, a mixed powder obtained by mixing and blending one or more of Cr 2 O 3 powder and GeO 2 powder, during or inert gas vacuum, at a temperature of 800 ~ 1100 ° C. It is characterized by pressure baking for 2 to 9 hours.
(5) The protective film for an optical recording medium according to the fifth aspect of the present invention is formed by sputtering using the oxide sputtering target of (1), and Sn: 7 at% or more with respect to the total metal component amount. And In: 0.1 to 35.0 at%, with the balance being Zn and inevitable impurities.
(6) The protective film for an optical recording medium according to the sixth aspect of the present invention is formed by sputtering using the oxide sputtering target of (2), and Sn: 7 at% or more with respect to the total amount of metal components. And In: 0.1 to 35.0 at%, and a total of at least one of Ge and Cr: 1.0 to 30.1 at%, with the balance being Zn and inevitable impurities It is an oxide having a component composition.

　本発明に係る酸化物スパッタリングターゲットによれば、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、かつ、ＳｎとＺｎとの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である成分組成の酸化物焼結体が、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有する。このため、ターゲット自体の比抵抗が一層低下するので、安定した直流（ＤＣ）スパッタリングが可能となる。また、本発明の酸化物スパッタリングターゲットを用いてスパッタリングすると、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物であって、ＳｎとＺｎとの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である成分組成を有するＳｎ－Ｉｎ－Ｚｎ－Ｏ四元系酸化物膜を成膜でき、しかも、柔らかく割れ難い膜が得られる。このような膜を有する記録媒体は高い保存性を有する。そのため、本発明の酸化物スパッタリングターゲットで成膜された酸化物膜は、有機色素の記録層を使用したＢＤ用の誘電体保護膜として好適である。 The oxide sputtering target according to the present invention contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, with the balance being Zn and inevitable impurities. and containing atomic ratio of Sn and Zn R1: Sn / (Sn + Zn) oxide sintered body of the component compositions is 0.5 or less, and a main phase of Zn 2 SnO 4 which in is dissolved tissue Have For this reason, since the specific resistance of the target itself further decreases, stable direct current (DC) sputtering becomes possible. Further, when sputtering is performed using the oxide sputtering target of the present invention, Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, with the balance being Zn and inevitable It is possible to form a Sn—In—Zn—O quaternary oxide film which is an impurity and has a component composition in which the atomic ratio R1: Sn / (Sn + Zn) between Sn and Zn is 0.5 or less. A film that is soft and difficult to break is obtained. A recording medium having such a film has high storage stability. Therefore, the oxide film formed by the oxide sputtering target of the present invention is suitable as a dielectric protective film for BD using an organic dye recording layer.

本発明の実施例に係る酸化物スパッタリングターゲット及び光記録媒体用保護膜の実施例において、酸化物スパッタリングターゲットの断面組織をＥＰＭＡ（電子線マイクロアナライザ）により測定した各元素の元素分布像である。In the Example of the oxide sputtering target which concerns on the Example of this invention, and the protective film for optical recording media, it is the element distribution image of each element which measured the cross-sectional structure | tissue of the oxide sputtering target with EPMA (electron beam microanalyzer). 実施例に係る透明酸化物膜形成用スパッタリングターゲットのＸ線回折（ＸＲＤ）の分析結果を示すグラフである。It is a graph which shows the analysis result of the X-ray diffraction (XRD) of the sputtering target for transparent oxide film formation which concerns on an Example. 比較例に係る透明酸化物膜形成用スパッタリングターゲットのＸ線回折（ＸＲＤ）の分析結果を示すグラフである。It is a graph which shows the analysis result of the X-ray diffraction (XRD) of the sputtering target for transparent oxide film formation concerning a comparative example.

　以下に、本発明の実施形態による酸化物スパッタリングターゲット及びその製造方法の実施形態について、具体的に、実施例を示して説明する。 Hereinafter, embodiments of the oxide sputtering target and the method for manufacturing the oxide sputtering target according to the embodiments of the present invention will be specifically described with reference to examples.

　本実施形態に係る酸化物スパッタリングターゲットは、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎとの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である成分組成の酸化物焼結体であり、この酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有する。このため、比抵抗が低く、安定した直流（ＤＣ）スパッタリングが可能である。そして、膜成分の反射率への影響が少なく、かつ、柔らかく割れ難い膜を成膜することができ、記録媒体として高い保存性を期待し得る。
　なお、酸化物焼結体において、比抵抗の低いＩｎが固溶したＺｎ２ＳｎＯ４を主相とした組織とすることにより、比抵抗の高い酸化亜鉛やＺｎ２ＳｎＯ４のいずれか、または両方を主相とした組織よりも、スパッタリングターゲット自体の比抵抗を下げることができる。この結果、スパッタリング時の異常放電や、パーティクル発生を抑制することができ、直流（ＤＣ）スパッタリングを安定化できる。 The oxide sputtering target according to the present embodiment contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and the balance is composed of Zn and inevitable impurities, The atomic ratio R1: Sn / Zn is an oxide sintered body having a component composition in which Sn / (Sn + Zn) is 0.5 or less. This oxide sintered body is Zn 2 SnO 4 in which In is dissolved. With a main phase. For this reason, specific resistance is low and stable direct current (DC) sputtering is possible. Further, it is possible to form a film that is less affected by the reflectance of the film component and is soft and difficult to break, and high storage stability can be expected as a recording medium.
Note that in the oxide sintered body, a structure having Zn 2 SnO 4 in which In having a low specific resistance is dissolved as a main phase is used, so that either or both of zinc oxide having a high specific resistance and Zn 2 SnO 4 are used. The specific resistance of the sputtering target itself can be lower than that of a structure having a main phase of. As a result, abnormal discharge during sputtering and particle generation can be suppressed, and direct current (DC) sputtering can be stabilized.

　本実施形態の酸化物スパッタリングターゲットは、例えば、ＢＤにおける有機色素で形成された記録層に積層される誘電体保護膜を作製するためのスパッタリングターゲットであって、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、かつ、ＳｎとＺｎとの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である成分組成に設定された酸化物焼結体で構成される。
　酸化物スパッタリングターゲットは、一般的には、絶縁性を示すため、酸化物スパッタリングターゲットでスパッタリングを実施する場合には、高周波（ＲＦ）スパッタリングが用いられ、直流（ＤＣ）スパッタリングを行うことは難しい。そこで、酸化物スパッタリングターゲットで直流（ＤＣ）スパッタリングを実施できるようにするためには、スパッタリングターゲット自体の比抵抗を、１Ω・ｃｍ以下とすることが望ましい。特に、異常放電が少なく、安定したスパッタリングを行うためには、その比抵抗を、０．１Ω・ｃｍ以下、さらには、０．０１Ω・ｃｍ以下とすることが望ましい。 The oxide sputtering target of this embodiment is a sputtering target for producing a dielectric protective film laminated on a recording layer formed of an organic dye in BD, for example, Sn: 7 at% or more, and In: 0.1 to 35.0 at%, the balance is composed of Zn and inevitable impurities, and the atomic composition ratio Sn / (Sn + Zn) between Sn and Zn is set to 0.5 or less. It consists of an oxide sintered body.
Since an oxide sputtering target generally exhibits insulating properties, when sputtering is performed with an oxide sputtering target, radio frequency (RF) sputtering is used, and direct current (DC) sputtering is difficult to perform. Therefore, in order to be able to perform direct current (DC) sputtering with an oxide sputtering target, it is desirable that the specific resistance of the sputtering target itself be 1 Ω · cm or less. In particular, in order to perform stable sputtering with less abnormal discharge, the specific resistance is desirably 0.1 Ω · cm or less, and further 0.01 Ω · cm or less.

　ここで、上記Ｉｎの含有量を、０．１～３５．０ａｔ％とした理由は、以下の通りである。０．１ａｔ％未満であると、直流（ＤＣ）スパッタリングが不安定になり、形成された膜の割れが発生しやすくなる。そして、Ｉｎの含有量が、３５．０ａｔ％を超えると、組織中の酸化インジウム（Ｉｎ２Ｏ３）の一部が還元し、金属インジウム（Ｉｎ）が溶出する可能性がある。このＩｎが溶出していると、製造時に炉内にＩｎが付着し、炉へのダメージとなるだけでなく、炉内の清掃による生産性の低下をもたらし、さらには溶出した分のＩｎによりスパッタリングターゲットの組成バラつきが問題となる。
　Ｉｎの含有量としては、８～２０ａｔ％がより望ましい。 Here, the reason why the content of In is set to 0.1 to 35.0 at% is as follows. When it is less than 0.1 at%, direct current (DC) sputtering becomes unstable, and the formed film is likely to crack. When the In content exceeds 35.0 at%, a part of indium oxide (In 2 O 3 ) in the structure may be reduced, and metal indium (In) may be eluted. If this In is eluted, In will adhere to the furnace during production, causing damage to the furnace, as well as reducing productivity due to cleaning in the furnace, and further sputtering by the eluted In. The compositional variation of the target becomes a problem.
The content of In is more preferably 8 to 20 at%.

　また、上記Ｓｎの含有量を、７ａｔ％以上とした理由は、７ａｔ％未満であると、形成された膜の硬度（押込み硬さ）が８００ｍｇｆ／μｍ２以上になり、硬くなってしまうためである。さらに、Ｓｎの含有量に関して、ＳｎとＺｎとの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）を０．５以下とした理由は、この比が、０．５を超えると、Ｓｎが多すぎて、スパッタリングターゲットの組織中に酸化スズ（ＳｎＯ２）相が多く残存してしまうためである。酸化スズ相はスパッタリング時に、パーティクルの発生や、異常放電の原因となりうるため、より安定したスパッタの実現が難しくなるおそれがある。また、同様な観点から、Ｓｎの含有量は、４６ａｔ％以下であることが望ましい。
　Ｓｎの含有量としては、２５～４６ａｔ％がより望ましい。
　さらに、ＳｎとＺｎとの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）は０．０８以上であることが好ましく、０．３～０．５がより好ましい。 The reason why the Sn content is 7 at% or more is that if it is less than 7 at%, the hardness (indentation hardness) of the formed film becomes 800 mgf / μm 2 or more, and it becomes hard. is there. Furthermore, regarding the Sn content, the reason why the atomic ratio R1: Sn / (Sn + Zn) between Sn and Zn is 0.5 or less is that when this ratio exceeds 0.5, there is too much Sn, This is because a large amount of tin oxide (SnO 2 ) phase remains in the structure of the sputtering target. Since the tin oxide phase can cause generation of particles and abnormal discharge during sputtering, it may be difficult to realize more stable sputtering. From the same viewpoint, the Sn content is desirably 46 at% or less.
The Sn content is more preferably 25 to 46 at%.
Further, the atomic ratio R1: Sn / (Sn + Zn) of Sn and Zn is preferably 0.08 or more, and more preferably 0.3 to 0.5.

　さらに、ＣｒおよびＧｅのうち１種以上を配合するとチャンバーからの膜剥がれを抑制することができる。Ｓｎ、Ｃｒ、Ｇｅの含有量について、含有原子比Ｒ２：（Ｓｎ+Ｃｒ+Ｇｅ）/（Ｓｎ+Ｃｒ+Ｇｅ+Ｚｎ）を０．６以下とする。この理由は、０．６を超えると、ターゲットの組織中に酸化スズ相、酸化クロム相、酸化ゲルマニウム相が多く残存してしまうためである。これらの相はパーティクルや異常放電の原因となるため、より安定したスパッタの実現が難しくなるおそれがある。含有原子比Ｒ２：（Ｓｎ+Ｃｒ+Ｇｅ）/（Ｓｎ+Ｃｒ+Ｇｅ+Ｚｎ）は０．０８以上であることが好ましく、０．３～０．６がより好ましい。
　また、Ｃｒの含有量が、３０ａｔ％を超えると、異常放電が増加する。Ｇｅの含有量も、３０ａｔ％を超えると、異常放電が増加してしまう。このため、Ｇｅ及びＣｒのうち１種以上の合計の含有量を３０ａｔ％以下とすることが好ましい。
　また、ＣｒまたはＧｅを添加させる場合には、確実にチャンバーからの膜剥がれを抑制するため、ＣｒまたはＧｅの含有量を１．０ａｔ％以上とすることが好ましい。さらに、より好ましいＣｒの含有量は１～１０ａｔ％であり、より好ましいＧｅの含有量は１～１０ａｔ％である。 Furthermore, when one or more of Cr and Ge are blended, film peeling from the chamber can be suppressed. About content of Sn, Cr, and Ge, content atomic ratio R2: (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) shall be 0.6 or less. This is because when the ratio exceeds 0.6, many tin oxide phases, chromium oxide phases, and germanium oxide phases remain in the target structure. Since these phases cause particles and abnormal discharge, it may be difficult to realize more stable sputtering. The atomic ratio R2: (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) is preferably 0.08 or more, and more preferably 0.3 to 0.6.
Further, when the content of Cr exceeds 30 at%, abnormal discharge increases. If the Ge content also exceeds 30 at%, abnormal discharge increases. For this reason, it is preferable that the total content of at least one of Ge and Cr is 30 at% or less.
In addition, when Cr or Ge is added, the Cr or Ge content is preferably 1.0 at% or more in order to reliably suppress film peeling from the chamber. Further, a more preferable Cr content is 1 to 10 at%, and a more preferable Ge content is 1 to 10 at%.

　また、本実施形態に係る酸化物スパッタリングターゲットの製造方法では、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成する。このため、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である組成の酸化物焼結体を作製でき、その酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有したものとなる。この様な組織とすることにより、スパッタリングターゲットの比抵抗を一層低くすることができ、安定した直流（ＤＣ）スパッタリングが可能となる。 Further, in the method of manufacturing an oxide sputtering target according to the present embodiment, the SnO 2 powder, an In 2 O 3 powder and a mixed powder obtained by mixing and blending the ZnO powder, vacuum or inert gas Medium is baked under pressure at a temperature of 800 to 1100 ° C. for 2 to 9 hours. For this reason, Sn: 7 at% or more and In: 0.1 to 35.0 at% with respect to the total amount of metal components, the balance is made of Zn and inevitable impurities, and the atomic ratio R1 of Sn and Zn is R1 : An oxide sintered body having a composition of Sn / (Sn + Zn) of 0.5 or less could be produced, and the oxide sintered body had a structure mainly composed of Zn 2 SnO 4 in which In was dissolved. It will be a thing. By setting it as such a structure, the specific resistance of a sputtering target can be made still lower and stable direct current (DC) sputtering becomes possible.

　本実施形態の変形例に係る酸化物スパッタリングターゲットの製造方法では、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し、さらに、Ｃｒ２Ｏ３粉末及びＧｅＯ２粉末のうち１種以上を配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成する。このため、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｒ１：Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下であり、且つ、Ｓｎ、Ｃｒ，Ｇｅ、Ｚｎの含有原子比Ｒ２：（Ｓｎ＋Ｃｒ＋Ｇｅ）／（Ｓｎ＋Ｃｒ＋Ｇｅ＋Ｚｎ）が０．６以下である組成の酸化物焼結体を作製でき、その酸化物焼結体は、前記酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有したものとなる。この様な組織とすることにより、スパッタリングターゲットの比抵抗を一層低くすることができ、安定した直流（ＤＣ）スパッタリングが可能となる。 In the method of manufacturing an oxide sputtering target according to the modification of the present embodiment, SnO 2 powder, In 2 O 3 powder, and ZnO powder are blended, and one of Cr 2 O 3 powder and GeO 2 powder is added. The mixed powder obtained by blending and mixing the seeds or more is subjected to pressure firing in a vacuum or an inert gas at a temperature of 800 to 1100 ° C. for 2 to 9 hours. For this reason, Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and a total of one or more of Ge and Cr: 1.0- 30.0 at%, the balance is made of Zn and inevitable impurities, the atomic ratio R1: Sn / (Sn + Zn) of Sn and Zn is 0.5 or less, and Sn, Cr, Ge, Zn Contained atomic ratio R2: An oxide sintered body having a composition of (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) of 0.6 or less can be produced, and the oxide sintered body has a solid solution of In. Thus, it has a structure whose main phase is Zn 2 SnO 4 . By setting it as such a structure, the specific resistance of a sputtering target can be made still lower and stable direct current (DC) sputtering becomes possible.

　なお、原料粉末の含有量としては、混合粉末全体に対し、ＳｎＯ２粉末は７～４８ｍｏｌ％、Ｉｎ２Ｏ３粉末は０．１～２０ｍｏｌ％、さらにＣｒ２Ｏ３粉末とＧｅＯ２粉末を含む場合には両者の合計：３３ｍｏｌ％未満であり、残部がＺｎＯ粉末となるように調整することが好ましい。また、加圧焼成する温度は９００～１０００℃が好ましく、加圧焼成する時間は３～５時間が好ましい。 As the content of the raw powder, including with respect to the entire mixed powder, SnO 2 powder is 7 ~ 48mol%, In 2 O 3 powder is 0.1 ~ 20 mol%, the more Cr 2 O 3 powder and GeO 2 powder In some cases, the total of both is less than 33 mol%, and it is preferable to adjust so that the balance is ZnO powder. In addition, the pressure baking temperature is preferably 900 to 1000 ° C., and the pressure baking time is preferably 3 to 5 hours.

　以上の様に製造された酸化物スパッタリングターゲットを用いて直流（ＤＣ）スパッタリングで成膜すると、柔らかく割れ難い膜を成膜することができる。また、反射層への影響を抑制した膜を成膜できるため、反射層の反射率の変化が少なくなり、このような膜を有する記録媒体は高い保存性を有する。このように、酸化物スパッタリングターゲットを用いて成膜された膜は、有機色素の記録層を使用したＢＤの保護膜として好適である。 When a film is formed by direct current (DC) sputtering using the oxide sputtering target manufactured as described above, a soft and hard-to-break film can be formed. In addition, since a film that suppresses the influence on the reflective layer can be formed, a change in the reflectance of the reflective layer is reduced, and a recording medium having such a film has high storage stability. Thus, a film formed using an oxide sputtering target is suitable as a protective film for BD using a recording layer of an organic dye.

　本実施例では、全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎとの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である組成の酸化物焼結体、若しくは全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下であり、且つ、Ｓｎ、Ｃｒ，Ｇｅ、Ｚｎの含有原子比（Ｓｎ＋Ｃｒ＋Ｇｅ）／（Ｓｎ＋Ｃｒ＋Ｇｅ＋Ｚｎ）が０．６以下である組成の酸化物焼結体であり、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有する酸化物スパッタリングターゲットを以下の手順で製造した。酸化亜鉛（化学式：ＺｎＯ、平均粒径：Ｄ５０＝１μｍ）、酸化スズ（化学式：ＳｎＯ２、Ｄ５０＝１６μｍ）、酸化インジウム（化学式：Ｉｎ２Ｏ３、Ｄ５０＝１１μｍ）、酸化ゲルマニウム（化学式：ＧｅＯ２、Ｄ５０＝１．０μｍ）、酸化クロム（化学式：Ｃｒ２Ｏ３、Ｄ５０＝０．４μｍ）を原料粉末として用意し、各原料粉末を、表１に示す所定の比率で秤量した。 In this example, Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, the balance is made of Zn and inevitable impurities, and Sn and Zn are contained. With respect to the oxide sintered body having a composition where the atomic ratio Sn / (Sn + Zn) is 0.5 or less, or the total metal component amount, Sn: 7 at% or more, In: 0.1 to 35.0 at% In addition, a total of one or more of Ge and Cr: 1.0 to 30.0 at%, the balance is made of Zn and inevitable impurities, and the atomic ratio of Sn and Zn Sn / (Sn + Zn) Is an oxide sintered body having a composition in which the atomic ratio of Sn, Cr, Ge, Zn (Sn + Cr + Ge) / (Sn + Cr + Ge + Zn) is 0.6 or less, and In is a solid solution. having a Zn 2 SnO 4 was used as a main phase organization An oxide sputtering target was prepared by the following procedure. Zinc oxide (chemical formula: ZnO, average particle size: D 50 = 1 μm), tin oxide (chemical formula: SnO 2 , D 50 = 16 μm), indium oxide (chemical formula: In 2 O 3 , D 50 = 11 μm), germanium oxide ( Chemical formula: GeO 2 , D 50 = 1.0 μm) and chromium oxide (Chemical formula: Cr 2 O 3 , D 50 = 0.4 μm) are prepared as raw material powders, and each raw material powder is prepared at a predetermined ratio shown in Table 1. Weighed.

　この秤量した原料粉末とその３倍量（重量比）のジルコニアボール（直径５ｍｍ）とをポリ容器に入れ、ボールミル装置にて２４時間湿式混合した。なお、この際の溶媒には、例えば、アルコールを用いた。次に、得られた混合粉末を乾燥後、造粒し、８００～１１００℃、望ましくは、９００～１０００℃にて、２～９時間、１００～５００ｋｇｆ／ｃｍ２の圧力にて、真空又は不活性ガス雰囲気中でホットプレスし、実施例１～８のスパッタリングターゲットを作製した。なお、ターゲットサイズは、直径１２５ｍｍ×厚さ５ｍｍとした。なお、本実施例では加圧焼結をホットプレスによって行ったが、加圧焼結方法として、ＨＩＰ法（熱間等方加圧式焼結法）等を採用しても構わない。 The weighed raw material powder and 3 times its amount (weight ratio) of zirconia balls (diameter 5 mm) were placed in a plastic container and wet mixed in a ball mill apparatus for 24 hours. In addition, alcohol was used for the solvent in this case, for example. Next, the obtained mixed powder is dried and granulated, and then vacuum or vacuum is applied at 800 to 1100 ° C., preferably 900 to 1000 ° C., for 2 to 9 hours at a pressure of 100 to 500 kgf / cm 2. Hot pressing was performed in an active gas atmosphere to produce the sputtering targets of Examples 1 to 8. The target size was 125 mm diameter x 5 mm thickness. In this embodiment, the pressure sintering is performed by hot pressing. However, as a pressure sintering method, an HIP method (hot isostatic pressing method) or the like may be employed.

〔比較例〕
　実施例と比較するため、比較例を用意した。比較例１は、原料粉末として、酸化インジウム（Ｉｎ２Ｏ３）粉末を用いなかった。比較例２～７では、作成された酸化物スパッタリングターゲットが本発明の組成範囲外となった。具体的には、表１に示す配合割合で、比較例１～７の酸化物スパッタリングターゲットを作製した。参考として、８０ｍｏｌ％のＺｎＳと２０ｍｏｌ％のＳｉＯ２とで形成されたスパッタリングターゲット（比較例８）、そして、ＩＴＯで形成されたスパッタリングターゲット（比較例９）を用意した。 [Comparative Example]
A comparative example was prepared for comparison with the examples. In Comparative Example 1, no indium oxide (In 2 O 3 ) powder was used as the raw material powder. In Comparative Examples 2 to 7, the prepared oxide sputtering target was out of the composition range of the present invention. Specifically, oxide sputtering targets of Comparative Examples 1 to 7 were produced at the blending ratios shown in Table 1. For reference, 80 mol% of ZnS and 20 mol% of a sputtering target formed of the SiO 2 (Comparative Example 8), and was prepared sputtering target formed of ITO (Comparative Example 9).

Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
  

　次に、上記で製造された実施例１～８及び比較例１～６の酸化物スパッタリングターゲットについて、ＩＣＰ（誘導結合プラズマ）により金属成分組成の分析を行った結果を表２に示した。なお、表２では、Ｒ１は、ＳｎとＺｎとの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）であり、Ｒ２は、Ｓｎ、Ｃｒ、Ｇｅの含有原子比（Ｓｎ+Ｃｒ+Ｇｅ）／（Ｓｎ+Ｃｒ+Ｇｅ+Ｚｎ）である。ここで、各元素記号は、含有量（ａｔ％）を表し、該当元素を含まない場合には、その元素の含有量を０ａｔ％として、含有原子比が計算された。 Next, Table 2 shows the results of analyzing the metal component composition by ICP (inductively coupled plasma) for the oxide sputtering targets of Examples 1 to 8 and Comparative Examples 1 to 6 manufactured as described above. In Table 2, R1 is the atomic ratio Sn / (Sn + Zn) of Sn and Zn, and R2 is the atomic ratio of Sn, Cr, Ge (Sn + Cr + Ge) / (Sn + Cr +). Ge + Zn). Here, each element symbol represents the content (at%), and when the element was not included, the content atomic ratio was calculated by setting the content of the element to 0 at%.

Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000002
  

　次に、これらの実施例１～２１及び比較例１～９の酸化物スパッタリングターゲットを用いて、以下の成膜条件により、光記録媒体用の保護膜として、Ｓｎ－Ｉｎ－Ｚｎ－Ｏ四元系酸化物膜を成膜し、実施例１～２１及び比較例１～９の酸化物膜を作製した。それらの酸化物膜について、金属成分組成の分析を行った結果を表３に示した。表３における含有量比Ｒ１、Ｒ２については、表２の場合と同様にして、各元素の含有量（ａｔ％）から計算された。 Next, using these oxide sputtering targets of Examples 1 to 21 and Comparative Examples 1 to 9, Sn—In—Zn—O quaternary was formed as a protective film for an optical recording medium under the following film forming conditions. A system oxide film was formed to prepare oxide films of Examples 1 to 21 and Comparative Examples 1 to 9. Table 3 shows the results of analyzing the metal component composition of these oxide films. The content ratios R1 and R2 in Table 3 were calculated from the content (at%) of each element in the same manner as in Table 2.

＜成膜条件＞
・電源：ＤＣ１０００Ｗ（ＤＣ（直流）スパッタができなかったものについては高周波（ＲＦ）スパッタを行った）
・全圧：０．４Ｐａ
・スパッタガス：Ａｒ＝４７．５ｓｃｃｍ、Ｏ２：２．５ｓｃｃｍ
・ターゲット－基板間（ＴＳ）距離：７０ｍｍ <Film formation conditions>
Power source: DC1000W (For those that could not be sputtered by DC (direct current), high frequency (RF) sputtering was performed)
・ Total pressure: 0.4Pa
Sputtering Gas: Ar = 47.5sccm, O 2: 2.5sccm
・ Target-to-board (TS) distance: 70mm

Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
  

　次いで、実施例１～２１及び比較例１～９の酸化物スパッタリングターゲットについて、密度比、比抵抗、Ｉｎの溶出の有無を、そして、それらの酸化物スパッタリングターゲットを用いてスパッタリングを行ったときの異常放電回数、パーティクルの量を評価した。さらに、そのスパッタリングで得られた酸化物膜に関して、膜の押し込み硬さ、膜の割れ、及び反射率の変化を求めた。これらの結果を、表４及び表５に示した。ここで用いられた評価・測定手法は、以下の様である。 Next, with respect to the oxide sputtering targets of Examples 1 to 21 and Comparative Examples 1 to 9, the density ratio, specific resistance, presence / absence of In elution, and when sputtering was performed using these oxide sputtering targets The number of abnormal discharges and the amount of particles were evaluated. Furthermore, regarding the oxide film obtained by the sputtering, the indentation hardness of the film, the cracking of the film, and the change in reflectance were determined. These results are shown in Tables 4 and 5. The evaluation / measurement methods used here are as follows.

＜密度比測定＞
　密度比は、焼結体を所定寸法に機械加工した後、重量を測定し、嵩密度を求めた後、理論密度ρｆｎで割ることで算出した。なお、理論密度ρｆｎについては、原料の重量に基づいて、以下に示した式により求めた。 <Density ratio measurement>
The density ratio was calculated by machining the sintered body to a predetermined size, measuring the weight, obtaining the bulk density, and then dividing by the theoretical density ρ fn . The theoretical density ρ fn was determined by the following formula based on the weight of the raw material.

Figure JPOXMLDOC01-appb-M000004
 
Figure JPOXMLDOC01-appb-M000004
  

　なお、上式において、ρ１はＩｎ２Ｏ３の密度、ρ２はＺｎＯの密度、ρ３はＳｎＯ２の密度、ρ４はＧｅＯ２の密度、ρ５はＣｒ２Ｏ３の密度、ρｆｎは理論密度であり、密度の単位はｇ／ｃｍ３である。また、Ｃ１はＩｎ２Ｏ３の重量％、Ｃ２はＺｎＯの重量％、Ｃ３はＳｎＯ２の重量％、Ｃ４はＧｅＯ２の重量％、Ｃ５はＣｒ２Ｏ３の重量％である。 In the above equation, ρ 1 is the density of In 2 O 3 , ρ 2 is the density of ZnO, ρ 3 is the density of SnO 2 , ρ 4 is the density of GeO 2 , ρ 5 is the density of Cr 2 O 3 , ρ fn is the theoretical density, and the unit of density is g / cm 3 . Also, C 1 is In 2 O 3 wt%, C 2 is ZnO wt%, C 3 is SnO 2 wt%, C 4 is GeO 2 wt%, and C 5 is Cr 2 O 3 wt%. is there.

＜比抵抗測定＞
　酸化物スパッタリングターゲット及び酸化物膜の比抵抗測定は、ナプソン株式会社製４探針法抵抗率測定器ＲＴ－７０を用いて測定した。当該測定器で測定できなかった場合には、「測定可能範囲外」と表記した。 <Specific resistance measurement>
The specific resistance of the oxide sputtering target and the oxide film was measured using a 4-probe resistivity meter RT-70 manufactured by Napson Corporation. When it was not possible to measure with the measuring instrument, it was described as “out of measurable range”.

＜異常放電回数＞
　上述の成膜条件において２時間のスパッタリングを行い、異常放電の回数（回数／時間）を計測した。その後、スパッタリングチャンバーを解放し、チャンバー内のパーティクルを確認した。なお、比較例８の酸化物スパッタリングターゲットの場合には、直流（ＤＣ）スパッタリングを実施できなかったため、「直流スパッタ不可」と表記し、成膜には、高周波スパッタリングで実施した。 <Number of abnormal discharge>
Sputtering was performed for 2 hours under the film forming conditions described above, and the number of abnormal discharges (number of times / hour) was measured. Thereafter, the sputtering chamber was released and particles in the chamber were confirmed. In the case of the oxide sputtering target of Comparative Example 8, since direct current (DC) sputtering could not be performed, it was described as “DC sputtering impossible” and the film formation was performed by high frequency sputtering.

＜Ｉｎの溶出＞
　Ｉｎの溶出はターゲット焼成後に目視による確認とＸＲＤ（Ｘ線回折）によって確認した。目視による確認において金属Ｉｎがターゲット表面に付着している場合、若しくはＸＲＤにおいて金属Ｉｎの回折ピークを確認した場合にＩｎ溶出「有」と判断し、表４に示した。 <Elution of In>
In elution was confirmed by visual inspection and XRD (X-ray diffraction) after firing the target. When the metal In was adhered to the target surface by visual confirmation, or when the diffraction peak of the metal In was confirmed by XRD, the In elution was judged as “present”, and the results are shown in Table 4.

＜ターゲットのＸＲＤ＞
　試料の準備：試料をＳｉＣ－Ｐａｐｅｒ（ｇｒｉｔ　１８０）を用いて湿式研磨、乾燥した後、ＸＲＤ用の測定試料を得た。以下の条件でＸＲＤを行い、その結果得られた主相、及びＺｎ２ＳｎＯ４の（４４０）反射を示す２θを表４に示した。
　装置：株式会社リガク製（ＲＩＮＴ－Ｕｌｔｉｍａ／ＰＣ）
　管球：Ｃｕ（ＣｕＫα1）
　管電圧：４０ｋＷ
　管電流：４０ｍＡ
　走査範囲（２θ）：５°～８０°
　スリットサイズ：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、受光（ＲＳ）０．８ｍｍ
　測定ステップ幅：２θで０．０２度
　スキャンスピード：毎分２度
　試料台回転スピード：３０ｒｐｍ <Target XRD>
Sample preparation: The sample was wet-polished and dried using SiC-Paper (grit 180) to obtain a measurement sample for XRD. The following conditions make XRD, the shown resulting main phase, and a Zn 2 SnO 4 a (440) 2 [Theta] showing reflection in Table 4.
Equipment: Rigaku Corporation (RINT-Ultima / PC)
Tube: Cu (CuKα1)
Tube voltage: 40kW
Tube current: 40 mA
Scanning range (2θ): 5 ° -80 °
Slit size: Divergence (DS) 2/3 degrees, Scattering (SS) 2/3 degrees, Light reception (RS) 0.8mm
Measurement step width: 0.02 degrees at 2θ Scan speed: 2 degrees per minute Sample stage rotation speed: 30 rpm

＜パーティクル＞
　上述の条件でプレスパッタを行い、ターゲット表面加工層を除去したのち、一旦チャンバーを大気開放して、防着板などのチャンバー部材の清掃を行った。その後、再び真空引きを行い、真空引き後、３０分のプレスパッタを行ってターゲット表面の大気吸着成分の除去を行ったのち、４インチのＳｉウェハ上に厚さ１００ｎｍの膜を成膜した。同じ条件で合計２５枚の膜を成膜し、成膜後のウェハについて市販の異物検査装置によりウェハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出した。なお、表４においては、パーティクルの個数がそれぞれ、２０以下の場合を「Ａ」、２１～５０の場合を「Ｂ」、５１～２００の場合を「Ｃ」、２０１以上の場合を「Ｄ」と表記した。 <Particle>
Pre-sputtering was performed under the above conditions to remove the target surface processed layer, and then the chamber was once opened to the atmosphere to clean the chamber members such as the deposition preventive plate. Thereafter, evacuation was performed again, and after evacuation, pre-sputtering for 30 minutes was performed to remove atmospheric adsorption components on the target surface, and then a film having a thickness of 100 nm was formed on a 4-inch Si wafer. A total of 25 films were formed under the same conditions, and the number of particles of 1.0 μm or more adhering to the wafer surface was measured with a commercially available foreign substance inspection apparatus for the wafers after film formation, and the average value of 25 sheets was calculated. In Table 4, “A” indicates that the number of particles is 20 or less, “B” indicates that the number of particles is 21 to 50, “C” indicates that the number is 51 to 200, and “D” indicates that the number of particles is 201 or more. It was written.

＜膜の押し込み硬さ＞
　上述の条件において基板をコーニング社製１７３７ガラス、目標膜厚を５００ｎｍとして成膜を行い、形成された膜に対し、押し込み加重を３５ｍｇｆとし、超微小押し込み硬さ試験機（エリオニクス社製ＥＮＴ－１１００ａ）を用いて測定を行った。なお、基板は２７℃の装置内にセットされ、その後１時間以上経過してから押し込み硬さを測定した。なお、１０点で測定された押し込み硬さの平均値を測定値として表５に示した。 <Indentation hardness of film>
Under the conditions described above, the substrate was formed with Corning 1737 glass and a target film thickness of 500 nm, and the indentation weight was set to 35 mgf, and an ultra-fine indentation hardness tester (ENTIONICS Corporation ENT- 1100a) was used for the measurement. The substrate was set in a 27 ° C. apparatus, and the indentation hardness was measured after 1 hour or more had passed. The average value of indentation hardness measured at 10 points is shown in Table 5 as a measured value.

＜膜の割れ＞
　上述の条件において、厚さ０．１ｍｍのＰＥＴフィルムに１００ｎｍの膜厚で成膜し、フィルムを１０回折り曲げた後、膜表面を顕微鏡により倍率１０００倍にて観察して割れの有無を調べた。 <Membrane cracking>
Under the above-mentioned conditions, a film of 100 nm was formed on a PET film having a thickness of 0.1 mm, the film was bent 10 times, and then the surface of the film was observed with a microscope at a magnification of 1000 to check for cracks. .

＜反射率の変化＞
　ポリカーボネート上にＡｇ９８．１Ｎｄ１．０Ｃｕ０．９合金をスパッタし、下記の色素を成膜した基板を用い、その上に上述の成膜条件において各実施例及び比較例の酸化物膜（保護膜）を厚さ１４ｎｍ成膜した。その後、８０℃、８５％の恒温恒湿器に１００時間静置して、その前後の反射率の変化を測定した。なお、反射率の測定には、紫外可視分光光度計（日本分光株式会社製Ｖ－５５０）を用いた。また、波長４０５ｎｍの光に対する反射率を求めた。 <Change in reflectance>
A substrate in which an Ag 98.1 Nd 1.0 Cu 0.9 alloy was sputtered on a polycarbonate and the following dye was formed was used, and the oxide films of the examples and comparative examples were formed on the substrate under the above-described film formation conditions. (Protective film) was formed to a thickness of 14 nm. Then, it was left to stand in a constant temperature and humidity chamber at 80 ° C. and 85% for 100 hours, and the change in reflectance before and after that was measured. The reflectance was measured using an ultraviolet-visible spectrophotometer (V-550 manufactured by JASCO Corporation). Moreover, the reflectance with respect to the light of wavelength 405nm was calculated | required.

色素：
　上記基板に成膜された色素として、例えば、アゾ系色素として、６－ヒドロキシ－２－ピリドン構造からなるカップラー成分と、イソキサゾールトリアゾールのジアゾ成分とを有する化合物と、該有機色素化合物が配位する金属イオンとから構成される金属錯体化合物が挙げられる。前記カップラー成分とジアゾ成分とを有する化合物をオクタフルオロペンタノール（ＯＦＰ）で１．０重量％に希釈した混合溶液をスピンコートで成膜した。 Dye:
As the dye formed on the substrate, for example, as an azo dye, a compound having a coupler component having a 6-hydroxy-2-pyridone structure and a diazo component of isoxazole triazole, and the organic dye compound are arranged. And metal complex compounds composed of metal ions that are positioned. A mixed solution in which the compound having the coupler component and the diazo component was diluted to 1.0% by weight with octafluoropentanol (OFP) was formed by spin coating.

Figure JPOXMLDOC01-appb-T000005
 
Figure JPOXMLDOC01-appb-T000005
  

Figure JPOXMLDOC01-appb-T000006
 
Figure JPOXMLDOC01-appb-T000006
  

　上記の表４に示された結果からわかるように、実施例１～２１のスパッタリングターゲットは、いずれも比抵抗が０．１Ω・ｃｍ以下であり、直流スパッタリングを実施でき、異常放電回数が非常に少ないことが確認できた。そして、実施例１～２１のいずれにおいても、Ｉｎの溶出も見られず、Ｉｎが固溶したＺｎ２ＳｎＯ４が主相であることも確認された。
　これに対して、比較例１のスパッタリングターゲットでは、Ｚｎ２ＳｎＯ４が主相ではあるが、Ｉｎを含有しないものであって、比抵抗が高く、異常放電が多発した。比較例２では、Ｉｎ２Ｏ３の配合が多いため、Ｉｎが溶出し、酸化物スパッタリングターゲットの作製に不適であることが確認された。比較例３のスパッタリングターゲットでは、ＩｎとＳｎの含有量の比Ｒ１が小さすぎるため、Ｉｎが固溶したＺｎ２ＳｎＯ４が主相とならなかった。比較例４のスパッタリングターゲットでは、ＳｎＯ２の配合が多すぎたため、ＳｎＯ２が主相になってしまい、Ｉｎが固溶したＺｎ２ＳｎＯ４が主相とならなかった。比較例５～７のスパッタリングターゲットでは、Ｉｎの溶出は無く、Ｉｎが固溶したＺｎ２ＳｎＯ４が主相となっているが、いずれも比抵抗が高く、異常放電が多発し、直流スパッタリングには不適であることが確認された。 As can be seen from the results shown in Table 4 above, the sputtering targets of Examples 1 to 21 all have a specific resistance of 0.1 Ω · cm or less, can perform direct current sputtering, and have a very high number of abnormal discharges. It was confirmed that there were few. In any of Examples 1 to 21, no elution of In was observed, and it was also confirmed that Zn 2 SnO 4 in which In was dissolved was the main phase.
On the other hand, in the sputtering target of Comparative Example 1, Zn 2 SnO 4 was the main phase, but it did not contain In, had a high specific resistance, and abnormal discharge occurred frequently. In Comparative Example 2, it was confirmed that since In 2 O 3 was mixed in a large amount, In was eluted and it was unsuitable for producing an oxide sputtering target. In the sputtering target of Comparative Example 3, since the ratio R1 of the In and Sn contents was too small, Zn 2 SnO 4 in which In was dissolved did not become the main phase. In the sputtering target of Comparative Example 4, since SnO 2 was blended too much, SnO 2 became the main phase, and Zn 2 SnO 4 in which In was dissolved did not become the main phase. In the sputtering targets of Comparative Examples 5 to 7, there is no elution of In, and Zn 2 SnO 4 in which In is dissolved is the main phase, but all have high specific resistance, frequent abnormal discharges, and are used for direct current sputtering. Was found to be inappropriate.

　また、成膜された酸化物膜（保護膜）に関しては、上記の表５に示された結果から分かるように、実施例１～２１のスパッタリングターゲットを用いて直流スパッタリングで成膜された場合には、いずれの場合も、柔らかく割れ難く、且つ、反射率の変化が小さい膜が得られることを確認できた。
　これに対して、比較例１の場合には、膜の押込み硬さの値が高く、しかも、膜の割れが発生しており、保護膜に適した柔らかい膜が得られなかった。比較例３の場合には、膜の割れは発生しなかったものの、膜の押込み硬さの値が高く、保護膜に適した柔らかい膜が得られなかった。 As for the oxide film (protective film) formed, as can be seen from the results shown in Table 5 above, when the film was formed by direct current sputtering using the sputtering targets of Examples 1 to 21. In any case, it was confirmed that a film that was soft and difficult to break and had a small change in reflectance was obtained.
On the other hand, in the case of Comparative Example 1, the indentation hardness value of the film was high, and the film was cracked, so that a soft film suitable for the protective film could not be obtained. In the case of Comparative Example 3, although the film did not crack, the value of indentation hardness of the film was high, and a soft film suitable for the protective film could not be obtained.

　以上の様に、上記各実施例の酸化物スパッタリングターゲットによれば、スパッタリングターゲットを構成する酸化物焼結体がＩｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有するので、ターゲット自体の比抵抗が一層低下し、安定した直流（ＤＣ）スパッタリングが可能であることを確認できた。また、各実施例の酸化物スパッタリングターゲットを用いて直流スパッタリングでＳｎ－Ｉｎ－Ｚｎ－Ｏ四元系酸化物膜を成膜でき、しかも、柔らかく割れ難い膜が得られることを確認できた。そのため、各実施例の酸化物スパッタリングターゲットで成膜された酸化物膜は、有機色素の記録層を使用したＢＤ用の誘電体保護膜として好適であり、記録媒体として高い保存性を有するものであることを確認できた。 As described above, according to the oxide sputtering target of each of the above examples, the oxide sintered body constituting the sputtering target has a structure whose main phase is Zn 2 SnO 4 in which In is dissolved, so that the target itself It was confirmed that the specific resistance was further reduced and stable direct current (DC) sputtering was possible. It was also confirmed that a Sn—In—Zn—O quaternary oxide film could be formed by direct current sputtering using the oxide sputtering target of each example, and that a soft and hard-to-break film could be obtained. Therefore, the oxide film formed with the oxide sputtering target of each example is suitable as a dielectric protective film for BD using an organic dye recording layer, and has high storage stability as a recording medium. I was able to confirm that there was.

　次に、代表的に実施例１及び比較例１のスパッタリングターゲットについて、Ｘ線回折（ＸＲＤ）した結果を図２及び図３に示す。この結果からわかるように、実施例１では、ＺｎＯに帰属する回折ピークと、ＳｎＯ２とＺｎＯとの複合酸化物であるＺｎ２ＳｎＯ４とに帰属する回折ピークが検出され（Ｐｏｗｄｅｒ　Ｄｉｆｆｒａｃｔｉｏｎ　Ｆｉｌｅ Ｎｏ．７４－２１８４を参照）、ＺｎＯ及びＺｎ２ＳｎＯ４の相の存在が確認された。また、実施例１は、Ｚｎ２ＳｎＯ４の回折ピークがＩｎの固溶により低角側へシフトしていることが確認された。 Next, the results of X-ray diffraction (XRD) of the sputtering targets of Example 1 and Comparative Example 1 are shown in FIG. 2 and FIG. As can be seen from the results, in Example 1, a diffraction peak attributed to ZnO and a diffraction peak attributed to Zn 2 SnO 4 which is a composite oxide of SnO 2 and ZnO were detected (Powder Diffraction File No. 1). 74-2184), the presence of ZnO and Zn 2 SnO 4 phases was confirmed. In Example 1, it was confirmed that the diffraction peak of Zn 2 SnO 4 was shifted to the low angle side due to the solid solution of In.

　また、実施例１のスパッタリングターゲットについて、ＥＰＭＡ（ＦＥ－ＥＰＭＡ：フィールドエミッション型電子線マイクロアナライザー）にて、反射電子像（ＣＰ）および各元素の組成分布を示す元素分布像を観察した。上記反射電子像および元素分布像を図１に示す。
　なお、ＥＰＭＡによる元素分布像は、本来カラー像であるが、白黒像に変換して記載しているため、図１において濃淡の淡い部分（比較的白い部分）が所定元素の濃度が高い部分となっている。
　これら画像から、実施例１のスパッタリングターゲットは、ＺｎＯとＺｎ２ＳｎＯ４との相からなり、ＩｎがＺｎ２ＳｎＯ４相に非常に均一に分散していることがわかる。 For the sputtering target of Example 1, a reflected electron image (CP) and an element distribution image showing the composition distribution of each element were observed with EPMA (FE-EPMA: field emission electron beam microanalyzer). The reflected electron image and element distribution image are shown in FIG.
The element distribution image by EPMA is originally a color image, but is converted into a black and white image. Therefore, in FIG. 1, a light and shaded portion (a relatively white portion) is a portion where the concentration of a predetermined element is high. It has become.
From these images, it can be seen that the sputtering target of Example 1 is composed of a phase of ZnO and Zn 2 SnO 4 and In is very uniformly dispersed in the Zn 2 SnO 4 phase.

　なお、本実施形態に係る酸化物焼結体を、スパッタリングターゲットとして利用するためには、面粗さ：５．０μｍ以下、より好ましくは１．０μｍ以下、粒径：２０μｍ以下、より好ましくは１０μｍ以下、金属系不純物濃度：０．１原子％以下、より好ましくは０．０５原子％以下、抗折強度：５０ＭＰａ以上、より好ましくは１００ＭＰａ以上であることが好ましい。上記各実施例は、いずれもこれらの条件を満たしていた。 In order to use the oxide sintered body according to this embodiment as a sputtering target, surface roughness: 5.0 μm or less, more preferably 1.0 μm or less, particle size: 20 μm or less, more preferably 10 μm. Hereinafter, it is preferable that the metal impurity concentration is 0.1 atomic% or less, more preferably 0.05 atomic% or less, and the bending strength is 50 MPa or more, more preferably 100 MPa or more. Each of the above examples satisfied these conditions.

　また、本発明の技術範囲は上記実施形態および上記実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
　例えば、上記実施形態および上記実施例では、加圧焼結をホットプレスによって行っているが、他の方法としてＨＩＰ法（熱間等方加圧式焼結法）等を採用しても構わない。 The technical scope of the present invention is not limited to the above-described embodiment and examples, and various modifications can be made without departing from the spirit of the present invention.
For example, in the above embodiment and the above examples, pressure sintering is performed by hot pressing, but as another method, a HIP method (hot isostatic pressing method) or the like may be employed.

　本発明によれば、光記録媒体保護膜形成用として、保存性が高く、柔らかく割れ難く、パーティクルの少ない膜を成膜可能であると共に、直流スパッタが可能な酸化物スパッタリングターゲットを提供できる。 According to the present invention, it is possible to provide an oxide sputtering target capable of forming a film having a high storage stability, soft and difficult to break, and having few particles, and capable of direct current sputtering, for forming an optical recording medium protective film.

Claims (6)

　全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下である組成の酸化物焼結体であり、
　前記酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有することを特徴とする酸化物スパッタリングターゲット。 Sn: 7 at% or more and In: 0.1 to 35.0 at% with respect to the total amount of metal components, the balance is made of Zn and inevitable impurities, and the atomic ratio of Sn to Zn Sn / (Sn + Zn ) Is an oxide sintered body having a composition of 0.5 or less,
The oxide sintered body is characterized in that the oxide sintered body has a structure whose main phase is Zn 2 SnO 4 in which In is dissolved. 　全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなり、ＳｎとＺｎの含有原子比Ｓｎ／（Ｓｎ＋Ｚｎ）が０．５以下であり、且つ、Ｓｎ、Ｃｒ，Ｇｅ、Ｚｎの含有原子比（Ｓｎ＋Ｃｒ＋Ｇｅ）／（Ｓｎ＋Ｃｒ＋Ｇｅ＋Ｚｎ）が０．６以下である組成の酸化物焼結体であり、
　前記酸化物焼結体は、Ｉｎが固溶したＺｎ２ＳｎＯ４を主相とした組織を有することを特徴とする酸化物スパッタリングターゲット。 It contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and a total of one or more of Ge and Cr: 1.0-30.0 at %, The balance is made of Zn and inevitable impurities, the atomic ratio Sn / (Sn + Zn) of Sn and Zn is 0.5 or less, and the atomic ratio of Sn, Cr, Ge, Zn (Sn + Cr + Ge) ) / (Sn + Cr + Ge + Zn) is an oxide sintered body having a composition of 0.6 or less,
The oxide sintered body is characterized in that the oxide sintered body has a structure whose main phase is Zn 2 SnO 4 in which In is dissolved. 　請求項１に記載の酸化物スパッタリングターゲットの製造方法であって、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成することを特徴とする酸化物スパッタリングターゲットの製造方法。 A method of manufacturing an oxide sputtering target according to claim 1, and SnO 2 powder, and In 2 O 3 powder, a mixed powder obtained by mixing and blending the ZnO powder, vacuum or inert A method for producing an oxide sputtering target, comprising performing pressure firing in a gas at a temperature of 800 to 1100 ° C. for 2 to 9 hours. 　請求項２に記載の酸化物スパッタリングターゲットの製造方法であって、ＳｎＯ２粉末と、Ｉｎ２Ｏ３粉末と、ＺｎＯ粉末とを配合し、さらに、Ｃｒ２Ｏ３粉末及びＧｅＯ２粉末のうち１種以上を配合し混合して得られた混合粉末を、真空中又は不活性ガス中、８００～１１００℃の温度で、２～９時間加圧焼成することを特徴とする酸化物スパッタリングターゲットの製造方法。 A method of manufacturing an oxide sputtering target according to claim 2, and SnO 2 powder was blended with In 2 O 3 powder and ZnO powder, further, Cr 2 O 3 of the powder and GeO 2 powder 1 Production of oxide sputtering target characterized in that mixed powder obtained by mixing and mixing seeds or more is subjected to pressure firing for 2 to 9 hours at a temperature of 800 to 1100 ° C. in vacuum or in an inert gas Method. 　請求項１に記載の酸化物スパッタリングターゲットを用いてスパッタリング成膜され、
　全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、残部がＺｎ及び不可避不純物からなることを特徴とする光記録媒体用保護膜。 Sputtered using the oxide sputtering target according to claim 1,
A protective film for an optical recording medium, comprising Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, the balance being made of Zn and inevitable impurities. 　請求項２に記載の酸化物スパッタリングターゲットを用いてスパッタリング成膜され、
　全金属成分量に対して、Ｓｎ：７ａｔ％以上と、Ｉｎ：０．１～３５．０ａｔ％とを含有し、さらに、Ｇｅ及びＣｒのうち１種以上の合計：１．０～３０．１ａｔ％を含有し、残部がＺｎ及び不可避不純物からなる成分組成の酸化物であることを特徴とする光記録媒体用保護膜。 Sputtered using the oxide sputtering target according to claim 2,
It contains Sn: 7 at% or more and In: 0.1-35.0 at% with respect to the total amount of metal components, and a total of one or more of Ge and Cr: 1.0-30.1 at %, And the balance is an oxide having a component composition consisting of Zn and inevitable impurities.
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