CN114008000A - 氧化物烧结体 - Google Patents

氧化物烧结体 Download PDF

Info

Publication number
CN114008000A
CN114008000A CN202080046931.9A CN202080046931A CN114008000A CN 114008000 A CN114008000 A CN 114008000A CN 202080046931 A CN202080046931 A CN 202080046931A CN 114008000 A CN114008000 A CN 114008000A
Authority
CN
China
Prior art keywords
sintered body
oxide sintered
atomic ratio
less
body according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202080046931.9A
Other languages
English (en)
Other versions
CN114008000B (zh
Inventor
笘井重和
上冈义弘
胜又聪
佐佐木健一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to CN202410029992.4A priority Critical patent/CN117819960A/zh
Publication of CN114008000A publication Critical patent/CN114008000A/zh
Application granted granted Critical
Publication of CN114008000B publication Critical patent/CN114008000B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/053—Fine ceramics
    • 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
    • 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
    • C04B35/44—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 aluminates
    • 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
    • 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
    • C04B35/44—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 aluminates
    • C04B35/443—Magnesium aluminate spinel
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
    • 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
    • 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
    • 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
    • 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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—Material
    • H01J37/3429—Plural materials
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C04B2235/3286—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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6586—Processes characterised by the flow of gas
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

氧化物烧结体，其包含锌、镁、金属元素X和氧作为构成元素，所述金属元素X为正3价或正4价，金属元素X相对于锌、镁和金属元素X的合计的原子比[X/（Zn+Mg+X）]为0.0001以上且0.6以下，镁相对于锌和镁的合计的原子比[Mg/（Zn+Mg）]为0.25以上且0.8以下。

Description

氧化物烧结体
技术领域
本发明涉及氧化物烧结体和用于形成薄膜的成膜用材料。
背景技术
MgO-ZnO系氧化物有在彩色液晶投影仪用透光性陶瓷（专利文献1）、氧化物半导体（专利文献2）、透明电极（专利文献3）等中的应用例。例如，专利文献3公开了下述烧结体，其原子比为Al/（Zn+Al+Mg）＝0.005~0.1，Mg/（Zn+Al+Mg）＝0.001~0.05，并包含：含有氧化锌且具有平均粒径为10μm以下的六方晶系纤锌矿型结构的颗粒（a）、以及含有铝且具有平均粒径为5μm以下的尖晶石结构的颗粒（b）。
上述烧结体是重视导电性的材料，但其以ZnO作为主成分，因此，在紫外线区域的透光性存在课题。
现有技术文献
专利文献
专利文献1：日本特开2009-184898号公报
专利文献2：日本特开2012-066968号公报
专利文献3：日本特开2011-063866号公报。
发明内容
本发明的目的之一在于，提供能够获得紫外线区域的透光性高且导电性也高的膜的氧化物烧结体。
本发明人等发现：通过使用向Mg和Zn系的氧化物中以特定的浓度添加有正3价或正4价的金属元素的氧化物烧结体并成膜，从而能够得到紫外线区域的透光性高且导电性也良好的膜。
根据本发明，提供以下的氧化物烧结体等。
1. 氧化物烧结体，其包含锌、镁、金属元素X和氧作为构成元素，所述金属元素为正3价或正4价，前述金属元素X相对于前述锌、前述镁和前述金属元素X的合计的原子比[X/（Zn+Mg+X）]为0.0001以上且0.6以下，前述镁相对于前述锌和前述镁的合计的原子比[Mg/（Zn+Mg）]为0.25以上且0.8以下。
2. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.625以上且0.8以下。
3. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.626以上且0.75以下。
4. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.628以上且0.74以下。
5. 根据2~4中任一项所述的氧化物烧结体，其包含固溶有Zn的立方晶的MgO和固溶有Zn的MgX2O4（X为正3价的金属元素）。
6. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.25以上且小于0.625。
7. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.30以上且0.60以下。
8. 根据1所述的氧化物烧结体，其中，前述原子比[Mg/（Zn+Mg）]为0.40以上且0.59以下。
9. 根据6~8中任一项所述的氧化物烧结体，其包含固溶有Zn的立方晶的MgO、固溶有Mg的六方晶的ZnO和固溶有Zn的MgX2O4（此处，X为正3价的金属元素）。
10. 根据1~9中任一项所述的氧化物烧结体，其中，前述原子比[X/（Zn+Mg+X）]为0.003以上且0.6以下。
11. 根据1~9中任一项所述的氧化物烧结体，其中，前述原子比[X/（Zn+Mg+X）]为0.007以上且0.5以下。
12. 根据1~9中任一项所述的氧化物烧结体，其中，前述原子比[X/（Zn+Mg+X）]为0.008以上且0.5以下。
13. 根据1~9中任一项所述的氧化物烧结体，其中，前述原子比[X/（Zn+Mg+X）]为0.01以上且0.5以下。
14. 根据1~13中任一项所述的氧化物烧结体，其中，前述X为Al和Ga中的至少一者。
15. 根据14所述的氧化物烧结体，其中，前述X为Al。
16. 根据14所述的氧化物烧结体，其中，前述X为Ga。
17. 成膜用材料，其包含1~16中任一项所述的氧化物烧结体。
18. 根据17所述的成膜用材料，其为成膜用平板。
19. 根据17所述的成膜用材料，其为溅射靶。
20. 薄膜，其是使用17~19中任一项所述的成膜用材料而得到的。
根据本发明，可提供能够获得紫外线区域的透光性高且导电性也高的膜的氧化物烧结体。
附图说明
图1是表示实施例1的氧化物烧结体的XRD谱图的分析结果的图。
图2是表示实施例2的氧化物烧结体的XRD谱图的分析结果的图。
图3是表示比较例1的氧化物烧结体的XRD谱图的分析结果的图。
图4是表示实施例7的氧化物烧结体的XRD谱图的分析结果的图。
图5是表示实施例8的氧化物烧结体的XRD谱图的分析结果的图。
图6是表示比较例2的氧化物烧结体的XRD谱图的分析结果的图。
具体实施方式
本发明的一个实施方式所述的氧化物烧结体包含锌（Zn）、镁（Mg）、金属元素（X）和氧（O）作为构成元素，所述金属元素（X）为正3价或正4价。并且，原子比[X/（Zn+Mg+X）]为0.0001以上且0.6以下，原子比[Mg/（Zn+Mg）]为0.25以上且0.8以下。
本实施方式中，作为正3价或正4价的金属元素X，可列举出Al、Ga、In、Sc、Y。优选为Al和/或Ga，更优选为Al。通过包含Al，从而氧化物烧结体的相对密度变高。相对密度高意味着可成为成膜时的异常放电的原因、产生结块（nodule）的起点的空隙少，因此，例如将氧化物烧结体作为溅射靶时，溅射时的破裂等的发生少，能够稳定溅射。
原子比[X/（Zn+Mg+X）]为0.0001以上且0.6以下。通过满足该范围，从而成为能够形成兼顾紫外线区域的透光性和导电性的膜的氧化物烧结体。
原子比[X/（Zn+Mg+X）]可以为0.006以上，也可以超过0.007，可以为0.008以上，也可以为0.01以上。此外，原子比[X/（Zn+Mg+X）]可以为0.5以下，也可以为0.2以下，还可以为0.1以下。
原子比[Mg/（Zn+Mg）]为0.25以上且0.8以下。通过满足该范围，从而成为能够形成兼顾紫外线区域的透光性和导电性的膜的氧化物烧结体。需要说明的是，原子比超过0.8时，即便对由氧化物烧结体得到的膜进行退火，也无法获得导电性高的膜。另一方面，小于0.25时，膜的紫外线透射率变低。
一个实施方式中，原子比[Mg/（Zn+Mg）]为0.625以上且0.8以下。通过满足该范围，从而主要成为能够获得紫外线区域的透光性优异的膜的氧化物烧结体。
原子比[Mg/（Zn+Mg）]可以为0.626以上，也可以为0.628以上。此外，原子比[Mg/（Zn+Mg）]可以为0.75以下，也可以为0.70以下，还可以为0.67以下。
一个实施方式中，原子比[Mg/（Zn+Mg）]为0.25以上且小于0.625。通过满足该范围，从而主要成为能够获得导电性优异的膜的氧化物烧结体。
原子比[Mg/（Zn+Mg）]可以为0.30以上，也可以为0.40以上。此外，原子比[Mg/（Zn+Mg）]可以为0.60以下，也可以为0.55以下。
锌、镁和金属元素X的原子比可通过调整起始原料的原子比来控制。氧化物烧结体的原子比与起始原料的原子比相比，存在锌的比率变高、金属元素X的原子比大致相同的倾向。
氧化物烧结体中包含的各元素的原子比可通过电感耦合等离子体发光分析装置（ICP-AES）对含有元素进行分析来求出。具体而言，利用喷雾器将溶液试样制成雾状，并导入至氩气等离子体（约5000~8000℃）时，试样中的元素吸收热能而被激发，轨道电子从基底状态转移至高能级轨道后，向更低能级的轨道转移。此时，将能量差以光的形式放射而发光。该光会显示元素固有的波长（谱线），因此，可根据谱线的有无来确认元素的存在（定性分析）。此外，谱线的大小（发光强度）与试样中的元素数成比例，因此，通过与已知浓度的标准液相对比而能够求出试样浓度（定量分析）。通过定性分析来确定所含的元素后，通过定量分析来求出含量，由其结果求出各元素的原子比。
本实施方式的氧化物烧结体的构成元素可以实质上由Mg、Zn、金属元素X和O组成（consisting essentially of）。本实施方式的氧化物烧结体的构成元素的例如70mol%以上、80mol%以上或90mol%以上可以为Mg、Zn、金属元素X和O。此外，本实施方式的氧化物烧结体的构成元素可以仅由Mg、Zn、金属元素X和O组成（consisting of）。此时，可以包含不可避免的杂质。
原子比[Mg/（Zn+Mg）]为0.625以上且0.8以下时，氧化物烧结体包含固溶有Zn的立方晶的MgO和固溶有Zn的MgX2O4（X为正3价的金属元素）。此外，原子比[Mg/（Zn+Mg）]为0.25以上且小于0.625时，氧化物烧结体包含固溶有Zn的立方晶的MgO、固溶有Mg的六方晶的ZnO和固溶有Zn的MgX2O4（此处，X为正3价的金属元素）。由此，即便是相对而言的轻金属的氧化物，也能够得到高密度的烧结体。
氧化物烧结体包含上述的各氧化物可通过将利用X射线衍射（XRD）法而得到的XRD谱图与ICDD（国际衍射数据中心）的数据库（PDF：Powder Diffraction File）进行对照来确认。此外，各结晶固溶有其它金属元素可通过将利用XRD而求出的晶格常数（实测值）与PDF中记载的晶格常数（PDF值）加以对比来判断。例如，在固溶有Zn的结晶的情况下，实测值大于PDF值。
本实施方式的氧化物烧结体可通过例如下述工序来制造：将原料粉末混合而制备混合粉末的工序、将混合粉末成型而制成成型体的工序、以及对成型体进行烧成的工序。
作为起始原料，可使用包含Mg的化合物的粉末、包含Zn的化合物的粉末和包含金属元素X的化合物的粉末。化合物优选为氧化物。可列举出例如MgO、ZnO、Al2O3、Ga2O3。
原料粉末的混合比例如可考虑想要获得的氧化物烧结体的原子比来调整。
原料粉末的平均粒径优选为0.1~1.2μm，更优选为0.5~1.0μm。原料粉末的平均粒径可利用激光衍射式粒度分布装置等进行测定。
原料的混合、成型方法没有特别限定，可采用公知方法。此外，在混合时可以添加粘结剂。
原料的混合例如可使用球磨机、珠磨机、喷射磨或超声波装置等公知装置来进行。混合时间进行适当调整即可，优选为6~100小时左右。
成型方法中，例如，可以将混合粉末进行加压成型而制成成型体。通过该工序，能够成型为制品的形状（例如作为溅射靶而言适合的形状）。
将混合粉末填充至模具中，通常，利用模具加压或冷等静压加压（CIP），以例如1000kg/cm2以上进行加压，由此能够得到成型体。
需要说明的是，在成型时，可以使用聚乙烯醇、聚乙二醇、甲基纤维素、聚蜡、油酸、硬脂酸等成型助剂。
将所得成型体以例如1200~1650℃的温度加热2小时以上，从而能够得到氧化物烧结体。
加热温度优选为1350~1600℃、更优选为1400~1600℃、进一步优选为1450~1500℃。加热时间优选为2~72小时、更优选为3~48小时、进一步优选为4~24小时。
烧成中，通常将成型体在大气气氛或氧气气氛中加热。氧气气氛优选氧浓度例如为10~50体积%的气氛。
本实施方式的氧化物烧结体可适合地用作用于形成具有氧化物烧结体的组成的薄膜的成膜用材料，例如通过真空蒸镀法、离子镀法进行成膜时使用的平板、溅射靶。由本实施方式的成膜用材料得到的薄膜可用作在紫外发光二极管、紫外发光激光二极管等的电极基板中使用的透明导电膜。
需要说明的是，通过在成膜后将膜以高温进行热处理，从而膜的紫外线透射率和导电性提高。刚成膜后的膜呈现锌氧化物与镁氧化物等均匀混合的状态。通过对该状态的膜进行热处理，从而发生氧化物的聚集、分离等，其结果可推测：因锌氧化物形成网络而表现出导电性，另一方面，因镁氧化物在锌氧化物的网络间隙中聚集而使紫外线发生透射。
电极层的热处理温度优选为750℃以上，更优选为900℃以上。
平板可通过例如对将原料成型为期望形状并烧成而得到的氧化物烧结体进行切削或研磨加工来制作。溅射靶可通过例如对氧化物烧结体进行切削或研磨加工，并粘合于背板来制作。
通过进行切削加工而能够去除凹凸的面。此外，能够制成指定的大小。可以对表面进行#200号或#400号、进而#800号的研磨。由此，能够抑制溅射中的异常放电、颗粒的产生。
根据需要对已研磨的氧化物烧结体进行清洗后，对接合面涂布金属铟焊料等接合材料，并与背板进行接合，从而能够得到溅射靶。
实施例
实施例1
（A）氧化物烧结体的制作
将平均粒径为1μm以下的氧化锌（ZnO）粉末、平均粒径为1μm以下的氧化镁（MgO）粉末和平均粒径为1μm以下的氧化镓（Ga2O3粉末）以各金属的原子比成为表1所示值的方式进行称量，并混合。需要说明的是，关于混合粉末的质量分数，ZnO为43.9质量%、MgO为40.8质量%、Ga2O3为15.3质量%。
将混合粉末投入至树脂制锅后，添加水，使用硬质ZrO2球作为粉碎介质，用湿式球磨机混合20小时。将所得混合浆料取出，进行过滤、干燥和造粒。将所得造粒物投入至模具中，利用冷等静压加压而加压至3ton/cm2，进行成型。
将所得成型体载置在烧结炉内，边以每0.1m3炉内容积为5L/分钟的比例流入氧气，边对成型体进行烧成。
将烧结炉内的温度以1℃/分钟从室温升温至1000℃为止，以3℃/分钟从1000℃升温至1470℃为止，以1470℃烧成5小时。其后，停止氧气的流入，将炉内温度以10℃/分钟从1470℃降温至1300℃为止。接着，边以每0.1m3炉内容积为10L/分钟的比例流入Ar，边将炉内温度以1300℃保持3小时。其后，通过自然冷却而得到氧化物烧结体。
针对所得的氧化物烧结体，评价组成和相对密度。将结果示于表2。
Figure 664501DEST_PATH_IMAGE001
Figure 378379DEST_PATH_IMAGE002
评价方法如下所示。
（1）氧化物烧结体中的金属元素的原子比
切出所得氧化物烧结体的一部分，溶解于酸后，利用电感耦合等离子体发光分析装置进行分析。
（2）相对密度
相对密度如下计算：通过使用水的阿基米德法来测定氧化物烧结体的实际密度，并除以由组成算出的理论密度。需要说明的是，理论密度由没有氧缺陷的MgO结晶、Zn氧化物和X（Ga或Al）的氧化物的质量分数来计算。
（3）XRD测定
利用下述装置和条件进行测定。
・装置：理学公司制的Ultima-III
・X射线：Cu-Kα射线（波长：1.5406Å、利用石墨单色器进行单色化）
・2θ-θ反射法、连续扫描（1.0°/分钟）
・取样间隔：0.02°
・狭缝DS、SS：2/3°、RS：0.6mm。
通过利用统合粉末X射线分析软件（理学公司制、PDXL2）对XRD测定的结果进行分析，从而求出氧化物烧结体中包含的晶体结构和晶格常数。需要说明的是，晶体结构利用下述的ICDD（PDF）卡来确认。
ZnO：01-079-0205（六方晶）
ZnO：01-077-0191（立方晶）
MgO：01-071-1176（立方晶）
MgAl2O4：01-084-0377
MgGa2O4：01-073-1721。
图1中示出XRD谱图的分析结果。由图1可确认：在氧化物烧结体中，作为晶体结构，包含ZnO、MgO和MgGa2O4。
根据晶格常数的实测值和PDF值，针对固溶有Zn的MgO和固溶有Zn的MgX2O4（X＝Ga或Al）的存在进行评价。
关于MgO的晶格常数a，实测值为4.2314，PDF值为4.217。关于ZnO的晶格常数a，实测值为3.2423，PDF值为3.242。关于MgGa2O4的晶格常数a，实测值为8.3116，PDF值为8.26。由该结果可确认MgO和MgGa2O4的晶格常数a之差大，判断在这些结晶中固溶有Zn。需要说明的是，晶格常数变化0.01以上时，判断为已固溶。
将结果示于表3。表中，包含时记作○、不含时记作×。
Figure 486013DEST_PATH_IMAGE003
（B）溅射靶的制作
针对所得的氧化物烧结体，将成为溅射面的面用杯磨石进行研磨，加工成直径100mm、厚度5mm。使用In系合金，在已研磨的氧化物烧结体上贴合背板，制作溅射靶。
使用由氧化物烧结体制作的溅射靶，实际形成薄膜，并进行评价。成膜条件如下所示。
将蓝宝石基板（厚度0.5mm）放入超声波清洗器中，用三氯乙烯清洗5分钟，用丙酮清洗5分钟，用甲醇清洗5分钟，最后，用蒸馏水清洗5分钟。
将该基板置于溅射装置（ULVAC公司制：ACS-4000）中，溅射气体使用Ar，以25℃进行成膜，在基板上形成厚度100nm的膜。
（2）热处理
对于通过上述（1）而形成有膜的基板，在氮气气氛以950℃热处理5分钟（活化退火）。针对热处理后的膜，使用三菱化学公司制的ロレスタFP，测定表面电阻。此外，使用分光光度计（岛津制作所制：UV-2600），评价紫外线透射率。
将评价结果示于表4。
Figure 680889DEST_PATH_IMAGE004
实施例2~6、比较例1
以各金属元素的原子比成为表1所示值的方式称量原料，并进行混合，除此之外，与实施例1同样操作，制作氧化物烧结体和溅射靶，并进行评价。将结果示于表2~4。需要说明的是，金属元素X为Al的实施例中，使用平均粒径为1μm以下的氧化铝（Al2O3粉末）。
图2中示出实施例2的氧化物烧结体的XRD谱图的分析结果。图3中示出比较例1的氧化物烧结体的XRD谱图的分析结果。
实施例7
（A）氧化物烧结体的制作
将平均粒径为1μm以下的氧化锌（ZnO）粉末、平均粒径为1μm以下的氧化镁（MgO）粉末和平均粒径为1μm以下的氧化镓（Ga2O3粉末）以各金属的原子比成为表5所示值的方式进行称量，并混合。需要说明的是，关于混合粉末的质量分数，ZnO为48.9质量%、MgO为36.3质量%、Ga2O3为14.8质量%。
将混合粉末投入至树脂制锅后，添加水，使用硬质ZrO2球作为粉碎介质，用湿式球磨机混合20小时。将所得混合浆料取出，进行过滤、干燥和造粒。将所得造粒物投入至模具中，利用冷等静压加压而加压至3ton/cm2，进行成型。
将所得成型体载置在烧结炉内，边以每0.1m3炉内容积为5L/分钟的比例流入氧气，边对成型体进行烧成。
将烧结炉内的温度以1℃/分钟从室温升温至1000℃为止，边以3℃/分钟从1000℃升温至1470℃为止，以1470℃烧成5小时。其后，停止氧气的流入，将炉内温度以10℃/分钟从1470℃降温至1300℃为止。接着，边以每0.1m3炉内容积为10L/分钟的比例流入Ar，边将炉内温度以1300℃保持3小时。其后，通过自然冷却而得到氧化物烧结体。
针对所得氧化物烧结体，与实施例1同样操作，评价组成和相对密度。将结果示于表6。
Figure 26420DEST_PATH_IMAGE005
Figure 645620DEST_PATH_IMAGE006
图4中示出XRD谱图的分析结果。由图4可确认：在氧化物烧结体中，作为晶体结构，包含ZnO（六方晶）、MgO（立方晶）、MgGa2O4和Ga2O3（ZnO）6。需要说明的是，关于Ga2O3（ZnO）6，因拟合率差而推测其存在。
根据晶格常数的实测值和PDF值，针对固溶有Zn的MgO（立方晶）、固溶有Mg的ZnO（六方晶）和固溶有Zn的MgX2O4（X＝Ga或Al）的存在进行评价。
关于MgO的晶格常数a，实测值为4.2307，PDF值为4.217。关于ZnO的晶格常数a，实测值为3.2482，PDF值为3.242。关于MgGa2O4的晶格常数a，实测值为8.3121，PDF值为8.26。像这样，由于晶格常数发生变化，因此，判断ZnO中固溶有Mg，此外，MgO和MgGa2O4中固溶有Zn。
将结果示于表7。表中，包含时记作○，不含时记作×。
Figure 912654DEST_PATH_IMAGE007
（B）溅射靶的制作
除了使用实施例7的氧化物烧结体之外，与实施例1同样操作，制作溅射靶，并进行评价。将结果示于表8。
Figure 642712DEST_PATH_IMAGE008
实施例8~13、比较例2
以各金属元素的原子比成为表5所示值的方式称量原料，并进行混合，除此之外，与实施例7同样操作，制作氧化物烧结体和溅射靶，并进行评价。将结果示于表6~8。需要说明的是，金属元素X为Al的实施例中，使用平均粒径为1μm以下的氧化铝（Al2O3粉末）。
图5中示出实施例8的氧化物烧结体的XRD谱图的分析结果。图6中示出比较例2的氧化物烧结体的XRD谱图的分析结果。
综上所述，对本发明的几个实施方式和/或实施例进行了详细说明，但本领域技术人员容易实质上不偏离本发明的新教导和效果地对这些例示的实施方式和/或实施例施加多种变更。因此，这些多种变更包括在本发明的范围内。
将该说明书记载的文献和成为本申请的基于巴黎公约的优先权基础的申请的内容全部引用。

Claims (20)

1.氧化物烧结体，其包含锌、镁、金属元素X和氧作为构成元素，所述金属元素X为正3价或正4价，
所述金属元素X相对于所述锌、所述镁和所述金属元素X的合计的原子比[X/（Zn+Mg+X）]为0.0001以上且0.6以下，
所述镁相对于所述锌和所述镁的合计的原子比[Mg/（Zn+Mg）]为0.25以上且0.8以下。
2.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.625以上且0.8以下。
3.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.626以上且0.75以下。
4.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.628以上且0.74以下。
5.根据权利要求2~4中任一项所述的氧化物烧结体，其包含固溶有Zn的立方晶的MgO和固溶有Zn的MgX2O4，其中，X为正3价的金属元素。
6.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.25以上且小于0.625。
7.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.30以上且0.60以下。
8.根据权利要求1所述的氧化物烧结体，其中，所述原子比[Mg/（Zn+Mg）]为0.40以上且0.59以下。
9.根据权利要求6~8中任一项所述的氧化物烧结体，其包含固溶有Zn的立方晶的MgO、固溶有Mg的六方晶的ZnO和固溶有Zn的MgX2O4，此处，X为正3价的金属元素。
10.根据权利要求1~9中任一项所述的氧化物烧结体，其中，所述原子比[X/（Zn+Mg+X）]为0.003以上且0.6以下。
11.根据权利要求1~9中任一项所述的氧化物烧结体，其中，所述原子比[X/（Zn+Mg+X）]为0.007以上且0.5以下。
12.根据权利要求1~9中任一项所述的氧化物烧结体，其中，所述原子比[X/（Zn+Mg+X）]为0.008以上且0.5以下。
13.根据权利要求1~9中任一项所述的氧化物烧结体，其中，所述原子比[X/（Zn+Mg+X）]为0.01以上且0.5以下。
14.根据权利要求1~13中任一项所述的氧化物烧结体，其中，所述X为Al和Ga中的至少一者。
15.根据权利要求14所述的氧化物烧结体，其中，所述X为Al。
16.根据权利要求14所述的氧化物烧结体，其中，所述X为Ga。
17.成膜用材料，其包含权利要求1~16中任一项所述的氧化物烧结体。
18.根据权利要求17所述的成膜用材料，其为成膜用平板。
19.根据权利要求17所述的成膜用材料，其为溅射靶。
20.薄膜，其是使用权利要求17~19中任一项所述的成膜用材料而得到的。
CN202080046931.9A 2019-06-27 2020-06-24 氧化物烧结体 Active CN114008000B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410029992.4A CN117819960A (zh) 2019-06-27 2020-06-24 氧化物烧结体

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2019-120056 2019-06-27
JP2019120057 2019-06-27
JP2019-120057 2019-06-27
JP2019120056 2019-06-27
PCT/JP2020/024740 WO2020262433A1 (ja) 2019-06-27 2020-06-24 酸化物焼結体

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN202410029992.4A Division CN117819960A (zh) 2019-06-27 2020-06-24 氧化物烧结体

Publications (2)

Publication Number Publication Date
CN114008000A true CN114008000A (zh) 2022-02-01
CN114008000B CN114008000B (zh) 2024-01-12

Family

ID=74060188

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202410029992.4A Pending CN117819960A (zh) 2019-06-27 2020-06-24 氧化物烧结体
CN202080046931.9A Active CN114008000B (zh) 2019-06-27 2020-06-24 氧化物烧结体

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202410029992.4A Pending CN117819960A (zh) 2019-06-27 2020-06-24 氧化物烧结体

Country Status (7)

Country Link
US (1) US20220356118A1 (zh)
EP (1) EP3992168A4 (zh)
JP (1) JPWO2020262433A1 (zh)
KR (1) KR20220023824A (zh)
CN (2) CN117819960A (zh)
TW (1) TW202106655A (zh)
WO (1) WO2020262433A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387684A (zh) * 2021-07-15 2021-09-14 中国科学院兰州化学物理研究所 一种具有良好红外辐射性能高熵氧化物的制备方法
WO2023189535A1 (ja) * 2022-03-30 2023-10-05 出光興産株式会社 酸化物焼結体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460425A (zh) * 2006-06-08 2009-06-17 住友金属矿山株式会社 氧化物烧结体、靶、用它制得的透明导电膜以及透明导电性基材
JP2012031491A (ja) * 2010-08-02 2012-02-16 Mitsubishi Materials Corp 透明導電膜用スパッタリングターゲットおよびその製造方法
CN102482156A (zh) * 2009-09-30 2012-05-30 出光兴产株式会社 In-Ga-Zn-O系氧化物烧结体
CN102666910A (zh) * 2009-12-16 2012-09-12 三菱综合材料株式会社 透明导电膜、利用该透明导电膜的太阳能电池及用于形成透明导电膜的溅射靶以及其制造方法
CN103518003A (zh) * 2011-05-10 2014-01-15 出光兴产株式会社 In2O3－ZnO系溅射靶
CN103748055A (zh) * 2012-07-09 2014-04-23 吉坤日矿日石金属株式会社 导电性氧化物烧结体及其制造方法
CN105008579A (zh) * 2013-02-18 2015-10-28 贺利氏德国有限及两合公司 ZnO-Al2O3-MgO溅射靶及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009184898A (ja) 2008-02-08 2009-08-20 Sumitomo Electric Ind Ltd 透光性セラミックス
JP2010024107A (ja) * 2008-07-22 2010-02-04 Sumitomo Electric Ind Ltd 透光性セラミックス
JP5418105B2 (ja) 2009-09-18 2014-02-19 東ソー株式会社 複合酸化物焼結体、酸化物透明導電膜、及びその製造方法
JP2012066968A (ja) 2010-09-24 2012-04-05 Kobelco Kaken:Kk 酸化物焼結体およびスパッタリングターゲット
KR20210075980A (ko) * 2018-09-26 2021-06-23 이데미쓰 고산 가부시키가이샤 산화물 적층체 및 그의 제조 방법
EP3875443A4 (en) * 2018-10-31 2022-08-03 Idemitsu Kosan Co., Ltd. SINTERED BODY

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460425A (zh) * 2006-06-08 2009-06-17 住友金属矿山株式会社 氧化物烧结体、靶、用它制得的透明导电膜以及透明导电性基材
CN102482156A (zh) * 2009-09-30 2012-05-30 出光兴产株式会社 In-Ga-Zn-O系氧化物烧结体
CN102666910A (zh) * 2009-12-16 2012-09-12 三菱综合材料株式会社 透明导电膜、利用该透明导电膜的太阳能电池及用于形成透明导电膜的溅射靶以及其制造方法
JP2012031491A (ja) * 2010-08-02 2012-02-16 Mitsubishi Materials Corp 透明導電膜用スパッタリングターゲットおよびその製造方法
CN103518003A (zh) * 2011-05-10 2014-01-15 出光兴产株式会社 In2O3－ZnO系溅射靶
CN103748055A (zh) * 2012-07-09 2014-04-23 吉坤日矿日石金属株式会社 导电性氧化物烧结体及其制造方法
CN105008579A (zh) * 2013-02-18 2015-10-28 贺利氏德国有限及两合公司 ZnO-Al2O3-MgO溅射靶及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
叶志镇等: "《氧化锌半导体材料掺杂技术与应用》", 31 January 2019, 浙江大学出版社 *

Also Published As

Publication number Publication date
KR20220023824A (ko) 2022-03-02
EP3992168A4 (en) 2023-08-02
CN117819960A (zh) 2024-04-05
TW202106655A (zh) 2021-02-16
US20220356118A1 (en) 2022-11-10
CN114008000B (zh) 2024-01-12
EP3992168A1 (en) 2022-05-04
JPWO2020262433A1 (zh) 2020-12-30
WO2020262433A1 (ja) 2020-12-30

Similar Documents

Publication Publication Date Title
TWI403602B (zh) In-Ga-Zn-based oxide sputtering target
US8858844B2 (en) In—Ga—Zn—O type sputtering target
WO2012017659A1 (ja) スパッタリングターゲットの製造方法およびスパッタリングターゲット
JP4891381B2 (ja) Ｉｎ−Ｇａ−Ｚｎ系焼結体、及びスパッタリングターゲット
CN114008000B (zh) 氧化物烧结体
TWI546273B (zh) In-Ga-Zn-based oxide sputtering target and a method for manufacturing the same
JP5381844B2 (ja) Ｉｎ−Ｇａ−Ｚｎ系複合酸化物焼結体およびその製造方法
CN112912355A (zh) 烧结体
CN114127029A (zh) 氧化物溅射靶
WO2023189535A1 (ja) 酸化物焼結体
JP7203088B2 (ja) 酸化物焼結体、スパッタリングターゲットおよび透明導電膜
JP6722736B2 (ja) 焼結体および、スパッタリングターゲット
CN109072417B (zh) 溅镀靶及其制造方法
JP2012017258A (ja) Ｉｎ−Ｇａ−Ｚｎ系酸化物スパッタリングターゲット
KR101056948B1 (ko) 알루미늄을 포함하는 비정질 산화물막용 금속산화물 타겟 및 그 제조방법
JP5526905B2 (ja) 導電性酸化物焼結体の製造方法
JP6551683B2 (ja) Ｓｎ−Ｚｎ−Ｏ系酸化物焼結体とその製造方法
JP2012056842A (ja) Ｉｎ−Ｇａ−Ｚｎ系酸化物、酸化物焼結体、及びスパッタリングターゲット

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant