WO2011102425A1 - Corps fritté à base d'oxydes, mélange d'oxydes, procédés de fabrication correspondant, et cibles les utilisant - Google Patents

Corps fritté à base d'oxydes, mélange d'oxydes, procédés de fabrication correspondant, et cibles les utilisant Download PDF

Info

Publication number
WO2011102425A1
WO2011102425A1 PCT/JP2011/053405 JP2011053405W WO2011102425A1 WO 2011102425 A1 WO2011102425 A1 WO 2011102425A1 JP 2011053405 W JP2011053405 W JP 2011053405W WO 2011102425 A1 WO2011102425 A1 WO 2011102425A1
Authority
WO
WIPO (PCT)
Prior art keywords
transparent conductive
oxide
resistance
titanium
zinc
Prior art date
Application number
PCT/JP2011/053405
Other languages
English (en)
Japanese (ja)
Inventor
邦彦 中田
岳 吉川
吉伸 中村
晶雄 鈴木
翔平 堀田
Original Assignee
住友化学株式会社
学校法人大阪産業大学
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
Priority claimed from JP2010268610A external-priority patent/JP2011190528A/ja
Application filed by 住友化学株式会社, 学校法人大阪産業大学 filed Critical 住友化学株式会社
Priority to CN2011800102349A priority Critical patent/CN102762518A/zh
Priority to KR1020127024066A priority patent/KR20120129972A/ko
Publication of WO2011102425A1 publication Critical patent/WO2011102425A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • 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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of metals or metal salts
    • 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
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • 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
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
    • C04B2235/30—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]
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • 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
    • C04B2235/652—Reduction treatment
    • 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
    • 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
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • 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
    • C04B2235/6582—Hydrogen containing atmosphere
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/407—Copper

Definitions

  • the present invention relates to an oxide sintered body, an oxide mixture, a production method thereof, and a target using them.
  • Transparent conductive films that combine electrical conductivity and light transmission have been used as electrodes in solar cells, liquid crystal display elements, and other various light receiving elements, as well as automotive windows, heat ray reflective films for buildings, and antistatic properties. It is used in a wide range of applications, such as transparent anti-fogging elements for anti-fogging in membranes and frozen showcases.
  • a transparent conductive film having a low resistance and excellent conductivity is suitable for a solar cell, a liquid crystal display element such as a liquid crystal, organic electroluminescence, and inorganic electroluminescence, a touch panel, and the like.
  • the transparent conductive film for example, a tin oxide (SnO 2 ) -based thin film, a zinc oxide (ZnO) -based thin film, and an indium oxide (In 2 O 3 ) -based thin film are known.
  • tin oxide-based transparent conductive film those containing antimony as a dopant (ATO) and those containing fluorine as a dopant (FTO) are known, and as a zinc oxide-based transparent conductive film, Those containing aluminum as a dopant (AZO) and those containing gallium as a dopant (GZO) are known, and indium oxide-based transparent conductive films include those containing tin as a dopant (ITO; Indium Tin Oxide). It has been. Among them, the most industrially used is an indium oxide-based transparent conductive film, and in particular, an ITO film is widely used because of its low resistance and excellent conductivity.
  • the target used as a film raw material in these film formation methods is made of a solid containing a metal element constituting the film to be formed, and is a sintered body or a mixture of metal, metal oxide, metal nitride, metal carbide, etc. Body, and in some cases, a single crystal.
  • the target when an oxide film such as ITO is formed by sputtering, the target is generally an alloy target made of a metal element constituting the film (In—Sn alloy in the case of an ITO film), Alternatively, an oxide target (a sintered body or a mixture made of In—Sn—O in the case of an ITO film) obtained by sintering or mixing an oxide containing a metal element constituting the film is used.
  • an alloy target when an alloy target is used, all the oxygen in the formed film is supplied from the oxygen gas in the atmosphere, so the amount of oxygen gas in the atmosphere tends to fluctuate, and as a result, the oxygen in the atmosphere It may be difficult to keep the film formation rate depending on the amount of gas and the characteristics (specific resistance, transmittance) of the film obtained constant.
  • oxide targets that is, oxide sintered bodies or oxide mixtures
  • an indium oxide-based transparent conductive film such as an ITO film is expensive and may be depleted of resources because In (indium), which is an essential raw material, is a rare metal, and has toxicity and is harmful to the environment and the human body.
  • In (indium) which is an essential raw material
  • ITO film has toxicity and is harmful to the environment and the human body.
  • an industrially versatile transparent conductive film that can be substituted for an ITO film because it may adversely affect the film.
  • a zinc oxide-based transparent conductive film that can be industrially manufactured by a sputtering method has attracted attention, and research is being conducted to improve its conductive performance.
  • Non-patent Document 1 attempts have been made to dope ZnO with various dopants in order to increase conductivity, and the optimum doping amount and the lowest resistivity have been reported for each of the various dopants.
  • the optimum doping amount is 2 wt%, and the minimum resistivity at that time is 5.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the zinc oxide-based transparent conductive film has been improved to obtain a low resistance comparable to that of the ITO film at the laboratory level.
  • conventional zinc oxide-based transparent conductive films are excellent in terms of conductivity, but have the disadvantage of being inferior in chemical durability such as heat resistance, moisture resistance, and chemical resistance (alkali resistance, acid resistance).
  • the zinc oxide-based transparent conductive film has poor chemical resistance (acid resistance and alkali resistance) as described above, it is necessary to pattern the zinc oxide-based transparent conductive film in a desired shape (for example, an element) In the case of use for such applications, there is a problem that an appropriate wet etching solution does not exist and patterning cannot be performed satisfactorily.
  • zinc oxide has a very high dissolution rate in acids and alkalis, etching with an acid or alkali on a zinc oxide-based transparent conductive film results in a very high etching rate. (Specifically, it is 100 times or more compared with the ITO film) and it immediately dissolved, and a good pattern shape could not be obtained.
  • the tin oxide-based transparent conductive film has excellent chemical resistance (acid resistance and alkali resistance) and is stable against acids and alkalis.
  • patterning by etching cannot be performed. Therefore, the zinc oxide-based transparent conductive film and the tin oxide-based transparent conductive film have a drawback that they can only be used for applications that do not require patterning. Therefore, as a means for enabling patterning of a zinc oxide-based thin film, it has been proposed that a specific acid can be used as an etchant and a specific element can be doped to reduce the etching rate (Patent Document 1). .
  • etching a zinc oxide-based thin film doped with 6 at% of Ti in ZnO (where “at%” is the number of atoms of the additive element with respect to the total number of atoms of zinc and the additive element of 100)
  • An example of etching a zinc oxide thin film doped with 3 at% Ti is disclosed.
  • Patent Document 2 describes that the durability of a zinc oxide-based transparent conductive film is improved by adding titanium oxide (TiO 2 ) having extremely strong durability to zinc oxide.
  • Patent Document 2 since the Ti element as the tetravalent element is substituted and dissolved in the site in the crystal of the zinc element, which is the divalent element, the charge balance is greatly lost, and the crystal structure is distorted. Since it is large and causes ionic impurity scattering, it is difficult to develop sufficient conductivity.
  • JP 2008-159814 A Japanese Patent No. 4295811
  • a first object of the present invention is to provide an oxide sintered body and an oxide mixture suitable for obtaining a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, and methods for producing the same. And a target using them.
  • the second object of the present invention is to provide a method for forming a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, a zinc oxide-based transparent conductive film formed by this method, and this film. It is to provide a transparent conductive substrate provided.
  • a third problem of the present invention is a zinc oxide thin film that has a sufficiently low etching rate at the time of patterning, can control the etching rate easily and reliably, has a good pattern shape, and has high conductivity. It is to provide a patterning method capable of obtaining the above.
  • the oxide sintered body of the present invention is substantially composed of zinc, titanium, and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium exceeds 0.02 and is 0.1 or less. It is.
  • the method for producing an oxide sintered body according to the present invention after molding a raw material powder containing the following (A) and / or (B), the obtained molded body is subjected to inert atmosphere, vacuum or reduction. This is a method of sintering at 600 ° C. to 1500 ° C. in an atmosphere.
  • the method for producing an oxide sintered body according to the present invention is as follows. After the raw material powder containing (A) and / or (B) is molded, the obtained molded body is sintered at 600 ° C. to 1500 ° C. in an air atmosphere or an oxidizing atmosphere, and then further vacuumed in an inert atmosphere. In this method, annealing is performed in a reducing atmosphere.
  • the oxide mixture of the present invention comprises zinc oxide and titanium oxide.
  • titanium with respect to the sum of zinc and titanium has an atomic ratio Ti / (Zn + Ti) of more than 0.02 and 0.1 or less.
  • the method for producing an oxide mixture according to the present invention is obtained by molding a raw material powder containing a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. In this method, the body is annealed at 50 ° C. or higher and lower than 600 ° C. in an air atmosphere, an inert atmosphere, a vacuum or a reducing atmosphere.
  • the target of the present invention is a target obtained by processing the oxide sintered body or the oxide mixture.
  • the method for forming a zinc oxide-based transparent conductive film according to the present invention comprises zinc oxide selected from the group consisting of a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, and an electron beam (EB) vapor deposition method.
  • a method of forming a transparent organic conductive film, which is substantially composed of zinc, titanium and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and not more than 0.1.
  • a target obtained by processing a certain oxide sintered body or oxide mixture is used.
  • the zinc oxide-based transparent conductive film of the present invention is a film formed by the method for forming the zinc oxide-based transparent conductive film.
  • the transparent conductive substrate of this invention is a board
  • the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1
  • the second target of the present invention is a target obtained by processing a zinc oxide-based transparent conductive film forming material.
  • the second method for forming a zinc oxide-based transparent conductive film according to the present invention is the sputtering method, ion plating method, pulse laser deposition method (PLD method) or electron beam (EB) vapor deposition using the second target.
  • PLD method pulse laser deposition method
  • EB electron beam
  • a zinc oxide-based transparent conductive film is formed by a method.
  • the transparent conductive substrate of this invention is a board
  • the patterning method according to the present invention is a method of patterning by etching a zinc oxide thin film with an acid, wherein the zinc oxide thin film contains zinc oxide as a main component, and the number of titanium atoms relative to the total of zinc and titanium.
  • the ratio Ti / (Zn + Ti) is a thin film having a ratio exceeding 0.02 and not more than 0.1.
  • a zinc oxide-based transparent conductive film having excellent conductivity and chemical durability can be formed by sputtering, ion plating, PLD, or EB vapor deposition.
  • the transparent conductive film formed in this manner is extremely useful industrially because it has the advantage that it does not require toxic indium, which is a rare metal.
  • a zinc oxide-based transparent conductive film having a good pattern shape and high conductivity can be obtained.
  • the oxide sintered body of the present invention is a titanium-doped zinc oxide sintered body substantially composed of zinc, titanium, and oxygen.
  • substantially means that 99% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, or oxygen.
  • the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less.
  • the value of Ti / (Zn + Ti) is 0.02 or less, chemical durability such as chemical resistance of a film formed using an oxide sintered body as a target is insufficient, and oxide sintering is performed. Since it becomes difficult for the zinc titanate compound to be formed in the body, the strength of the sintered body is reduced, making it difficult to process the target.
  • the value of Ti / (Zn + Ti) exceeds 0.1, there is a high possibility that a titanium oxide crystal phase that is desired not to be included in the oxide sintered body is formed as described later.
  • the oxide sintered body of the present invention is preferably composed of a zinc oxide phase and a zinc titanate compound phase, or composed of a zinc titanate compound phase.
  • the oxide titanate contains a zinc titanate compound phase in this way, the strength of the sintered body itself increases, so cracks occur. It is hard to produce.
  • the zinc titanate compound include ZnTiO 3 and Zn 2 TiO 4 , those in which a titanium element is dissolved in these zinc sites, those in which oxygen deficiency is introduced, and those having a Zn / Ti ratio. Non-stoichiometric compositions slightly deviating from the compound are also included.
  • examples of zinc oxide include ZnO, a solution in which a titanium element is dissolved, a material in which oxygen deficiency is introduced, and a material having a non-stoichiometric composition due to zinc deficiency.
  • the zinc oxide phase usually has a wurtzite structure.
  • the oxide sintered body of the present invention does not substantially contain a titanium oxide crystal phase.
  • the oxide sintered body contains a crystal phase of titanium oxide, the resulting film may lack uniformity in physical properties such as specific resistance.
  • titanium oxide since the value of Ti / (Zn + Ti) described above is 0.1 or less, titanium oxide usually reacts completely with zinc oxide, and titanium oxide is contained in the oxide sintered body. A crystalline phase is unlikely to occur. Examples of the crystalline phase of titanium oxide include TiO 2 , Ti 2 O 3 , and TiO, as well as substances in which other elements such as Zn are dissolved in these crystals.
  • the oxide sintered body of the present invention contains at least one element selected from the group consisting of gallium, aluminum, tin, silicon, germanium, zirconium and hafnium (hereinafter sometimes referred to as “additive element”), Furthermore, it is preferable to contain.
  • additive element the specific resistance of the oxide sintered body itself can be reduced in addition to the specific resistance of the film formed using the oxide sintered body as a target.
  • the film formation rate during DC sputtering depends on the specific resistance of the oxide sintered body as a sputtering target, and the productivity during film formation is improved by lowering the specific resistance of the oxide sintered body itself. Can do.
  • the total content is 0.05% or less with respect to the total amount of all the metal elements which comprise oxide sinter by atomic ratio. If the content of the additive element exceeds 0.05%, the specific resistance of the film formed using the oxide sintered body as a target may increase.
  • the additive element may be present in the oxide sintered body in the form of an oxide, or may be present in a form substituted (solid solution) in the zinc site of the zinc oxide phase, or titanic acid.
  • the zinc compound phase may exist in a form substituted (solid solution) with titanium sites and / or zinc sites.
  • the oxide sintered body of the present invention may contain other elements such as indium, iridium, ruthenium, rhenium as impurities in addition to the essential elements and additive elements of zinc and titanium.
  • the total content of elements contained as impurities is preferably 0.5% or less in terms of atomic ratio with respect to the total amount of all metal elements constituting the oxide sintered body.
  • the specific resistance of the oxide sintered body of the present invention is preferably 5 k ⁇ ⁇ cm or less.
  • the deposition rate during direct current sputtering depends on the specific resistance of the oxide sintered body as a sputtering target. Therefore, if the specific resistance of the oxide sintered body exceeds 5 k ⁇ ⁇ cm, the direct current sputtering is stable. There is a risk that film formation cannot be performed.
  • the specific resistance of the oxide sintered body of the present invention is preferably as low as possible. Specifically, it should be 100 ⁇ ⁇ cm or less.
  • the oxide sintered body of the present invention is preferably obtained by a method for producing an oxide sintered body according to the present invention described later, but is not limited to those obtained by these production methods.
  • a combination of titanium metal and zinc oxide powder or zinc hydroxide powder, or a combination of titanium oxide and zinc metal may be obtained as a raw material powder.
  • the method for producing an oxide sintered body according to the present invention includes forming the raw material powder containing the following (A) and / or (B), and then sintering the obtained molded body, This is a method for obtaining an oxide sintered body.
  • the raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder, a mixed powder of titanium oxide powder and zinc hydroxide powder, or a powder containing zinc titanate compound powder. It may be a mixed powder of zinc powder and zinc titanate compound powder or a mixed powder of titanium oxide powder, zinc hydroxide powder and zinc titanate compound powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder.
  • the oxide sintered body of the present invention is In that case, titanium or zinc metal particles are likely to be present in the oxide sintered body, and when this is used as a target, the metal particles on the surface of the target melt during the film formation. There is a tendency that the composition of the obtained film and the composition of the target are largely different without being released.
  • titanium oxide powder titanium oxide (TiO 2 ) made of tetravalent titanium, titanium oxide (Ti 2 O 3 ) made of trivalent titanium, titanium oxide (TiO) made of divalent titanium, or the like is used.
  • Ti 2 O 3 powder it is preferable to use Ti 2 O 3 powder. Because the crystal structure of Ti 2 O 3 is trigonal and the zinc oxide mixed with it has a hexagonal wurtzite structure, the symmetry of the crystal structure is the same, and it is replaced when solid-phase sintering is performed. It is because it can be considered that it dissolves easily.
  • the purity of the titanium oxide powder is preferably 99% by weight or more.
  • the ratio of the low-valent titanium oxide mixture can be controlled.
  • the structure of this low-valence titanium oxide can be confirmed by the results of instrumental analysis such as an X-ray diffraction apparatus (X-ray diffraction, XRD), an X-ray photoelectron spectrometer (X-ray Photoelectron Spectroscopy, XPS).
  • the zinc oxide powder a powder of ZnO or the like having a wurtzite structure is usually used, and a powder obtained by firing this ZnO in advance in a reducing atmosphere and containing oxygen deficiency may be used.
  • the purity of the zinc oxide powder is preferably 99% by weight or more.
  • the zinc hydroxide powder may be either amorphous or crystalline.
  • the zinc titanate compound powders of ZnTiO 3 , Zn 2 TiO 4 and the like can be used, and it is particularly preferable to use Zn 2 TiO 4 powder.
  • the average particle size of each compound (powder) used as the raw material powder is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the BET specific surface area of raw material powder is not specifically limited.
  • the mixing ratio of each powder is Ti / (Zn + Ti) in atomic ratio in the finally obtained oxide sintered body, depending on the type of compound (powder) used. What is necessary is just to set suitably so that a value may become said range. At that time, considering that zinc has a higher vapor pressure than titanium and is likely to be volatilized when sintered, the desired composition of the desired oxide sintered body (atomic ratio of Zn and Ti), It is preferable to set the mixing ratio in advance so that the amount of zinc increases.
  • the easiness of volatilization of zinc varies depending on the atmosphere during sintering.
  • the atmosphere during sintering For example, when zinc oxide powder is used, only the volatilization of zinc oxide powder itself occurs in an air atmosphere or an oxidizing atmosphere.
  • zinc oxide When sintered in a reducing atmosphere, zinc oxide is reduced, and it becomes easier to volatilize metal zinc than zinc oxide, so the amount of zinc lost increases (however, as described later, it is once sintered)
  • the amount of zinc to be increased with respect to the target composition may be set in consideration of the sintering atmosphere or the like.
  • each of the compounds (powder) used as the raw material powder may be only one kind, or two or more kinds may be used in combination.
  • the method for molding the raw material powder is not particularly limited, and for example, the raw material powder may be mixed and the obtained mixture may be molded.
  • the mixing can be performed using a known mixing method such as a ball mill, a vibration mill, an attritor, a dyno mill, or a dynamic mill.
  • the raw material powder and the aqueous solvent are mixed, and the obtained slurry is sufficiently mixed, then solid-liquid separated, dried and granulated, and the obtained granulated product may be formed.
  • the wet mixing may be performed by, for example, a wet ball mill using a hard ZrO 2 ball or a vibration mill, and the mixing time in the case of using a wet ball mill or a vibration mill is preferably about 12 to 78 hours.
  • raw material powder may be dry-mixed as it is, wet mixing is more preferable.
  • Known methods may be employed for solid-liquid separation, drying, and granulation.
  • the obtained granulated product is molded, for example, the granulated product is put into a mold and 1 ton using a cold forming machine such as a cold press or a cold isostatic press (CIP), a uniaxial press or the like. It can be formed by applying a pressure of / cm 2 or more.
  • a cold forming machine such as a cold press or a cold isostatic press (CIP), a uniaxial press or the like. It can be formed by applying a pressure of / cm 2 or more.
  • Sintering of the obtained compact is performed in an inert atmosphere (nitrogen, argon, helium, neon, etc.), vacuum, reducing atmosphere (carbon dioxide, hydrogen, ammonia, etc.), air atmosphere and oxidizing atmosphere (oxygen concentration is higher than air). High atmosphere) at 600 ° C. to 1500 ° C.
  • an annealing treatment in an inert atmosphere, a vacuum, or a reducing atmosphere applied after sintering in an air atmosphere or an oxidizing atmosphere causes oxygen deficiency in the oxide sintered body and lowers the specific resistance. To do. Therefore, even if sintering is performed in an inert atmosphere, a vacuum, or a reducing atmosphere, if it is desired to further reduce the specific resistance, it is preferable to perform annealing after the sintering.
  • the sintering temperature is preferably 600 ° C. to 1700 ° C., more preferably 600 ° C. to 1500 ° C., further preferably 1000 ° C. to 1500 ° C., and most preferably 1000 ° C. to 1300 ° C. And If the sintering temperature is lower than 600 ° C., the sintering does not proceed sufficiently, so that the target density is lowered. On the other hand, if it exceeds 1500 ° C., zinc oxide itself decomposes and disappears.
  • the rate of temperature increase is 5 ° C./min to 10 ° C./min up to 1000 ° C., and 1 ° C./min to 4 ° C. over 1000 ° C. to 1500 ° C. / Min is preferable in terms of making the sintered density uniform.
  • Sintering is performed, for example, by preventing the decomposition in a state where the molded body is buried in the ZnO powder, whereby the density of the obtained sintered body is preferably 80% or more, more preferably 90%. It is preferable to do.
  • a target composed of a high-density sintered body is preferable for reducing fine particles in the ablation plume, which may cause deterioration in film quality, that is, crystallinity and surface morphology, particularly in the case of the fs-PLD method. .
  • the sintering time (that is, the holding time at the sintering temperature) is preferably 0.5 to 48 hours, more preferably 3 to 15 hours.
  • Sintering is not particularly limited, and may be performed using an electric furnace, a gas furnace, a reduction furnace, or the like. Atmospheric pressure firing method, hot press method, hot isobaric press (HIP) method, discharge plasma Known methods such as a sintering (SPS) method and a cold isostatic pressing (CIP) method can be employed.
  • SPS sintering
  • CIP cold isostatic pressing
  • Examples of the atmosphere in performing the annealing treatment include an atmosphere made of at least one selected from the group consisting of nitrogen, argon, helium, carbon dioxide and hydrogen, and a vacuum.
  • a method of annealing treatment for example, a method of heating at normal pressure while introducing a non-oxidizing gas such as nitrogen, argon, helium, carbon dioxide, hydrogen, or a method of heating under vacuum (preferably 2 Pa or less)
  • the former method is advantageous from the viewpoint of production cost.
  • the annealing temperature is preferably 1000 ° C. to 1400 ° C., more preferably 1100 ° C. to 1300 ° C.
  • the annealing time is preferably 7 hours to 15 hours, more preferably 8 hours to 12 hours. If the annealing temperature is less than 1000 ° C., introduction of oxygen vacancies by annealing may be insufficient. On the other hand, when it exceeds 1400 ° C., zinc is likely to be volatilized, and the composition of the obtained oxide sintered body (atom ratio of Zn and Ti) may be different from a desired ratio.
  • the oxide mixture of the present invention comprises zinc oxide and titanium oxide. That is, the oxide mixture of the present invention is a mixture substantially consisting of zinc, titanium and oxygen. Here, “substantially” means that 99% or more of all atoms constituting the oxide mixture are composed of zinc, titanium, or oxygen.
  • the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less.
  • the above-described titanium oxide powder can be used.
  • Zinc oxide usually has a wurtzite structure.
  • the oxide mixture of the present invention is obtained by mixing zinc oxide powder and titanium oxide powder and molding the mixture, for example, uniaxial press molding. In order to increase the mechanical strength of the oxide mixture, the shaped oxide mixture may be heated below 600 ° C. If zinc oxide and titanium oxide are less than 600 ° C., they are not sintered to produce a composite oxide or the like.
  • Titanium (III) oxide is oxidized in an atmosphere containing oxygen (air atmosphere and oxidizing atmosphere) and heated to 400 ° C. or higher to change to titanium (IV) oxide.
  • the heating temperature is less than 600 ° C. in a reducing atmosphere and an inert atmosphere in which oxygen is not present, it can exist as a mixture without sintering.
  • the atmosphere contains oxygen (oxidizing atmosphere and air atmosphere), it is preferable to heat at less than 400 ° C. By heating in this way, the mechanical strength of the oxide mixture can be increased. Since the strength of the mixture itself increases, for example, even if a film is formed under severe conditions (high power, etc.) as a target, cracks are hardly generated.
  • the oxide mixture of the present invention may contain the above-described additive elements and impurities.
  • the contents of additive elements and impurities are as described above.
  • the method for producing the oxide mixture of the present invention comprises forming the mixed powder of titanium oxide powder and zinc oxide powder or the mixed powder of titanium oxide powder and zinc hydroxide powder, thereby forming the oxide mixture of the present invention. Is the way to get.
  • the raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder.
  • these titanium oxide powder, zinc oxide powder and zinc hydroxide powder those similar to the above-mentioned oxide sintered body can be used.
  • the mixing ratio of each powder depends on the type of compound (powder) used, What is necessary is just to set suitably so that the value of Ti / (Zn + Ti) may become the above-mentioned range by atomic ratio in the oxide mixture finally obtained.
  • the method for forming the raw material powder is not particularly limited, and is performed, for example, by the same method as that for the oxide sintered body.
  • the obtained molded body is heated and annealed to increase the mechanical strength.
  • Annealing is performed by a known method such as an atmospheric annealing method, a hot press method, an HIP method, an SPS method, or a CIP method.
  • an atmosphere for example, nitrogen, argon, helium, carbon dioxide, vacuum (preferably 2 Pa or less), hydrogen, etc.
  • an air atmosphere such as an air atmosphere, an inert atmosphere, a vacuum, a reducing atmosphere, or an oxidizing atmosphere (oxygen concentration higher than air) (Atmosphere) is performed at 50 ° C or higher and lower than 600 ° C.
  • an oxidizing atmosphere oxygen concentration higher than air
  • annealing is advantageously performed at normal pressure.
  • the annealing time (that is, the holding time at the annealing temperature) is preferably 1 hour to 15 hours. If the annealing time is less than 1 hour, the mechanical strength is not sufficiently improved.
  • the target of the present invention is a target used for film formation by, for example, a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, or an electron beam (EB) evaporation method.
  • PLD method pulse laser deposition method
  • sputtering method a sputtering method
  • ion plating method a ion plating method
  • EB electron beam
  • the solid material used at the time of such film-forming may be called a "tablet”, in this invention, these are described as a "target.”
  • a general film forming method such as another vacuum film forming method such as a vacuum vapor deposition method, a chemical vapor deposition method, a mist CVD method, or a sol-gel method.
  • the target of the present invention is obtained by processing the above-described oxide sintered body or oxide mixture of the present invention into a predetermined shape and predetermined dimensions.
  • a processing method in particular is not restrict
  • the surface of the oxide sintered body or the oxide mixture is subjected to surface grinding and the like, then cut to a predetermined size, and then attached to a support base, whereby the target of the present invention can be obtained.
  • a plurality of oxide sintered bodies or oxide mixtures may be divided into divided shapes to form a large area target (composite target).
  • PLD method Pulse laser deposition method
  • the PLD method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described target (film forming material) is used, and known methods and conditions may be appropriately employed.
  • PLD method is demonstrated, it is not limited to these.
  • a pulse laser beam is focused on a film forming material such as a target, and the film forming material (a mixture of titanium oxide and zinc oxide) on the surface of the target is obtained by the high power density of the focused laser pulse.
  • the film forming material a mixture of titanium oxide and zinc oxide
  • both the target and the substrate are installed in a high vacuum chamber, and their operations are controlled by a feedthrough mechanism.
  • the most widely used pulse laser source in the PLD method is an excimer laser.
  • the excimer laser has a pulse width of several nanoseconds (ns) and a wavelength in the UV region. Its typical fluence (energy range density) is a few J / cm 2 for a typical 10 mm 2 focused spot.
  • the nanosecond laser PLD method generates large droplets having a size of several microns, and is not suitable for a wide range of industrial nanosecond PLDs. Therefore, it is preferable to use a femtosecond laser or a similar ultrashort pulse laser as an ablation energy source (pulse laser source) used in the PLD method.
  • femtosecond to picosecond laser pulses have a much higher peak power due to their ultrashort pulse width, and the ablation mechanism is essentially that of nanosecond laser ablation.
  • the basic difference is that during the femtosecond pulse width, only negligible heat conduction occurs inside the target, so ablation basically occurs in an unmelted situation. Therefore, it is preferable to use the femtosecond PLD method (fs-PLD method) because a thin film in which no droplet is generated can be obtained.
  • the pulse width of the laser beam of the femtosecond pulse laser to be used is usually 10 fs to 1 ps, and the pulse energy is usually 2 ⁇ J to 100 mJ.
  • the beam is magnified 10 times with a microscope, and then condensed on the target surface with a condenser lens. By condensing this small, the fluence (energy density) at the focused spot can be changed to a maximum of 250 J / cm 2 with a spot size of 400 ⁇ m 2 .
  • the ablation threshold of the film-forming material (Ti-containing ZnO) when using a femtosecond laser is the case for a nanosecond pulse laser Is relatively low.
  • a fluence higher than 1 J / cm 2 is sufficient to ablate the Ti-containing ZnO target and generate ablation plasma.
  • a high fluence of up to 5 J / cm 2 is preferred to reduce the number of particles in the plasma plume.
  • a transparent thin film can be deposited by pulse laser on a simple substrate, or a multilayer periodic structure can be deposited directly.
  • a pulse laser is incident from the back surface of the substrate and is focused on the target through the substrate, the film forming material ablated from the target adheres to the surface of the substrate facing the target.
  • the distance from the substrate to the target can be changed by translating the substrate relative to the target. If the substrate is away from the target, a large area thin film can be formed.
  • a fine pattern with the same size as the laser focused spot is formed on the substrate due to the short distance between the substrate and the target and the narrow angular distribution of the ablation plume at the base. can do.
  • a pattern structure for example, periodic lines, lattices, dots
  • a multilayer periodic dielectric structure can be deposited by alternately performing two deposition processes using different materials at each of a long distance and a short distance between the substrate and the target.
  • the substrate is mounted on a substrate heater that can be heated up to 900 ° C.
  • the substrate manipulator then applies lateral and rotational motion to the surface of the substrate, and the substrate manipulator can be used to adjust the distance between the substrate and the target.
  • the vacuum system is operated at a base pressure of 1.5 ⁇ 10 ⁇ 8 Torr by being evacuated by a turbo molecular pump.
  • different gases can be filled into the chamber from the inlet and outlet, for example, the chamber can be filled with 0.1-20 milliTorr of oxygen.
  • Laser ablation occurs when a laser beam is focused on the target surface.
  • the laser focused spot is fixed, while the disk-type target is rotated around its surface vertical axis to perform lateral translation back and forth along its surface. Do. This corresponds to scanning the laser beam across the target surface.
  • the angular velocity of rotation is usually about 1 rev / sec.
  • the translational velocity in the lateral direction is usually about 0.3 mm / second, and the fluence is usually about 20 J / cm ⁇ 2 .
  • the pulse repetition frequency is kept at 1 kHz.
  • the substrate Before condensing the laser beam on the target surface, the substrate is heated to a maximum of 600 ° C. to release the gas, and then the substrate is treated with oxygen plasma for about 5 minutes to carbonize the substrate. It is preferable to remove the contamination due to hydrogen.
  • pre-ablation pre-ablation
  • the purpose of pre-ablation is to clean the target surface that is dirty during the manufacturing process. During pre-ablation, a shutter is inserted between the target and the substrate to protect the substrate surface.
  • a sputtering method may be employed as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described film forming materials are used, and a known sputtering method and conditions may be appropriately employed.
  • Film formation by sputtering is performed, for example, by placing a target in a sputtering apparatus, introducing a sputtering gas into the apparatus, and applying a direct current (dc) or a high frequency (rf) electric field or performing sputtering.
  • dc direct current
  • rf high frequency
  • an inert gas for example, Ar
  • an oxidizing gas or a reducing gas can be used in combination.
  • oxygen it is preferable not to contain oxygen qualitatively, and the oxygen concentration is preferably less than 0.05%, for example.
  • the film formation conditions by the sputtering method are not particularly limited.
  • the pressure is usually 0.1 to 10 Pa
  • the substrate temperature is usually 25 to 300 ° C.
  • the method of sputtering is not particularly limited.
  • the sputtering method direct current sputtering method
  • the RF sputtering method high frequency sputtering method
  • the AC sputtering method alternating current sputtering method
  • the DC sputtering method has an advantage that the film forming speed is higher than other methods, the sputtering efficiency is excellent, and the DC sputtering apparatus is inexpensive, easy to control, and consumes less power.
  • these methods cannot be employed when the target is an insulator.
  • the RF sputtering method can be used even if the target is an insulator.
  • an ion plating method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • a film forming material evaporation material
  • the evaporation material is heated by irradiating, for example, argon plasma to the evaporation material.
  • argon plasma argon plasma
  • each particle of the vapor deposition material that has passed through the plasma is formed on a substrate placed at a position facing the hearth or the like.
  • the specific method and conditions of the ion plating method are not particularly limited except that the film forming material described above is used, and a known method and conditions of the ion plating method may be appropriately employed.
  • FIG. 1 shows an example of an ion plating apparatus suitable for performing the ion plating method.
  • the ion plating apparatus 10 includes a vacuum vessel 12 that is a film forming chamber, a plasma gun (plasma beam generator) 14 that is a plasma source that supplies a plasma beam PB into the vacuum vessel 12, and a bottom portion in the vacuum vessel 12.
  • An anode member 16 that is disposed and on which the plasma beam PB is incident is provided, and a transport mechanism 18 that appropriately moves a substrate holding member WH that holds a substrate W to be deposited above the anode member 16.
  • the plasma gun 14 is a pressure gradient type, and its main body is provided on the side wall of the vacuum vessel 12.
  • Reference numeral 20a indicates a carrier gas introduction path made of an inert gas such as Ar, which is the source of the plasma beam PB.
  • the anode member 16 includes a hearth 16a as a main anode for guiding the plasma beam PB downward, and an annular auxiliary anode 16b disposed around the hearth 16a.
  • the hearth 16a is controlled to an appropriate positive potential and sucks the plasma beam PB emitted from the plasma gun 14 downward.
  • a through hole TH is formed at a central portion where the plasma beam PB is incident, and a vapor deposition material 22 is loaded in the through hole TH.
  • the vapor deposition material 22 is a tablet formed into a columnar shape or a rod shape, and is heated and sublimated by an electric current from the plasma beam PB to generate a vapor deposition material.
  • the hearth 16a has a structure for gradually raising the vapor deposition material 22, and the upper end of the vapor deposition material 22 always protrudes from the through hole TH of the hearth 16a by a certain amount.
  • the auxiliary anode 16b is composed of an annular container arranged concentrically around the hearth 16a, and a permanent magnet 24a and a coil 24b are accommodated in the container.
  • the permanent magnet 24a and the coil 24b are magnetic field control members, and form a cusp-like magnetic field directly above the hearth 16a, whereby the direction of the plasma beam PB incident on the hearth 16a is controlled and corrected.
  • the transport mechanism 18 has a large number of rollers 18b arranged in the transport path 18a at equal intervals in the horizontal direction to support the substrate holding member WH, and rotates the rollers 18b to move the substrate holding member WH horizontally at a predetermined speed. And a drive device (not shown) to be moved.
  • the substrate W is held by the substrate holding member WH.
  • the substrate W may be fixedly disposed above the inside of the vacuum vessel 12 without providing the transport mechanism 18 for transporting the substrate W.
  • Reference numeral 20b indicates a supply path for supplying an atmospheric gas other than oxygen
  • reference numeral 20c indicates a supply path for supplying an inert gas such as Ar to the hearth 16a.
  • Reference numeral 20d denotes an exhaust system.
  • the vapor deposition material 22 is attached to the through hole TH of the hearth 16a disposed at the lower part of the vacuum vessel 12.
  • the substrate W is disposed at an opposing position above the hearth 16a.
  • a process gas corresponding to the film forming conditions is introduced into the vacuum vessel 12.
  • a DC voltage is applied between the cathode 14a of the plasma gun 14 and the hearth 16a.
  • a discharge is generated between the cathode 14a of the plasma gun 14 and the hearth 16a, thereby generating a plasma beam PB.
  • the plasma beam PB reaches the hearth 16a by being guided by a magnetic field determined by the steering coil 14 and the permanent magnet 24a in the auxiliary anode 16b. At this time, since argon gas is supplied around the steamed material 22, the plasma beam PB is easily attracted to the hearth 16a.
  • the vapor deposition material 22 exposed to the plasma is gradually heated.
  • the vapor deposition material 22 sublimates and the vapor deposition material evaporates (emits).
  • the vapor deposition material is ionized by the plasma beam PB, adheres (incides) to the substrate W, and is formed into a film.
  • the flight direction of the vapor deposition material can be controlled by controlling the magnetic field above the hearth 16a by the permanent magnet 24a and the coil 24b, the plasma activity distribution and the reactivity of the substrate W above the hearth 16a.
  • the film formation speed distribution on the substrate W can be adjusted in accordance with the distribution, and a thin film having a uniform film quality can be obtained over a wide area.
  • An electron beam (EB) vapor deposition method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described film forming material is used, and a known electron beam (EB) vapor deposition method and conditions may be appropriately employed.
  • EB electron beam
  • a raw material target (tablet) is heated and evaporated by irradiating an electron beam in a vacuum, and this is deposited on an opposing transparent substrate for vapor deposition. Can be made on top.
  • the zinc oxide-based transparent conductive film of the present invention is a transparent conductive film made of titanium-doped zinc oxide formed by the above-described method for forming a zinc oxide-based transparent conductive film.
  • the atomic ratio (Ti / (Zn + Ti)) of titanium and zinc contained in the zinc oxide-based transparent conductive film of the present invention is as described above. As a result, the film can exhibit excellent conductivity due to the doping effect of titanium, and has excellent chemical durability.
  • titanium is substituted and dissolved in zinc sites of a zinc oxide wurtzite crystal structure.
  • the film thickness of the zinc oxide-based transparent conductive film of the present invention may be appropriately set according to the application, and is not particularly limited, but is preferably 50 nm to 600 nm, more preferably 100 nm to 500 nm. If the thickness is less than 50 nm, sufficient specific resistance may not be ensured. On the other hand, if the thickness exceeds 600 nm, the film may be colored.
  • the transparent conductive substrate of the present invention comprises the above-described zinc oxide-based transparent conductive film on a transparent base material.
  • the transparent substrate is not particularly limited as long as it can maintain the shape in various film forming methods.
  • inorganic materials such as various glasses, thermoplastic resins and thermosetting resins (for example, epoxy resin, polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, polyolefin, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose)
  • a plate-like material, a sheet-like material, a film-like material or the like formed of a resin such as a plastic such as polyimide can be used, and a glass plate, a resin film, or a resin sheet is particularly preferable.
  • the visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more.
  • the roll-to-roll film formation method used in the industry is used. It is preferable to form a film in a state where a tensile stress is applied while being controlled. Further, the resin film or the resin sheet may be formed in a heated state in advance, or the resin film or the resin sheet may be cooled during the film formation. It is also effective to increase the speed of transporting the resin film or resin sheet (for example, at 1.0 m / min or more) in order to reduce the time for damage during film formation. Film formation is possible even if the distance between the target resin film or resin sheet and the target is short, which is advantageous as an industrial process.
  • the transparent base material may be formed with any of a single layer or multiple layers of an insulating layer, a semiconductor layer, a gas barrier layer, or a protective layer as required.
  • the insulating layer include a silicon oxide film and a silicon nitride oxide film.
  • the semiconductor layer include a thin film transistor (TFT), and the semiconductor layer is mainly formed on a glass substrate.
  • the gas barrier layer include a silicon oxide film, a silicon nitride oxide film, and a magnesium aluminate film, and the gas barrier layer is formed on a resin plate or a resin film as a water vapor barrier film.
  • a protective layer is for protecting the surface of a base material from a damage
  • one layer or two or more layers of inorganic compounds can be stacked.
  • the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1, and the main component is zinc oxide. It consists of an oxide mixture or oxide sintered body containing at least one oxide of gallium and aluminum and titanium oxide.
  • the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms.
  • the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient.
  • gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, resulting in a decrease in conductivity and a decrease in transmittance.
  • Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 0.5% or more and 6% or less in the total amount thereof.
  • the oxide mixture or oxide sintered body As the manufacturing method of the oxide mixture or oxide sintered body here, the oxide mixture or oxidation described above is used except that a mixed powder further added with aluminum oxide powder or gallium oxide powder is used as the raw material powder. This is the same as the manufacturing method of the sintered product.
  • the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms.
  • the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient.
  • gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, leading to a decrease in conductivity and a decrease in transmittance.
  • Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 1% or more and 6% or less in the total amount thereof.
  • the oxide mixture and oxide sintered body are prepared by mixing zinc oxide powder, titanium oxide powder and aluminum oxide powder, or mixing zinc oxide powder, titanium oxide powder and gallium oxide powder, and press-molding. Is.
  • the titanium oxide powder is as described above, and trivalent titanium oxide (III) or divalent titanium oxide (II) is preferable.
  • the crystal phase of titanium oxide is specifically Ti 2 O 3 (III) and TiO (II).
  • the zinc oxide-based transparent conductive film-forming material of the present invention may contain the above-described additive elements (however, excluding gallium and aluminum) and impurities.
  • the contents of additive elements and impurities are as described above.
  • the specific resistance of the formed transparent conductive film is reduced, and the conductivity can be improved.
  • the content of the additive element exceeds 0.05%, the specific resistance of a film formed from the obtained zinc oxide-based transparent conductive film forming material may increase.
  • the additive element may be present in the oxide mixture or oxide sintered body in the form of an oxide, or is present in the form substituted (solid solution) in the zinc site of the zinc oxide phase. Alternatively, it may be present in a form substituted (solid solution) in the titanium site of the titanium oxide phase.
  • the oxide sintered body constituting the zinc oxide-based transparent conductive film forming material of the present invention preferably has a relative density of 93% or more, more preferably 95% to 100%.
  • the relative density is defined as the density of the oxide sintered body divided by the theoretical density and multiplied by 100. If the relative density is less than 93%, the characteristic of the sintered body, that is, the high film formation rate may be impaired.
  • the oxide mixture and the oxide sintered body are not particularly limited, and are manufactured by the above-described method, for example.
  • the zinc oxide-based transparent conductive film forming material of the present invention is processed into a target used for film formation by, for example, sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) evaporation.
  • a zinc oxide-based transparent conductive film is formed using the processed target, and a transparent conductive substrate is obtained by forming the conductive film on the transparent substrate.
  • the zinc oxide thin film as described above is etched with an acid.
  • the etching solution that can be used in the present invention is not particularly limited as long as it contains an acid.
  • an etching solution used for patterning a conventional transparent conductive film such as an ITO film can be used.
  • the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrohalic acid (such as hydroiodic acid and hydrobromic acid), and mixtures thereof (such as aqua regia), Examples include organic acids such as oxalic acid, acetic acid, formic acid, propionic acid, succinic acid, malonic acid, butyric acid, citric acid.
  • Etching solutions containing these are usually used as (water) solutions dissolved in a suitable solvent.
  • the acid itself may be used.
  • various salts such as ammonium sulfate and ferric chloride can be dissolved in the etching solution. Only 1 type may be used for etching liquid and it may use 2 or more types together.
  • the concentration of the etching solution is not particularly limited, and may be set as appropriate according to the liquid temperature of the etching solution, the curing level of the film, and the like so as to obtain a desired etching rate.
  • the temperature of the etching solution is preferably 10 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C. If the temperature of the etching solution is less than 10 ° C., etching may not be possible. On the other hand, if the temperature exceeds 150 ° C., a solvent such as water tends to volatilize and it may be difficult to control the concentration of the etching solution. .
  • etching solution there is no particular limitation on the processing method when performing etching using the etching solution.
  • an appropriate solvent for example, methyl cellosolve acetate
  • the specific method and conditions for forming and removing the resist film and removing the exposed portion with the etching solution For example, in a wet etching process applied to a conventional transparent conductive film such as an ITO film. What is necessary is just to carry out suitably according to a method and conditions.
  • the thin film patterned according to the present invention has high conductivity.
  • the transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent substrate has a specific resistance. Usually, it is 2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, preferably 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, more preferably 8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
  • the surface resistance (sheet resistance) varies depending on the application, but is usually 5 to 10,000 ⁇ / ⁇ , preferably 10 to 300 ⁇ / ⁇ .
  • the thin film patterned by the present invention is usually excellent in transparency.
  • a transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent base material is transparent.
  • the rate is usually 85% or more, preferably 90% or more in the visible light region.
  • the total light transmittance is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 10% or less, more preferably 5% or less.
  • the transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention has excellent conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (resistance to resistance).
  • the transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention is used as a transparent radio wave absorber, an ultraviolet absorber, and a transparent semiconductor device as another metal. It can also be used in combination with a film or a metal oxide film.
  • the thin film patterned by the present invention is obtained by sufficiently controlling the etching rate, the formed pattern shape is accurate.
  • the heat resistance after the heat test is 1.5 times or less than the surface resistance before the heat test, it can be said that the heat resistance is excellent.
  • ⁇ Alkali resistance> The transparent conductive substrate was immersed in a 3% NaOH aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
  • ⁇ Acid resistance> The transparent conductive substrate was immersed in a 3% HCl aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
  • Example 1 ⁇ Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 94: 6 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained molded body was annealed by holding it in an air atmosphere at 300 ° C. for 1 hour to obtain an oxide mixture (1).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of the oxide mixture (1) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
  • the obtained oxide mixture (1) is processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and a transparent conductive film is formed by sputtering using the sputtering target to produce a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 94: 6.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 2 ⁇ Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 95: 5 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (2).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (2) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target.
  • a transparent film having a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a conductive film was formed to produce a transparent conductive substrate.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 9.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.
  • titanium oxide powder Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the Zn: Ti atomic number ratio of 99: 1, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (C1).
  • an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation)
  • the obtained oxide mixture (C1) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a transparent conductive film was formed by sputtering in the same manner as in Example 1.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 24 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
  • Example 3 Manufacture of oxide sinter>
  • the disk-shaped molded body obtained in the same manner as in Example 1 was heated up to 1000 ° C. at 5 ° C./min, over 1000 ° C. up to 1500 ° C. at 1 ° C./min, and sintered at the sintering temperature. Sintering was performed by holding at 1500 ° C. for 5 hours, and then annealing treatment was performed at 1300 ° C. for 5 hours in an inert atmosphere (100% Ar atmosphere) to obtain an oxide sintered body (3).
  • the obtained oxide sintered body (3) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness was formed on the substrate by sputtering as in Example 1.
  • a 500 nm transparent conductive film was formed.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 12.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 4 Manufacture of oxide sinter>
  • the disc-shaped molded body obtained in the same manner as in Example 2 was heated up to 1000 ° C. at 5 ° C./min, in excess of 1000 ° C. to 1300 ° C. at 1 ° C./min in an inert atmosphere (100% Ar atmosphere).
  • the oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (4).
  • the crystal structure of the oxide sintered body (4) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the obtained oxide sintered body (4) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Comparative Example 2 Manufacture of oxide sinter>
  • the disc-shaped molded body obtained in the same manner as in Comparative Example 1 was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min.
  • the oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (C2).
  • the obtained oxide sintered body (C2) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 70% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
  • Example 5 ⁇ Manufacture of oxide sinter (hot press method)> Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the element number ratio of zinc element to titanium element is 97.0: 3.0 Were weighed so as to be, put in a polypropylene container, and further 2 mm ⁇ zirconia balls and ethanol as a mixed solvent were added. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (5).
  • the crystal structure of the oxide sintered body (5) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (5) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 6 ⁇ Manufacture of oxide sinter (hot press method)> Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (Ti 2 O 3 (III), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the ratio of the number of elements of zinc element and titanium element is 97.0: It weighed so that it might be set to 3.0, it put into the container made from a polypropylene, and also ethanol was added as a 2 mm diameter zirconia ball
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (6).
  • the obtained oxide sintered body (6) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • Example 7 ⁇ Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size) 1 ⁇ m or less, manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, put them in a resin pot at a Zn: Ti atomic ratio of 97: 3, and wet-mixed by a wet ball mill mixing method did. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (7) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
  • the obtained oxide sintered body (7) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (C3) was obtained by sintering at 1300 ° C. which is a sintering temperature for 5 hours.
  • the obtained oxide sintered body (C3) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1.
  • Zn: Ti (atomic ratio) 88 : 12.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film having both transparency and chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), but high resistance. It is clear.
  • Example 8 ⁇ Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the Zn: Ti atomic ratio of 93: 7, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (8) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
  • the obtained oxide sintered body (8) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 9 Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the atomic ratio of Zn: Ti of 91: 9, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. Sintering was carried out by holding at 1300 ° C., which is a sintering temperature, for 5 hours to obtain an oxide sintered body (9).
  • the obtained oxide sintered body (9) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 44.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 10 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • the obtained oxide mixture (10) was processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 10.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the acrylic transparent resin sheet before film formation averaged 93%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 93%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm.
  • This molded body was first annealed at 500 ° C. for 3 hours in an atmospheric atmosphere of normal pressure (101.325 kPa) to obtain an oxide mixture (11).
  • the crystal structure of the oxide mixture (11) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), it was a mixture of crystal phases of zinc oxide (ZnO) and titanium oxide.
  • the obtained oxide mixture (11) was processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. .
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • 5N Ar gas
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 62% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • oxide mixture (C4) was obtained by 3 hours in an argon atmosphere at normal pressure (101.325 kPa) to obtain an oxide mixture (C4).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the target was prepared by processing the obtained oxide mixture (C4) into a disk shape of 50 mm ⁇ , and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film quartz glass substrate
  • sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a transparent conductive film having a thickness of 200 nm on the substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 125 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the obtained film on the transparent conductive substrate is transparent, but has high resistance and poor chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that
  • the obtained oxide sintered body (C5) was processed into a shape of 4 inches ⁇ and 6 mmt, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on condition of the following, the transparent conductive film with a film thickness of 300 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained.
  • the Al content in the formed film was 2.3% by weight.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 25.3 ⁇ / ⁇ .
  • the transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 55% in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 3.2 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 7.0 times the surface resistance before the heat test, and it was found that the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the obtained film on the transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • crystal structure of the oxide mixture (13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) And no titanium oxide was present.
  • the obtained oxide sintered body (13) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • a target is prepared, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the obtained oxide sintered body (15) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C6).
  • ZnO manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • titanium oxide powder Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88
  • the target oxide is produced by processing the obtained oxide sintered body (C6) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • Zn: Ti atomic ratio
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 440 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C7).
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • the crystal structure of the oxide sintered body (C7) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the target oxide is produced by processing the obtained oxide sintered body (C7) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • a transparent conductive film quartz glass substrate
  • sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • Zn: Ti atomic ratio
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (16) (hot pressing method).
  • the obtained oxide sintered body (16) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 12.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (17) (hot press method).
  • the crystal structure of the oxide sintered body (17) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the target oxide is produced by processing the obtained oxide sintered body (17) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was heated at 500 ° C.
  • the target was produced by processing the obtained oxide mixture (18) into a disk shape of 20 mm ⁇ , and a transparent conductive film was formed by using the PLD method to obtain a transparent conductive substrate.
  • a transparent conductive film was formed by using the PLD method to obtain a transparent conductive substrate.
  • the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.7 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 20 A target was produced by processing the oxide mixture (18) obtained in Example 19 into a disk shape of 20 mm ⁇ . Using this target, the transparent substrate (quartz glass substrate) in Example 19 was replaced with an acrylic transparent resin sheet (80 mm ⁇ 80 mm ⁇ 2 mmt flat plate), and the film formation conditions (Substrate Temperature) were changed as follows. In the same manner as in Example 19, a 300 nm-thick transparent conductive film was formed by the PLD method with a film formation time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. Further, this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 21 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the resin sheet before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 21 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was sintered at 800 ° C.
  • the obtained oxide sintered body (19) is processed into a disk shape of 20 mm ⁇ to produce a target, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • PS-2000 pulse laser deposition apparatus
  • the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.7 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was heated at 400 ° C.
  • oxide mixture (C8) was obtained by 3 hours under an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide mixture (C8).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (C8) was processed into a disk shape of 20 mm ⁇ to prepare a target, and using this, the PLD method was performed in a film formation time of 120 minutes in the same manner as in Example 19.
  • a transparent conductive film having a thickness of 320 nm was formed.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1.
  • this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.34 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 73.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm).
  • the transmittance in the visible region of the quartz glass substrate before film formation is the same as in Example 19.
  • the surface resistance after the moisture resistance test was 2.4 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.2 times the surface resistance before the heat test, which is inferior in heat resistance.
  • the film on the transparent conductive substrate obtained is transparent, but has high resistance and poor conductivity, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that the transparent conductive film is inferior.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to form a transparent conductive substrate. Obtained. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 13.3 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed in such a ratio that the Zn: Ti atomic ratio was 97: 3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (22) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.)
  • the above target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( Using a “Comex 205 type” manufactured by Co., Ltd., a transparent conductive film having a film thickness of 300 nm was formed under the following film forming conditions with a film forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, and heat treatment at 1000 ° C. for 4 hours.
  • a disk-shaped oxide sintered body (23) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 13.3 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (24) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C9) (hot press sintering).
  • C9 hot press sintering
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 367.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C10) (hot press sintering).
  • C10 hot press sintering
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 800.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 500 ° C.
  • an oxide mixture 25.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • a tablet is produced by processing the obtained oxide mixture (25) into a disk shape of 20 mm ⁇ , and a transparent conductive film is formed by ion plating using this to form a transparent conductive substrate. Obtained.
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a transparent substrate a non-alkali glass substrate having a thickness of 0.7 mm.
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 36.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ion plating is performed under the following conditions, and the film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a transparent substrate a non-alkali glass substrate having a thickness of 0.7 mm.
  • a 150 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 467 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the transparent conductive substrate obtained is a transparent conductive film that is transparent but has high resistance and inferior chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 160 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is transparent and low resistance even when the film thickness is 100 nm or less, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 42.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 85% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the heat-resistant transparent resin film before film formation in the visible region (380 nm to 780 nm) was 90% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 90% on average.
  • the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is transparent and low resistance even when the substrate is a heat resistant film, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
  • Example 30 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm.
  • This compact was sintered at 800 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • the obtained oxide sintered body (26) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • Atmospheric gas conditions during film formation: Argon 160 sccm
  • Oxygen 2 sccm
  • Discharge current during film formation 100 A Deposition time: 200 seconds
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 39.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (27).
  • the crystal structure of the oxide sintered body (27) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • a tablet is produced, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 36.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. Further, the sintered body was sintered at 800 ° C.
  • oxide sintered body 28
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • RINT2000 X-ray diffractometer
  • crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (28) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • Atmospheric gas conditions during film formation: Argon 160 sccm
  • Oxygen 2 sccm
  • Discharge current during film formation 100 A Deposition time: 200 seconds
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 95: 5.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 98.5: 1.5 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • oxide sintered body (C12) was obtained by 4 hours in an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (C12).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of the oxide sintered body (C12) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 98.5: 1.5.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 60.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the film on the obtained transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance) Is clear.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 88:12 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • oxide sintered body (C13) was obtained by 4 hours in an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (C13).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of this oxide sintered body (C13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (C13) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet.
  • a transparent conductive film is formed by ion plating using the tablet.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 1200.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 73% on average in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (30).
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 55.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (31).
  • the obtained oxide sintered body (31) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 47.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 36 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, gallium element, and titanium element is 93.0: 2.0: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • Relative density 100 ⁇ [(density of sintered body) / (theoretical density)]
  • theoretical density (Zinc oxide simple substance density ⁇ mixing weight ratio + gallium oxide simple substance density ⁇ mixing weight ratio + titanium oxide simple substance density ⁇ mixing weight ratio)
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.7 ⁇ 10 ⁇ 4 ⁇ cm.
  • the surface resistance was 9.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 300 ° C. in an air atmosphere to obtain an oxide mixture. The obtained oxide mixture was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Sputtering device "E-200S” manufactured by Canon Anelva Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 ⁇ 10 ⁇ 4 Pa Ar pressure: 0.5 Pa
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 9.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 57% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the obtained sintered body was processed into a shape of 4 inches ⁇ and 6 mm thick, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on the following conditions, the transparent conductive film with a film thickness of 500 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained.
  • the Al content in the formed film was 2.3% by weight.
  • Sputtering equipment Canon Anelva “E-200S” Sputtering method: DC magnetron sputtering Magnetic field strength: 1000 Gauss (directly above the target, horizontal component)
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.1 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
  • Example 38 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element, and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 8.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 39 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 94.6%.
  • the relative density is obtained in the same manner as in Example 36.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 9.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 40 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 93.9% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 41 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.7% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 42 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.5% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 43 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 94.0%.
  • the relative density is obtained in the same manner as in Example 36.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 10.6 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 44 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 96.5: 0.5: 3.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 45 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 94.5: 0.5: 5.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours.
  • the relative density of the sintered body was calculated from the size of the sintered body and found to be 95.6%. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 46 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.9% when the relative density of this sintered compact was computed from the size of the sintered compact.
  • the relative density is obtained from the following formula.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • Relative density 100 ⁇ [(density of sintered body) / (theoretical density)]
  • theoretical density (Zinc oxide simple substance density ⁇ mixing weight ratio + Aluminum oxide simple substance density ⁇ mixing weight ratio + titanium oxide simple substance density ⁇ mixing weight ratio)
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 8.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 47 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 9.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 48 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 49 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 50 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.7% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 51 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 52 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 96.5: 0.5: 3.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 53 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 94.5: 0.5: 5.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body and found to be 95.8%. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 93.0%.
  • the relative density is obtained in the same manner as in Example 46.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. The surface resistance was 164 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.3 times the surface resistance before the moisture resistance test and was excellent in moisture resistance.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that has both chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), alkali resistance, and acid resistance. Although it is a film, it has low near-infrared transmittance and high resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by High Purity Chemicals Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • ZnO manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • Ti 2 O 3 titanium oxide powder
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • RINT2000 X-ray diffractometer
  • a target is prepared by processing the obtained oxide mixture (32) into a disk shape of 50 mm ⁇ , and a zinc oxide-based thin film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 8.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the zinc oxide thin film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • oxide mixture (C14) was obtained by 3 hours under an atmospheric pressure (0.1013 MPa) argon atmosphere to obtain an oxide mixture (C14).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (C14) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.25 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 112.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
  • a zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
  • Example 54 the etching rate of the formed thin film was examined and found to be 1.5 nm / second.
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio where the atomic ratio of Zn: Ti was 92: 8. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of this oxide mixture (34) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
  • a target is prepared by processing the obtained oxide mixture (34) into a disk shape of 50 mm ⁇ , and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 7.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 15.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Example 57 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Example 58 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (36).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C15).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.16 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained. Although the etching rate was sufficiently controllable, the resistance was high.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (37).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of decrease in film thickness (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.33 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • a zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
  • the etching rate of the formed thin film was examined in the same manner as in Example 1, it was 1.5 nm / second.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IQ” manufactured by Tencor). As a result, the etching rate of the formed thin film was 2.42 nm / second.
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more.
  • this thin film is patterned using an acetic acid aqueous solution similar to that in Example 59 as an etchant using a mask having a predetermined pattern, it is good. It was difficult to form an etching pattern.

Landscapes

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

Abstract

Le corps fritté à base d'oxydes selon la présente invention est sensiblement constitué de zinc, de titane, et d'oxygène, le rapport atomique du titane sur la somme du zinc et du titane (Ti/(Zn+Ti) étant supérieur à 0,02 sans dépasser 0,1. Le mélange d'oxydes selon l'invention est constitué d'oxyde de zinc et d'oxyde de titane, le rapport atomique du titane sur la somme du zinc et du titane (Ti/(Zn+Ti) étant supérieur à 0,02 sans dépasser 0,1. En utilisant le corps fritté à base d'oxydes ou le mélange d'oxydes selon l'invention, il est possible de former un film d'oxyde de zinc transparent électroconducteur présentant d'excellentes propriétés de conductivité et de durabilité chimique.
PCT/JP2011/053405 2010-02-18 2011-02-17 Corps fritté à base d'oxydes, mélange d'oxydes, procédés de fabrication correspondant, et cibles les utilisant WO2011102425A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2011800102349A CN102762518A (zh) 2010-02-18 2011-02-17 氧化物烧结体、氧化物混合物、它们的制造方法以及使用它们的靶
KR1020127024066A KR20120129972A (ko) 2010-02-18 2011-02-17 산화물 소결체, 산화물 혼합체, 이들의 제조 방법 및 이들을 이용한 타겟

Applications Claiming Priority (24)

Application Number Priority Date Filing Date Title
JP2010033844 2010-02-18
JP2010-033843 2010-02-18
JP2010-033844 2010-02-18
JP2010033843 2010-02-18
JP2010035722 2010-02-22
JP2010-035722 2010-02-22
JP2010-040198 2010-02-25
JP2010040198 2010-02-25
JP2010052251 2010-03-09
JP2010-052253 2010-03-09
JP2010-052251 2010-03-09
JP2010052253 2010-03-09
JP2010-267726 2010-11-30
JP2010267727 2010-11-30
JP2010267726 2010-11-30
JP2010-267727 2010-11-30
JP2010268610A JP2011190528A (ja) 2010-02-18 2010-12-01 酸化亜鉛系透明導電膜の形成方法、酸化亜鉛系透明導電膜および透明導電性基板
JP2010-268611 2010-12-01
JP2010268611 2010-12-01
JP2010-268610 2010-12-01
JP2010281041 2010-12-16
JP2010281043 2010-12-16
JP2010-281043 2010-12-16
JP2010-281041 2010-12-16

Publications (1)

Publication Number Publication Date
WO2011102425A1 true WO2011102425A1 (fr) 2011-08-25

Family

ID=44483011

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/053405 WO2011102425A1 (fr) 2010-02-18 2011-02-17 Corps fritté à base d'oxydes, mélange d'oxydes, procédés de fabrication correspondant, et cibles les utilisant

Country Status (1)

Country Link
WO (1) WO2011102425A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121298A1 (fr) * 2011-03-07 2012-09-13 住友化学株式会社 Corps fritté d'oxyde, son procédé de fabrication et cible l'utilisant
JP2013209277A (ja) * 2012-03-02 2013-10-10 Sumitomo Chemical Co Ltd 酸化亜鉛系焼結体の製造方法およびターゲット
CN114592175A (zh) * 2018-03-30 2022-06-07 Ｊｘ金属株式会社 溅射靶部件及其制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04317455A (ja) * 1991-04-15 1992-11-09 Sumitomo Metal Mining Co Ltd Ｉｔｏ焼結体の製造方法
JP2008159814A (ja) * 2006-12-22 2008-07-10 Mitsui Mining & Smelting Co Ltd 酸化亜鉛系薄膜用エッチャント及び酸化亜鉛系薄膜のパターニング方法
JP4295811B1 (ja) * 2008-09-17 2009-07-15 三井金属鉱業株式会社 酸化亜鉛系ターゲット
JP2009167515A (ja) * 2008-01-15 2009-07-30 Kanazawa Inst Of Technology 透明導電膜製造用スパッタリングターゲット及び透明導電膜形成方法
JP2009298649A (ja) * 2008-06-13 2009-12-24 Sumitomo Metal Mining Co Ltd 酸化物焼結体、ターゲット、およびそれを用いて得られる透明導電膜、導電性積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04317455A (ja) * 1991-04-15 1992-11-09 Sumitomo Metal Mining Co Ltd Ｉｔｏ焼結体の製造方法
JP2008159814A (ja) * 2006-12-22 2008-07-10 Mitsui Mining & Smelting Co Ltd 酸化亜鉛系薄膜用エッチャント及び酸化亜鉛系薄膜のパターニング方法
JP2009167515A (ja) * 2008-01-15 2009-07-30 Kanazawa Inst Of Technology 透明導電膜製造用スパッタリングターゲット及び透明導電膜形成方法
JP2009298649A (ja) * 2008-06-13 2009-12-24 Sumitomo Metal Mining Co Ltd 酸化物焼結体、ターゲット、およびそれを用いて得られる透明導電膜、導電性積層体
JP4295811B1 (ja) * 2008-09-17 2009-07-15 三井金属鉱業株式会社 酸化亜鉛系ターゲット

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAKUYA SAKAI ET AL.: "TZO Usumaku Tomei Dodenmaku no Tei Teikoritsuka", ANNUAL SYMPOSIUM OF THE VACUUM SOCIETY OF JAPAN, vol. 50TH, 4 November 2009 (2009-11-04), pages 106 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121298A1 (fr) * 2011-03-07 2012-09-13 住友化学株式会社 Corps fritté d'oxyde, son procédé de fabrication et cible l'utilisant
JP2013209277A (ja) * 2012-03-02 2013-10-10 Sumitomo Chemical Co Ltd 酸化亜鉛系焼結体の製造方法およびターゲット
CN114592175A (zh) * 2018-03-30 2022-06-07 Ｊｘ金属株式会社 溅射靶部件及其制造方法

Similar Documents

Publication Publication Date Title
TWI402862B (zh) 氧化物燒結體、其製法、使用它之透明導電膜之製法與所得到的透明導電膜
KR20120129972A (ko) 산화물 소결체, 산화물 혼합체, 이들의 제조 방법 및 이들을 이용한 타겟
JP5593612B2 (ja) 酸化物焼結体、ターゲット、およびそれを用いて得られる透明導電膜、並びに透明導電性基材
JP5339100B2 (ja) Ｚｎ−Ｓｉ−Ｏ系酸化物焼結体とその製造方法およびスパッタリングターゲットと蒸着用タブレット
TWI500786B (zh) 透明導電膜之製造方法、透明導電膜之製造裝置、濺鍍靶及透明導電膜
JP4982423B2 (ja) 酸化亜鉛薄膜形成用スパッタターゲットと、それを用いて得られる酸化亜鉛薄膜を有する表示素子及び太陽電池
WO2011115177A1 (fr) Films conducteurs transparents
JP2007314364A (ja) 酸化物焼結体、ターゲット、及びそれを用いて得られる酸化物透明導電膜ならびにその製造方法
JP2011184715A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
WO2011102425A1 (fr) Corps fritté à base d'oxydes, mélange d'oxydes, procédés de fabrication correspondant, et cibles les utilisant
JP2011190528A (ja) 酸化亜鉛系透明導電膜の形成方法、酸化亜鉛系透明導電膜および透明導電性基板
JP2012132090A (ja) 酸化亜鉛系透明導電膜の形成方法、酸化亜鉛系透明導電膜および透明導電性基板
JP2012158825A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、酸化亜鉛系透明導電膜の形成方法および透明導電性基板
JP2011207742A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
WO2011152682A2 (fr) Couche conductrice transparente, cible pour couche conductrice transparente et procédé de production de la cible pour couche conductrice transparente
JP2012193073A (ja) 酸化物成形体、酸化物焼結体、および透明導電膜形成材料
JP5952031B2 (ja) 酸化物焼結体の製造方法およびターゲットの製造方法
JP2012106880A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
JP2012106879A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
JP2003100154A (ja) 透明導電膜およびその製造方法並びにその用途
JP2012197216A (ja) 酸化物焼結体、その製造方法およびそれを用いたターゲット
WO2014021374A1 (fr) Corps fritté d'oxyde et comprimé obtenu par le traitement dudit corps
JP2012140673A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
JP2012140696A (ja) 酸化亜鉛系透明導電膜形成材料、その製造方法、それを用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
TW201200616A (en) Oxide sintered body, oxide mixture, manufacturing methods for same, and targets using same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180010234.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11744711

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20127024066

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11744711

Country of ref document: EP

Kind code of ref document: A1