WO2008044474A1 - Procédé de formation de film transparent électroconducteur - Google Patents

Procédé de formation de film transparent électroconducteur Download PDF

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Publication number
WO2008044474A1
WO2008044474A1 PCT/JP2007/068789 JP2007068789W WO2008044474A1 WO 2008044474 A1 WO2008044474 A1 WO 2008044474A1 JP 2007068789 W JP2007068789 W JP 2007068789W WO 2008044474 A1 WO2008044474 A1 WO 2008044474A1
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Prior art keywords
transparent conductive
conductive film
titanium oxide
gas
forming
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PCT/JP2007/068789
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English (en)
Japanese (ja)
Inventor
Yoshikazu Kondo
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Konica Minolta Holdings, Inc.
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Priority to JP2008538629A priority Critical patent/JPWO2008044474A1/ja
Publication of WO2008044474A1 publication Critical patent/WO2008044474A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/218—V2O5, Nb2O5, Ta2O5
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/1525—Deposition methods from the vapour phase by cvd by atmospheric CVD
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making

Definitions

  • the present invention relates to a method for forming a transparent conductive film mainly composed of titanium oxide having excellent light transmittance and conductive performance.
  • organic electroluminescence organic electroluminescence
  • EL display abbreviated as EL
  • flat display transparent electrode such as plasma display panel, field emission display, solar cell transparent electrode, electronic paper, touch panel, electromagnetic shielding material, infrared reflection film, etc. It's being used.
  • the transparent conductive film Pt Au, Ag, a metal thin film such as Cu, SnO, In O, CdO, ZnO, Sn_ ⁇ 2: Sb, Sn_ ⁇ 2: F, ZnO: Al, In O: Sn etc.
  • a metal thin film such as Cu, SnO, In O, CdO, ZnO, Sn_ ⁇ 2: Sb, Sn_ ⁇ 2: F, ZnO: Al, In O: Sn etc.
  • non-oxides such as complex oxide films, chalcogenides, LaB, TiN, and TiC.
  • tin-doped indium oxide (hereinafter also referred to as ITO) film strength is most widely used because of its excellent electrical characteristics and ease of processing by etching.
  • a transparent conductive film such as ITO is mainly formed by a wet film formation method typified by coating, or a vacuum film formation method such as a sputtering method, a vacuum evaporation method, or an ion plating method. It was.
  • the vacuum evaporation method and the sputtering method can obtain a transparent conductive film with low resistance, and industrially, it has excellent conductivity with a specific resistance of 10-4 ⁇ 'cm order using a DC magnetron sputtering device.
  • An ITO film can be obtained.
  • a thin film formed of TiO alone has a resistivity on the order of 1 to 1 ⁇ cm, and a thin film composed of TiO doped with force niobium, which is an insufficient property as a conductive film, , Its resistivity is reduced by 2 ⁇ orders of magnitude, a transparent conductive film with low resistivity is obtained, and after forming a thin film, heat treatment is performed at 250 ° C to 500 ° C in a reducing atmosphere (reduction As a technology to replace ITO, a TiO transparent conductive film using niobium as a doped metal can be applied to thin display members, solar cells, etc. Is being discovered.
  • the method described in the above non-patent document is that the method for forming a TiO-based transparent conductive film using a glass substrate or a metal substrate is 250 °. It is necessary to form a TiO-based transparent conductive film in a high temperature environment of C to 500 ° C, followed by post-treatment (also called heat treatment or reduction annealing treatment) at 250 ° C to 500 ° C in the same reducing atmosphere. For this reason, for example, when a transparent conductive film is formed as an electrode on a color filter used in a thin display member or the like, a color filter is configured in a high temperature environment of 250 ° C. to 500 ° C. It becomes difficult to apply due to the heat resistance of coloring materials.
  • liquid crystal and organic EL have been used in the fields of thin display members, solar cells, etc., in recent years, where needs for lightening, thinning, impact resistance, flexibility, etc. are increasing.
  • the heat resistance of commonly used transparent resin base materials is usually 150 ° C or lower, and even if it is a material with higher heat resistance, the upper limit is about 220 ° C. Therefore, the base materials that can be used are naturally restricted, and this is a major obstacle to the application in the above fields.
  • Non-patent literature l Furubayashi et al., Appl. Phys. Lett. 86, 252101 (2005)
  • Non-patent literature 2 The 67th JSAP academic conference, Proceedings (Autumn 2006) 566-567, 30p-RA- 12 ⁇ 16
  • the present invention has been made in view of the above problems, and its object is to provide a transparent conductive film mainly composed of titanium oxide, which is excellent in transparency and conductivity without being restricted by the base material. It is to provide a formation method.
  • the film is a thin film mainly composed of titanium oxide having a dopant
  • the post-treatment introduces a transparent conductive film mainly composed of titanium oxide formed on the substrate in advance into the discharge space.
  • a method for forming a transparent conductive film is characterized in that the plasma treatment is performed to treat a thin film containing titanium oxide as a main component by exposing the substrate to a gas in a plasma state in a plasma state.
  • the transparent conductive film containing titanium oxide as a main component is formed by sputtering, vapor deposition, and CVD. 5. The method for forming a transparent conductive film according to any one of 1 to 4, wherein the film is formed by at least one method selected from the group consisting of force and force.
  • the transparent resin includes polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethersulfone (PES), polycarbonate (PC), polymethyl methacrylate (PMMA) and polyethylene naphthalate ( 10.
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • PES polyethersulfone
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PEN polyethylene naphthalate
  • the transparent conductive film mainly composed of titanium oxide and the post-treatment are repeatedly performed to deposit a transparent conductive layer mainly composed of titanium oxide.
  • FIG. 1 is a schematic diagram showing an example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
  • FIG. 2 is a schematic view showing another example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
  • FIG. 3 shows an example of a two-frequency jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
  • FIG. 4 is a schematic view showing an example of another two-frequency plasma jet atmospheric pressure plasma discharge treatment apparatus in which power sources of different frequencies are installed on each electrode.
  • FIG. 5 is a schematic view showing an example of a direct atmospheric pressure plasma discharge treatment apparatus applicable to the present invention.
  • FIG. 6 is a schematic view showing an example of another two-frequency direct atmospheric pressure plasma discharge treatment apparatus in which power sources having different frequencies are installed on each electrode.
  • the present inventor has formed a transparent conductive film containing titanium oxide as a main component on a base material, and then performs a post-treatment.
  • the transparent conductive film mainly composed of titanium oxide is a thin film mainly composed of titanium oxide having a dopant, and the post-treatment is based on the titanium oxide previously formed on the substrate.
  • the transparent conductive film is a plasma treatment in which a thin film containing titanium oxide as a main component is treated by introducing a gas into the discharge space to form a plasma state and exposing the substrate to the plasma state gas.
  • the plasma treatment method is employed to expose the substrate on which the transparent conductive film mainly composed of titanium oxide is formed at an excessively high temperature at a relatively low temperature.
  • a transparent conductive film mainly composed of titanium oxide having excellent transparency and conductivity without being greatly restricted by applicable substrates could be obtained.
  • the transparent conductive film mainly composed of titanium oxide formed in the film forming step is reduced to a plasma state containing hydrogen gas or water vapor.
  • the amount of oxygen deficiency in the transparent conductive film could be suppressed to an appropriate amount, and a transparent conductive film mainly composed of titanium oxide having excellent film homogeneity was obtained.
  • the film is formed at 220 ° C or lower.
  • the transparent conductive film is formed by using at least one method selected from a sputtering method, a vapor deposition method and a CVD method to form a transparent titanium oxide oxide conductive film to which a dopant is added at a low temperature. I was able to.
  • a transparent conductive material mainly composed of titanium oxide.
  • atmospheric pressure plasma CVD as a film formation method, a chemical reaction at the molecular level can be performed in a dense plasma atmosphere in a low temperature environment. As a result, a dense and high-quality transparent conductive film is formed. I was able to film.
  • a transparent resin is used as the base material.
  • a specific resin base material is used as the base material.
  • the transparent conductive layer mainly composed of titanium oxide is formed by repeatedly forming and conducting a post-treatment of the transparent conductive film mainly composed of titanium oxide.
  • the reducing gas molecules activated by the plasma treatment in the post-treatment can reach the details in the depth direction in the film and increase the reduction effect.
  • a transparent conductive film mainly composed of titanium oxide of the present invention a transparent conductive film mainly composed of titanium oxide mainly composed of titanium oxide having a dopant was formed on a substrate. Thereafter, the transparent conductive film containing titanium oxide as a main component is subjected to plasma treatment as a post-treatment to reduce the resistance.
  • the transparent conductive film containing titanium oxide as a main component according to the present invention is formed using titanium oxide having a dopant as a main component on a base material.
  • the substrate used in the present invention is a plate-like, sheet-like or film-like planar shape, or a three-dimensional shape such as a lens or other molded article, and a thin film can be formed on the surface thereof.
  • a plane shape or a three-dimensional shape may be a glass plate, a resin film, or the like.
  • the ability to use various materials such as glass, resin, ceramics, metals, and non-metals S, the ability to perform post-processing in a low-temperature environment according to the present invention can be demonstrated more and it can be applied to a wide range of fields. From this point of view, it is preferable to use a transparent resin (film) having good light transmission and high heat resistance as the substrate.
  • Transparent resins include, for example, polymethylmetatalylate (PMMA), acrylonitrile butadiene styrene resin (ABS), ethylene acetate resin (EVAC), ethylene-butyl alcohol resin (EVOH), polyamide ( PA), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polymethylpentene (PMP), polypropylene ( PP), polystyrene (PS), poly (vinyl chloride) (PVC), polyvinylidene chloride (PVDC), styrene acrylonitrile resin (SAN), triacetyl cellulose (TAC), cellulose triacetate, cellulose diacetate, cellulose acetate propio Nate or cellulose acetate butyrate A cellulose ester, a film made of resin and the like.
  • PMMA polymethylmetataly
  • the transparent resin substrate is made of polyethylene terephthalate (PET), triacetylenocellulose (TAC), polyethylene naphthalate (PEN), polyethersulfone (PE S),
  • PET polyethylene terephthalate
  • TAC triacetylenocellulose
  • PEN polyethylene naphthalate
  • PE S polyethersulfone
  • PC polycarbonate
  • acrylic resin is preferable from the viewpoint of forming a transparent conductive film mainly composed of titanium oxide that is highly permeable, lightweight, and has low resistance, and can be post-treated. Better!/,.
  • an antiglare layer, a clear hard coat layer, a noc coat layer, and the like can be coated on the substrate according to the present invention as necessary.
  • the transparent conductive film mainly composed of titanium oxide according to the present invention is a thin film mainly composed of titanium oxide having a dopant.
  • the transparent conductive film mainly composed of titanium oxide according to the present invention mainly composed of titanium oxide having a dopant is applied to the film forming method and film forming conditions to be applied. Therefore, the composition of the obtained transparent conductive film mainly composed of titanium oxide is slightly different, and the titanium oxide layer does not typically have a composition of TiO as a whole. Since there is a component such as a trace component (element) taken from the source gas or a dopant according to the present invention, the main component of titanium oxide in the present invention is at least as a composition.
  • the method for forming a thin film mainly composed of titanium oxide on the above-mentioned base material there is no particular limitation on the method for forming a thin film mainly composed of titanium oxide on the above-mentioned base material.
  • sputtering RF method, VHF method, DC method, magnetron
  • ion beam method ion beam method
  • ECR method electrospray method
  • collimation method evaporation method
  • EB method ion rating
  • thermal CVD method plasma CVD method
  • PLD pulse laser deposition
  • the sputtering method, vapor deposition method, and CVD method are preferable in that a dense and high-quality film is formed at a low temperature or formed on a large-area substrate.
  • the sputtering method can form a film relatively easily even with a high melting point material or compound, and it is not necessary to dissolve the material to be formed into a thin film in the thermal process unlike the vapor deposition method.
  • a film having a high melting point such as titanium oxide can be easily formed.
  • a reactive gas such as a sputtering gas (in an atmosphere of several Pa) gas, hydrogen gas or oxygen gas is introduced into a metal target.
  • a substrate is placed facing DC discharge sputtering, RF sputtering, or a target, and a magnet is placed near the target to be sputtered to apply a magnetic field so that ions or neutrals on the target surface can be applied.
  • Any method such as a magnetron method in which the collision rate of particles is increased to increase the film forming speed may be used.
  • an evaporation method place the substrate and the film forming material to be cane deposited into the container, and the entire vacuum state (10-3 to 10-about 4 Pa), dissolved feedstock with hot (Evaporate). As a result, the raw material becomes gas molecules and collides with and adheres to the substrate to form a film.
  • the heating and melting method there are resistance heating type, electron beam type, high frequency induction type and laser type.
  • CVD method under vacuum (10 3 about Pa), and take advantage of the reaction at the surface of the gas phase of the gaseous raw material, thin film on a substrate that a component of the elements contained in the raw material molecule It is a method to deposit on.
  • the substrate on which the thin film is to be deposited is heated and the source molecules are decomposed by thermal energy.
  • the reaction method is called thermal CVD.
  • plasma CVD plasma of a gas containing a discharge gas and source molecules is generated, and source molecules (for example, titanium tetraethoxide, etc. are included by electrons accelerated in the plasma.
  • Source gas is decomposed.
  • no heating is required for the film deposition itself.
  • a discharge gas such as a rare gas is added.
  • These film forming methods can form a thin film mainly composed of titanium oxide at a low temperature even when V is shifted, and do not require a force vacuum facility. It is particularly preferable to apply an atmospheric pressure plasma CVD method that can form and process continuously or semi-continuously from the viewpoint of further achieving the objective effect of the present invention. The details of the atmospheric pressure plasma CVD method that can be preferably applied to the present invention will be described later.
  • the transparent film mainly composed of titanium oxide is used.
  • the gas for forming the conductive film is a gas that receives energy from the discharge gas in the discharge space and enters an excited state or a plasma state to form a transparent conductive film mainly composed of titanium oxide, or controls the reaction or reacts. It is also a gas that promotes. Formation gas of the transparent conductive film containing titanium oxide as a main component, 0.1 01 in total gas; this and force S preferably contained 10% by volume, more preferably 0.1;! In 1-3 volumes 0/0 is there.
  • the raw material used for forming the transparent conductive film mainly composed of titanium oxide according to the present invention includes an organic titanium compound, a titanium hydrogen compound, a titanium halide, etc.
  • the organic titanium compound include: Triethoxytitanium, trimethoxytitanium, triisopropoxytitanium, tributoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, ethyltitanium, triisopropyltitanium, tributyltitanium, tetraethyltitanium, tetrisopropyltitanium, tetrabutyltitanium, tetradimethylamino Titanium, Dimethyltitanium di (2,4 Pentedionate), Ethyltitanium Tri (2,4 Pentedionate), Titanium Tris (2,4 Pentedionate), Titanium Tris (acetomethylacetate
  • One feature of the present invention is to use doped TiO.
  • the doping material it is preferable to use mainly metal elements whose periodic table valence is different from that of Ti element of TiO.
  • V, Nb, Ta, B, Al, Ga, In, Tl Among them, Nb, Ta, V, and the like are preferably used from the viewpoint of forming a low-resistance transparent conductive film that is an object effect of the present invention.
  • niobium in titanium oxide niobium functions as a dopant in the transparent conductive film containing titanium oxide as a main component, carriers (electrons) are generated, and conductivity (resistance performance) is improved. it can.
  • the transparent conductive film mainly composed of titanium oxide according to the present invention is formed, for example, by applying the atmospheric pressure plasma CVD method which is a particularly preferable embodiment, a niobium compound is contained in the source gas. Contain.
  • niobium compounds useful as a starting material useful for the present invention include organic niobium compounds, niobium hydroxide compounds, niobium halides, and the like.
  • organic niobium compounds include pentaethoxyniobium, Penter n-butoxyniobium, pentater n-butoxyschobium, niobium phenoxide, tetrakis (2, 2, 6, 6-tetramethyl-3,5-heptanedionat) niobium
  • niobium hydroxide compounds include niobium hydroxide, halogen As the niobium chloride, niobium trichloride oxide, niobium chloride and the like can be used.
  • the amount contained in the source gas is preferably 1 to 20% by mass, more preferably 5 to 10% by mass as a dopant in the thin film mainly composed of titanium oxide. It is preferable to adjust the ratio of the dopant compound in the source gas so as to be in the range of%
  • the transparent conductive film mainly composed of titanium oxide when the formation of the transparent conductive film mainly composed of titanium oxide is performed by applying the atmospheric pressure plasma CDV method, water is added to the forming gas for the transparent conductive film mainly composed of titanium oxide.
  • a reducing gas selected from hydrocarbons such as elemental, methane, and water the transparent conductive film mainly composed of titanium oxide can be formed into a more uniform and dense film. From the viewpoint of improving the properties, adhesion, and crack resistance.
  • the reducing gas is preferably from 0.0001 to 5% by volume, more preferably from 0.0001 to 10% by volume based on 100% by volume of the total gas.
  • the transparent conductive film mainly composed of titanium oxide according to the present invention can be formed by exposing a discharge gas and an oxidizing gas to a gas excited to a plasma state.
  • the oxidizing gas used can be oxygen, ozone, hydrogen peroxide, carbon dioxide, etc.
  • a gas selected from helium, argon, and nitrogen can be cited.
  • the concentration of the oxidizing gas component in the mixed gas composed of the oxidizing gas and the discharge gas is preferably 0.000;! To 30% by volume, more preferably 0.001 to 15% by volume, especially 0.01 to It is preferable to contain 10 volume%.
  • the optimum value of each concentration of the discharge gas selected from the oxidizing gas species, helium, argon, and nitrogen can be appropriately selected depending on the substrate temperature, the number of oxidation treatments, and the treatment time.
  • the oxidizing gas is preferably oxygen or carbon dioxide, more preferably a mixed gas of oxygen and argon.
  • a transparent conductive film containing titanium oxide as a main component of the present invention a transparent conductive film containing titanium oxide as a main component is formed on a substrate according to the above method, and then the formed transparent conductive film is formed on the transparent conductive film.
  • the plasma treatment is performed by introducing a gas into the discharge space to bring it into a plasma state, and exposing the substrate to the plasma state gas to treat a thin film mainly composed of titanium oxide.
  • the plasma treatment is preferably an atmospheric pressure plasma treatment in which a film is formed under atmospheric pressure or a pressure near atmospheric pressure.
  • helium, neon, argon, krypton, xenon, radon, nitrogen and the like are used as the discharge gas constituting the gas, and hydrogen gas or steam reducing gas is used as the reaction gas.
  • Application can improve the conductivity of the formed transparent conductive film mainly composed of titanium oxide.
  • the reducing gas of hydrogen gas or water vapor is preferably 0.001 to 10% by volume based on 100% by volume of the total gas, more preferably 10% by volume. Is 0 ⁇ 00;! ⁇ 5% by volume.
  • the substrate temperature in the post-treatment is preferably an atmospheric pressure plasma treatment at 220 ° C or lower, and is preferably S, more preferably 100 to 220 ° C.
  • the post-treatment using the atmospheric pressure plasma processing apparatus is performed by applying a transparent conductive film mainly composed of titanium oxide on the substrate. Even if it is an off-line system in which post-processing is performed in an independent form after forming, or after forming a transparent conductive film mainly composed of titanium oxide by arranging a plurality of atmospheric pressure plasma processing apparatuses, Then, post-processing may be performed on-line.
  • the film-forming step of the transparent conductive film mainly composed of titanium oxide according to the present invention and a post-treatment to be performed thereafter It is also preferable to repeat the above and deposit a transparent conductive film mainly composed of titanium oxide.
  • the atmospheric pressure plasma processing apparatus used in the formation of the transparent conductive film mainly composed of titanium oxide or the post-treatment of the present invention the atmospheric pressure plasma processing apparatus of each method described below can be applied without limitation. .
  • a reactive gas helium, neon, argon, krypton, xenon, radon, nitrogen, etc.
  • a reducing gas containing hydrogen gas or water vapor are excited into a plasma state.
  • the formed transparent conductive film mainly composed of titanium oxide to the reducing gas at a constant temperature, preferably at a substrate temperature of 220 ° C. or lower for a certain period of time, it is uniform. And it can be set as a precise
  • the method for forming a transparent conductive film mainly composed of titanium oxide of the present invention it is preferably used for forming an atmospheric pressure plasma processing apparatus used in post-processing and a transparent conductive film mainly composed of titanium oxide. Details of the atmospheric pressure plasma processing apparatus will be described.
  • the atmospheric pressure plasma processing method for performing plasma CVD processing near atmospheric pressure does not need to be reduced in pressure and has a higher plasma density than plasma CVD method under vacuum. For this reason, the film formation speed is high and the average free process of gas is very short under high pressure conditions under atmospheric pressure compared to the conditions of normal CVD method. A quality film is obtained.
  • the transparent conductive film mainly composed of titanium oxide according to the present invention is formed into a thin film mainly composed of titanium oxide in a discharge space in which a high-frequency electric field is generated under atmospheric pressure or a pressure near the atmospheric pressure. It is formed by supplying a gas containing a gas to be excited and exposing the substrate to the excited gas.
  • the atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to UOkPa, and 93 kPa to 104 kPa is preferable for obtaining the good effects described in the present invention.
  • the excited gas as used in the present invention means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy.
  • a thin film formation mainly composed of titanium oxide containing a discharge gas and a metal oxide gas (for example, titanium tetraethoxide) is set between the opposing electrodes (discharge space) at atmospheric pressure or in the vicinity thereof.
  • a gas is introduced between the counter electrodes, and a high-frequency voltage is applied between the counter electrodes to change the thin film forming gas mainly composed of titanium oxide into a plasma state, and subsequently to form a thin film mainly composed of titanium oxide in the plasma state.
  • a transparent base material is exposed to gas, and a thin film mainly composed of titanium oxide is formed on the transparent base material.
  • the atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is not particularly limited, but can be roughly classified into the following two methods.
  • One method is a method called a plasma jet type atmospheric pressure plasma discharge treatment apparatus, in which a high-frequency voltage is applied between counter electrodes, a mixed gas containing a discharge gas is supplied between the counter electrodes, In this method, the mixed gas is converted into plasma, and then the plasma mixed gas and the transparent conductive layer forming gas are associated and mixed, and then sprayed onto the transparent substrate to form the transparent conductive layer.
  • the other method is a method using a direct atmospheric pressure plasma discharge treatment apparatus V, and after mixing a mixed gas containing a discharge gas and a transparent conductive layer forming gas, a transparent substrate is placed between the counter electrodes. In the supported state, the gas is introduced into the discharge space, and a high frequency voltage is applied between the opposing electrodes to form a transparent conductive layer on the transparent substrate.
  • FIG. 1 shows an example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
  • FIG. The present invention is not limited to this.
  • the following explanation may include assertive expressions for terms, etc., but it is a preferred example of the present invention and limits the meaning and technical scope of the terms of the present invention. It is not a thing.
  • an atmospheric pressure plasma discharge treatment apparatus 21 is provided in parallel with a pair of electrodes 41 a and 41 b connected to a power source 31 in parallel. At least one of the electrodes 41a and 41b is covered with a dielectric 42, and a high frequency voltage is applied by a power source 31 to a discharge space 43 formed between the electrodes.
  • the inside of the electrodes 41a and 41b has a hollow structure 44 so that heat generated by the discharge can be taken by water, oil, etc. during discharge and heat exchange can be performed so as to maintain a stable temperature. There is.
  • the gas 22 containing the discharge gas necessary for the discharge is supplied to the discharge space 43 through the flow path 24, and a high frequency voltage is applied to the discharge space 43.
  • the gas 22 including the discharge gas is turned into plasma.
  • the plasma gas 22 is injected into the mixing space 45.
  • the mixed gas 23 containing the gas necessary for forming the transparent conductive layer supplied by each gas supply means passes through the flow path 25 and is also carried to the mixing space 45, where the plasma
  • the transparent discharge gas 22 is merged and mixed, and sprayed onto the transparent substrate placed on the moving stage 47 or the substrate 46 including the transparent substrate on the outermost surface.
  • the transparent conductive layer forming gas in contact with the plasma mixed gas is activated by the energy of the plasma to cause a chemical reaction, and a transparent conductive layer is formed on the substrate 46.
  • the plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a mixed gas containing a gas necessary for forming a transparent conductive layer is sandwiched or surrounded by an activated discharge gas. Yes.
  • the moving stage 47 on which the substrate is placed has a structure capable of reciprocating scanning or continuous scanning, and if necessary, heat exchange similar to that of the electrode is performed so that the temperature of the substrate can be maintained. It has a structure that can
  • a waste gas exhaust passage 48 for exhausting the gas blown onto the substrate 46 can be provided as necessary. This quickly releases unwanted by-products formed in the space. It can be removed from the electric space 45 or the base material 46.
  • This plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a discharge gas is turned into plasma and activated, and then merged with a mixed gas containing a gas necessary for forming a transparent conductive layer. As a result, deposition of a film-formed product on the electrode surface can be prevented. However, as described in Japanese Patent Application No. 20 03-095367, by attaching an antifouling film or the like to the electrode surface, it can be prevented before discharge. A structure in which the discharge gas and the gas necessary for forming the transparent conductive layer are mixed is used.
  • FIG. 2 is a schematic view showing another example of the plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
  • the flow path 24 for supplying the gas 22 containing the discharge gas and the flow path 25 for supplying the mixed gas 23 containing the gas necessary for forming the transparent conductive layer are provided in parallel.
  • the flow path 24 for supplying the gas 22 containing the discharge gas is formed obliquely to increase the mixing efficiency with the mixed gas 23 supplied from the flow path 25. It's okay.
  • the high frequency power supply is operated in one frequency band.
  • FIG. 3 is a schematic diagram showing an example of a two-frequency jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
  • the jet type atmospheric pressure plasma discharge processing apparatus has a gas supply means and an electrode temperature adjusting means, which are not shown in FIG. And V, the device.
  • the atmospheric pressure plasma discharge treatment apparatus 110 has a counter electrode composed of a first electrode 111 and a second electrode 112, and the first power supply 121 is connected to the first electrode 111 between the counter electrodes.
  • a first high-frequency electric field of frequency ⁇ , electric field strength V, and current I is applied, and the second electrode 11
  • the first power supply 121 has a higher high-frequency electric field strength than the second power supply 122 ( V> V), and the first frequency ⁇ of the first power source 121 is the second frequency of the second power source 122.
  • a frequency lower than the frequency ⁇ can be applied.
  • a first filter 123 is installed between the first electrode 111 and the first power supply 121, and it is easy to pass a current from the first power supply 121 to the first electrode 111. It is designed so that the current from the second power source 122 to the first power source 121 does not easily pass through the current from the 122.
  • a second filter 124 is provided between the second electrode 112 and the second power source 122 to facilitate passage of a current from the second power source 122 to the second electrode. It is designed to ground the current from 121 and make it difficult to pass the current from the first power supply 121 to the second power supply 122.
  • Gas G is introduced from the gas supply means between the opposing electrodes (discharge space) 113 of the first electrode 111 and the second electrode 112, and a high-frequency electric field is applied from the first electrode 111 and the second electrode 112.
  • a discharge is generated, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side (the lower side of the paper), and the processing space formed by the lower surface of the counter electrode and the substrate F is formed into a plasma state gas G
  • a thin film is formed in the vicinity of the processing position 114 on the base material F that is filled with the temperature and is transported from the previous process. During the thin film formation, the electrode heats or cools the electrode through the pipe from the electrode temperature adjusting means.
  • the properties and composition of the resulting thin film may change, and it is desirable to appropriately control this.
  • the temperature control medium insulating materials such as distilled water and oil are preferably used.
  • it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur.
  • Fig. 3 shows a measuring instrument used for measuring the high-frequency electric field strength (applied electric field strength) and the discharge starting electric field strength.
  • 125 and 126 are high frequency voltage probes
  • 127 and 128 are oscilloscopes.
  • FIG. 4 is a schematic view showing an example of another two-frequency plasma jet type atmospheric pressure plasma discharge treatment apparatus in which power sources having different frequencies are installed on the respective electrodes.
  • the basic configuration is the same as in FIG. 1 above.
  • the second high frequency filter 101b and the second high frequency power supply 31b are connected to the force electrode 41b, and the electrode 41a is connected to the first high frequency Phi
  • the filter 101a and the first high frequency power supply 31a are connected so that two different high frequency voltages are applied.
  • the ability of film formation can be improved by arranging these plasma jet type atmospheric pressure plasma discharge treatment apparatuses in the scanning direction of a plurality of stages.
  • V, N, and V are electrodes.
  • the inside of the apparatus can be in a certain gas atmosphere, and a desired high-quality transparent antistatic film can be formed.
  • FIG. 5 is a schematic diagram showing an example of a direct atmospheric pressure plasma discharge treatment apparatus applicable to the present invention.
  • two electrodes 41 connected to the power source 31 are provided side by side so as to be parallel to the moving stage electrode 47, respectively. At least one of the electrodes 41 and 47 is covered with a dielectric 42, and a high frequency voltage is applied by the electrode 31 to a space 43 formed between the electrodes 41 and 47. .
  • the inside of the electrode 41 and the moving stage 47 has a hollow structure 44, so that heat generated by the discharge can be removed by water, oil, etc. during discharge, and heat exchange can be performed so as to maintain a stable temperature. It has become.
  • the gas 22 containing the discharge gas necessary for the discharge passes through the flow path 24, and the mixed gas 23 containing the gas necessary for forming the transparent conductive layer is It passes through the flow path 25 and merges and mixes in the mixing space 45.
  • the mixed gas G passes between the electrodes 41 and is supplied to the space 43 between the electrodes 41 and 47.
  • a plasma discharge is generated and the gas G is turned into plasma.
  • the gas G that has been turned into plasma activates the gas for forming the transparent conductive layer, causing a chemical reaction, and transparent conductive on the substrate (transparent substrate or liquid crystal optical element unit including the transparent substrate on the outermost surface) 46 A layer is formed.
  • the stage 47 on which the substrate is mounted has a structure capable of reciprocating scanning or continuous scanning. If necessary, heat exchange similar to the above electrode is performed so that the temperature of the substrate can be maintained. It has a structure that can
  • a waste gas exhaust passage 48 for exhausting the gas blown onto the base material 46 is provided. It can also be attached. Thereby, unnecessary by-products formed in the space can be quickly removed from the discharge space 45 or the substrate 46.
  • the antifouling film or the like is placed on the surface of the electrode to mix the discharge gas and the gas necessary for forming the transparent conductive layer before discharge. It's easy to make a structure.
  • the high-frequency power supply is used in one frequency band.
  • the method described in Japanese Patent Application Laid-Open No. 2003-96569 and each electrode as shown in Fig. 6 are used. It can also be implemented by installing power sources with different frequencies.
  • FIG. 6 is a schematic diagram showing an example of another two-frequency direct atmospheric pressure plasma discharge treatment apparatus in which power sources having different frequencies are installed on the respective electrodes.
  • FIG. 6 the basic configuration is the same as in FIG. 5 above.
  • the first high frequency filter 101a and the first high frequency power source 31a are connected to the two electrodes 41, and the moving stage electrode 47 is connected to the moving stage electrode 47.
  • the second high frequency filter 101b and the second high frequency power supply 31b are connected to each other so that two different high frequency voltages are applied.
  • the ability to form a film can be improved by arranging these direct atmospheric pressure plasma discharge treatment apparatuses in the scanning direction of a plurality of stages.
  • This direct-type atmospheric pressure plasma discharge treatment apparatus has a structure such that! /, Na! /, Surrounds the electrodes and the entire stage and does not allow outside air to enter. Thus, a desired high-quality thin film can be formed.
  • the high frequency power source is a high frequency power source (3kHz) manufactured by Shinko Electric, a high frequency power source (5kHz) manufactured by Shinko Electric, a high frequency power source (15kHz) manufactured by Shinko Electric, and a high frequency power manufactured by Shinko Electric.
  • Power supply 50kHz
  • HEIDEN Laboratory high frequency power supply continuous mode use, 100kHz
  • Pearl Industrial high frequency power supply 200kHz
  • Pearl Industrial high frequency power supply 800kHz
  • Pearl Industrial high frequency power supply (2MHz)
  • JEOL A high-frequency power source 13.
  • a power supply that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.
  • the power applied between the opposing electrodes is the second electrode (second high-frequency electric field).
  • Is supplied with power (power density) of lW / cm 2 or more excites the discharge gas to generate plasma, and imparts energy to the thin film forming droplets to form a thin film.
  • the upper limit value of the power supplied to the second electrode is preferably 50 W / cm 2 , more preferably 20 W / cm 2 .
  • the lower limit is preferably 1.2 W / cm 2 .
  • the discharge area (cm 2 ) refers to the area in the range where discharge occurs in the electrode.
  • the output density can be increased while maintaining the uniformity of the second high frequency electric field. It can be improved. As a result, a further uniform high-density plasma can be generated, and a further improvement in film quality and improvement in film quality can be achieved.
  • it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called continuous mode and an intermittent oscillation mode called pulse mode that performs ON / OFF intermittently. Either of them can be used, but at least the second electrode side (second The high-frequency electric field of the continuous sine wave is preferable because a denser and better quality film can be obtained.
  • the method for forming a transparent conductive film containing titanium oxide as a main component according to the present invention using an atmospheric pressure plasma apparatus has been described above.
  • the main component is titanium oxide, which is a feature of the present invention.
  • the resistance reduction treatment (anneal treatment, post-treatment) of the transparent conductive film by atmospheric pressure plasma treatment is also performed using the same equipment as the reactive gas, helium, neon, argon, krypton, xenon, radon, nitrogen as the discharge gas.
  • a transparent conductive film mainly composed of titanium oxide formed in the reducing gas is excited at a constant temperature, preferably a substrate temperature. By exposing to a temperature of 220 ° C or lower for a certain period of time, a thin film with high thin film uniformity and high resistance can be obtained.
  • PET biaxially stretched polyester
  • Dipentaerythritol hexaatalylate monomer 60 parts by weight Dipentaerythritol hexaatalylate dimer 20 parts by weight Dipentaerythritol hexaatalylate trimer or higher component 20 parts by weight Irgacure 18 4 (Ciba Specialty Chemicals ( 2 parts by mass Isopropyl alcohol 50 parts by mass
  • the clear hard coat layer coating composition was extruded and coated using a coater under the condition of a dry film thickness of 6 ⁇ , and then dried in a drying section set at 80 ° C. Thereafter, ultraviolet rays were irradiated using an ultraviolet irradiation facility.
  • the UV lamp used for UV irradiation used an output of 3 kW (high pressure mercury type manufactured by Eye Graphic Co., Ltd.), and the illuminance was 0 ⁇ lW / cm 2 .
  • the holding plate was set so that the surface temperature of the substrate was 25 ° C during irradiation.
  • a SiO film was formed under the condition that the film thickness was 25 nm according to the following conditions.
  • Power supply 1 High frequency side 13. 56MHz 6W / cm 2
  • Power supply 2 Low frequency side lOOKHz 5w / cm 2
  • Source gas Si_ ⁇ as 2 raw material was tetraethoxysilane (TEOS) is vaporized by bubbling (N Gas: lslm, 40 ° C)
  • the movable gantry electrode was manufactured by spraying alumina as a dielectric on the surface of a 200 mm wide and 300 mm long titanium plate.
  • a heat sink and a heater were installed on the back side so that the temperature of the substrate surface was always constant.
  • Electrode width 200mm
  • a substrate was placed on the movable gantry electrode, and a thin film was formed while continuously scanning to form a 25 ⁇ m SiO thin film.
  • a direct two-frequency method shown in FIG. 6 was used, and a titanium oxide transparent conductive film 1 having niobium as a dopant was formed on a substrate 1 according to the conditions shown below.
  • Power supply 1 Pearl Industry high frequency power supply, high frequency side 13. 56MHz 5W / cm 2
  • Power supply 2 SEREN high frequency power supply, low frequency side lOOKHz 5w / cm 2 [electrode condition]
  • the square electrode of the second electrode was manufactured by spraying alumina as a dielectric on a 30mm square hollow titanium pipe.
  • Electrode width 300mm
  • Second electrode slit gap 1.0 mm Gap between electrodes: 1 ⁇ Omm
  • Tetrizopropoxy titanium was vaporized by publishing as a raw material for TiO film formation (N gas: 3slm 60 ° C)
  • the movable gantry electrode was manufactured by spraying alumina as a dielectric on the surface of a 200 mm wide and 300 mm long titanium plate.
  • a heat sink and a heater were installed on the back side so that the temperature of the substrate surface was always constant.
  • Electrode width 200mm
  • the base temperature was adjusted so that the film formation temperature shown in Table 1 was reached.
  • the substrate 1 was placed on the mobile pedestal electrode, and film was formed while continuously scanning. A doped TiO film was formed.
  • the base material 1 having the titanium oxide transparent conductive film 1 produced above is post-treated with a reactive gas containing hydrogen according to the conditions shown below using the single-frequency direct-type atmospheric pressure plasma discharge treatment apparatus shown in FIG. (Resistance reduction treatment) is applied to make transparent conductive film sample 1.
  • High frequency power supply manufactured by Adtech Plasma Technology, 27MHz 10W / cm 2 (electrode condition)
  • the square electrode is a ceramic as a dielectric against a 30 mm square hollow titanium pipe.
  • the spray spraying process was performed.
  • Electrode width 300mm
  • Electrode (discharge) gap 2.0 mm
  • a transparent conductive film was formed in the same manner except that the titanium oxide transparent conductive film 2 was formed under the following gas conditions using a compound containing tantalum as a dopant in the titanium oxide transparent conductive film.
  • Membrane sample 2 was prepared.
  • Tetrizopropoxy titanium was vaporized by publishing as a raw material for TiO film formation (N gas: 3slm, 60 ° C).
  • Pentaethoxytantalum was vaporized by bubbling as a doping material (N gas: 3slm, 90. C).
  • the other conditions were the same as the conditions for forming the titanium oxide transparent conductive film 1.
  • a transparent conductive film sample 3 was prepared in the same manner as in the preparation of the transparent conductive film sample 1 except that the substrate temperature at the time of preparing the titanium oxide transparent conductive film was changed to 100 ° C.
  • a transparent conductive film sample 4 was prepared in the same manner as in the preparation of the transparent conductive film sample 1 except that the substrate temperature in post-treatment (annealing) was changed to 100 ° C.
  • the transparent conductive film sample 1 In the production of the transparent conductive film sample 1, the transparent conductive film was similarly prepared except that water vapor was used in place of hydrogen gas as an auxiliary gas as a gas condition during atmospheric pressure plasma discharge treatment in post-treatment (anneal treatment). Sample 5 was prepared.
  • transparent conductive film sample 1 In the production of transparent conductive film sample 1 above, instead of PET, the substrate was changed to a commercially available non-alkali glass (Coung, # 1737) with a thickness of 200 mm x 200 mm and a titanium oxide transparent conductive film was produced.
  • a transparent conductive film sample 6 was prepared in the same manner except that the substrate temperature at the time was changed to 200 ° C, the substrate temperature for post-treatment (annealing) was changed to 200 ° C, and the processing time was changed to 15 seconds. .
  • the transparent conductive film sample 7 was produced in the same manner except that the titanium oxide transparent conductive film was formed by the following sputtering method instead of the atmospheric pressure plasma CVD method. did.
  • TiO powder (99. 99%) and Nb O powder (99. 99%) were mixed at a ratio of 95: 5, then shaped and fired, and a 20cm diameter TiO-Nb O-based high-density sintered body (target) ) was produced.
  • the obtained target was attached to a batch type DC magnetron sputtering apparatus to form a film.
  • the magnetic flux density on the target was lOOOGauss.
  • the ultimate vacuum within the chamber one, not more than 5 X 10- 6 Pa, gas pressure during the sputtering was set to 2 X 10- 4 Pa.
  • As sputtering gas, argon gas and a mixed gas of argon and oxygen were used and introduced into the chamber by a separate system. Under these conditions, a film thickness of 100 ⁇ is formed on the glass substrate held by a 200 ° C heat insulating plate.
  • m Nb: TiO thin film was formed.
  • the mass ratio of argon to oxygen was 500: 1.
  • a transparent conductive film sample 8 was produced in the same manner except that the post-treatment (anneal treatment) was changed to the following vacuum plasma treatment method.
  • a plasma chemical vapor deposition apparatus shown in FIG. 3 described in JP-A-2002-127294 was used. That is, the base material was mounted in the chamber of the plasma chemical vapor deposition apparatus, and then the pressure in the chamber was reduced to an ultimate vacuum of 4.0 X 1CT 3 Pa by an oil rotary pump and an oil diffusion pump. Next, an electrode was placed near the coating drum so as to face the coating drum, and a high frequency power of 13.56 MHz was applied between the coating drum and the electrode. Then, under the condition that the substrate temperature is 100 ° C., hydrogen gas 50 sccm and argon gas lOOOsccm are introduced from the gas inlet provided near the electrode in the chamber 1, and the valve between the vacuum pump and the chamber 1 is introduced. By controlling the degree of opening and closing, the film forming chamber was kept at 6.7 Pa and annealing was performed.
  • a transparent conductive film sample 9 was prepared in the same manner except that the post-treatment (annealing) was changed to the following low-temperature thermal annealing method (reduction annealing method).
  • a glass substrate having a transparent conductive film Into the chamber one, it was placed a glass substrate having a transparent conductive film, the ultimate vacuum, 5 X 10 - 6 Pa after less, introducing hydrogen gas until the gas pressure becomes 0. 9 X 10 3 kPa Then, annealing was performed for 5 minutes under the condition of a substrate temperature of 200 ° C. The substrate temperature was raised to 200 ° C. over about 15 minutes, and after a desired time (amount time), the heat removal time was set to 15 minutes, and after purging with nitrogen, the substrate was taken out from the chamber.
  • the light transmittance at 550 nm of each transparent conductive film sample and each substrate used therefor was measured using a spectrophotometer V-530 manufactured by JASC O, and the light transmittance was determined according to the following equation.
  • Light transmittance (Transmissivity of transparent conductive film sample) / (Transmissivity of substrate) X 100
  • resistance value (ohm / mouth) was measured using the Hiresta MCP-HT450 type
  • the resistance value measured here has a certain degree of correlation with the homogeneity of the formed transparent conductive film, and indicates that the lower the resistance value, the higher the film homogeneity.
  • Table 1 shows the results obtained as described above.
  • the present invention water treatment gas pressure high pressure C pressure DV
  • the present invention Hydrogen gas pressure large pressure glass C VD
  • the present invention vacuum treatment water pressure atmospheric pressure C VD
  • the transparent conductive film sample prepared according to the method for forming a transparent conductive film mainly composed of titanium oxide of the present invention has light transmission performance and resistance performance compared to the comparative example.

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Abstract

La présente invention concerne un procédé de formation d'un film transparent électroconducteur essentiellement fait d'oxyde de titane et présentant d'excellentes qualités de transparence et d'électroconductivité sans être limité par un substrat. L'invention concerne plus particulièrement un procédé de formation de ce film transparent électroconducteur principalement fait d'oxyde de titane sur un substrat avec un traitement ultérieur. Ce procédé de formation de film transparent électroconducteur se caractérise en ce que le film transparent électroconducteur essentiellement fait d'oxyde de titane est un film mince essentiellement composé d'oxyde de titane comportant un dopant, et que le traitement ultérieur est un traitement au plasma dans lequel un gaz est introduit dans un espace de décharge et amené à l'état de plasma, à la suite de quoi le film transparent électroconducteur essentiellement fait d'oxyde de titane et formé sur le substrat subit un traitement consistant en une exposition au gaz à l'état de plasma.
PCT/JP2007/068789 2006-10-12 2007-09-27 Procédé de formation de film transparent électroconducteur WO2008044474A1 (fr)

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WO2010063530A2 (fr) * 2008-11-05 2010-06-10 Oerlikon Solar Ip Ag, Truebbach Dispositif de cellules solaires et procédé de fabrication associé
EP2211369A1 (fr) * 2009-01-23 2010-07-28 Applied Materials, Inc. Dispositif pour le traitement de substrats par un plasma
JP2010238400A (ja) * 2009-03-30 2010-10-21 Sumitomo Chemical Co Ltd 透明導電性基板の製造方法
WO2011139523A3 (fr) * 2010-04-27 2012-02-02 Ppg Industries Ohio, Inc. Procédé de dépôt d'un film de dioxyde de titane dopé par du niobium sur un substrat et substrat revêtu fabriqué par ce procédé
WO2013016369A1 (fr) * 2011-07-28 2013-01-31 Pilkington Group Limited Apcvd d'oxyde de titane dopé et article revêtu obtenu par ce procédé
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JP2017091898A (ja) * 2015-11-13 2017-05-25 株式会社日本製鋼所 プラズマ発生部およびプラズマスパッタ装置
US9899209B2 (en) 2014-12-08 2018-02-20 Samsung Electronics Co., Ltd. Electrically conductive thin films
JP2018039254A (ja) * 2016-07-26 2018-03-15 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ 電気性能を向上させるために金属改質及びプラズマ処理を施した熱可塑性材料
WO2021002753A1 (fr) * 2019-07-03 2021-01-07 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Plasma à commande spatiale

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US8551609B2 (en) 2010-04-27 2013-10-08 Ppg Industries Ohio, Inc. Method of depositing niobium doped titania film on a substrate and the coated substrate made thereby
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