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WO2009157177A1 - Ｆｔｏ／ｉｔｏ積層体を有する透明導電膜 - Google Patents

Ｆｔｏ／ｉｔｏ積層体を有する透明導電膜 Download PDF

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Publication number
WO2009157177A1
WO2009157177A1 PCT/JP2009/002844 JP2009002844W WO2009157177A1 WO 2009157177 A1 WO2009157177 A1 WO 2009157177A1 JP 2009002844 W JP2009002844 W JP 2009002844W WO 2009157177 A1 WO2009157177 A1 WO 2009157177A1
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Prior art keywords
film
fto
ito
transparent conductive
conductive film
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PCT/JP2009/002844
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English (en)
French (fr)
Inventor
山田茂男
大芦竜也
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority to JP2010517752A priority Critical patent/JP5601686B2/ja
Priority to US13/000,206 priority patent/US8557404B2/en
Priority to CN2009801235213A priority patent/CN102067243B/zh
Priority to KR1020137016698A priority patent/KR20130088886A/ko
Priority to EP20090769887 priority patent/EP2296154A4/en
Publication of WO2009157177A1 publication Critical patent/WO2009157177A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H10F77/247—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers comprising indium tin oxide [ITO]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to a transparent conductive film used for a transparent electrode plate and the like, and particularly to an FTO / ITO laminated film suitable for a transparent electrode of a dye-sensitized solar cell.
  • the dye-sensitized solar cell is a solar cell of a type that generates electricity by absorbing light and releasing electrons by a dye that absorbs sunlight.
  • EPFL Michael Gratzel of autoimmune Polytechnique Federale de Lausanne
  • the mechanism is that when light strikes the battery, the dye in the battery is excited and emits electrons. The electrons reach the transparent electrode via titanium oxide (TiO 2 ) and flow to the outside.
  • the dye that has become a cation by emitting electrons receives the electrons supplied from the other electrode via iodine (I) in the electrolyte and returns to the original state.
  • I iodine
  • Requirement for the transparent electrode used in such a solar cell includes low resistance, thermal stability, chemical stability, high permeability, moisture resistance, low cost, and the like.
  • a transparent conductive film for electrodes satisfying such conditions generally a tin oxide film (FTO film) doped with fluorine, which is resistant to heat and chemical conditions, is preferable to an indium oxide film (ITO film) doped with tin. .
  • Patent Document 1 it is preferable that the thickness of the ITO film is 100 nm to 1000 nm, the thickness of the FTO film is at least 30 nm to 350 nm, and that the thickness of the FTO film is 1 at a temperature of 250 to 700 ° C. It is described that the conductivity does not decrease even with heating for a period of time. Further, it is described that the FTO film must be continuously formed after the ITO film is formed.
  • a raw material compound solution that becomes an FTO film is immediately sprayed on a glass plate still at about 400 to 500 ° C., and before the ITO film deteriorates, a spray pyrolysis method (SPD method) is used. It is described that it is necessary to form an FTO film. However, the above method is not sufficient in that the entire film is thick and there is a problem in cost, and because the thickness of the FTO film is thick, the advantages of ITO cannot be fully utilized.
  • a transparent conductive film having an FTO / ITO laminated film that can be used for a transparent electrode plate of a solar cell, particularly a transparent electrode of a dye-sensitized solar cell, making use of the merits of FTO and ITO and meeting the cost. It was a challenge to do.
  • the inventors of the present invention have continuously conducted the process of moving the glass plate on the conveyor in the film forming furnace when the FTO / ITO laminated film is produced on the glass substrate by the pyrosol method.
  • the surface of the FTO film becomes an orthorhombic film, and even when the thickness of the FTO film is 20 nm or less, a laminated film having excellent heat resistance can be obtained. And completed the invention.
  • the present invention (1) A transparent conductive film comprising an ITO film and an FTO film for lamination on a substrate, wherein a part or all of the crystal structure on the surface of the FTO film is orthorhombic. film, (2) The change rate of the sheet resistance value after heating at 350 ° C. for 1 hour is 1.5 times or less, the transparent conductive film according to (1), (3) The transparent conductive film according to (1) or (2), wherein the sheet resistance value is 300 ⁇ / ⁇ or less.
  • the present invention also provides: (4) The transparent film according to any one of (1) to (3), wherein an ITO film is formed on a substrate by a pyrosol method, and then an FTO film is continuously formed on the ITO film.
  • the present invention relates to a method for manufacturing a conductive film.
  • the present invention also provides: (5) A transparent conductive film comprising an ITO film and an FTO film to be laminated on a substrate, wherein the FTO film has a thickness of 5 nm to 20 nm, and the FTO film is a continuous film Transparent conductive film, (6) The transparent conductive film according to (5), wherein the rate of change in sheet resistance after heating at 350 ° C. for 1 hour is 1.5 times or less, (7) The transparent conductive film according to (5) or (6), wherein the sheet resistance value is 300 ⁇ / ⁇ or less.
  • the present invention also provides: (8) The transparent film according to any one of (5) to (7), wherein an ITO film is formed on a substrate by a pyrosol method, and then an FTO film is continuously formed on the ITO film.
  • the present invention relates to a method for manufacturing a conductive film.
  • the transparent conductive film comprising the FTO / ITO laminated film of the present invention has an orthorhombic crystal structure on part or all of the FTO film surface, it has excellent heat resistance even when the film thickness is as thin as 5 nm to 20 nm. A good result was obtained that the rate of change in sheet resistance after heating at 350 ° C. for 1 hour was 1.5 times or less. Therefore, not only can it be used for a transparent electrode plate such as a liquid crystal display element or a solar battery, but it can also be used as a transparent electrode for a dye-sensitized solar battery. is there.
  • FIG. It is a figure which shows the X-ray-diffraction result of the thin film surface of an Example, the comparative example 1, and the comparative example 2.
  • FIG. It is a figure which shows the cross-section structure observation result by the cross-sectional TEM method of the laminated body of an Example. It is a figure which shows the cross-section observation result by the cross-sectional TEM method of the laminated body of the comparative example 1.
  • Transparent conductive film In the transparent conductive film of the present invention, an ITO film is provided on the substrate side, and an FTO film is laminated thereon. Part or all of the surface of the FTO film has an orthorhombic crystal structure.
  • a part of the surface is orthorhombic means a state in which orthorhombic crystals are included in an amount necessary for at least the rate of change of the sheet resistance value to be 1.5 times or less.
  • the rest is a tetragonal crystal or other crystal system, and is usually in a mixed crystal state.
  • the orthorhombic crystal is one of the seven crystal systems (cubic, hexagonal, rhombohedral, tetragonal, orthorhombic, monoclinic, triclinic) commonly used in the field of crystallography.
  • the length relationship is a ⁇ b ⁇ c
  • the identification of the crystal system is performed by X-ray diffraction, neutron diffraction, electron diffraction or the like of single crystals and powders.
  • the film is transferred onto a substrate that is transferred on a belt in a film forming furnace in which a plurality of film forming furnaces are connected.
  • the continuous film refers to a film in which crystals are arranged without gaps.
  • the film thickness of the ITO film and the FTO film is not limited as long as it can be used as a transparent electrode plate for liquid crystal display elements, solar cells, etc., but can take advantage of the advantages of FTO and ITO, cost, etc. From this point, the thickness of the FTO film is preferably 5 nm to 20 nm, and more preferably 10 nm to 20 nm. On the other hand, the thickness of the ITO film is preferably 20 nm to 60 nm, and more preferably 30 nm to 50 nm. Each of the FTO film and the ITO film is composed of at least one layer and can be laminated in multiple layers as long as the film thickness is not exceeded.
  • the laminated film of the ITO film and the FTO film described in Patent Document 1 has an ITO film thickness of 100 nm to 1000 nm and an FTO film thickness of 30 nm to 350 nm. According to this document, the thickness of the FTO film is required to be at least 30 nm for the protection of ITO, and the transparent conductive film of the present invention can be made thin for both the ITO film and the FTO film. It is.
  • the transparent conductive film of the present invention has excellent heat resistance against a temperature of 350 ° C. or higher even when the FTO film is as thin as 5 to 20 nm, and the rate of change in sheet resistance after heating for 1 hour at a temperature of 350 ° C. is 1. .5 times or less, preferably 1.2 times or less.
  • the sheet resistance value is required to be 300 ⁇ / ⁇ or less, particularly when used as a transparent electrode of a dye-sensitized solar cell, but can be adjusted to 300 ⁇ / ⁇ or less by adjusting the film thickness. Is possible.
  • the transparent conductive film of the present invention is laminated on a substrate.
  • a transparent substrate is usually used as the substrate, but it may not be transparent.
  • Specific examples of the transparent substrate include glass such as alkali glass and quartz glass, polyester such as polycarbonate, polyethylene terephthalate, and polyarylate, polyethersulfone resin, amorphous polyolefin, polystyrene, and acrylic resin. These materials are appropriately selected according to the intended use of the final product.
  • An inorganic oxide film can be formed between the base material and the transparent conductive film as needed to prevent an alkali component or the like from entering the transparent conductive film.
  • Transparent conductive film manufacturing method As a method for producing the transparent conductive film, any method can be used as long as it can form a film having the object physical property value of the present invention. Specifically, a sputtering method, an electron beam method, an ion plating method, a screen printing method. Or a chemical vapor deposition method (CVD method), a spray pyrolysis method (SPD method), a pyrosol method, etc. can be illustrated, but especially a pyrosol method can be illustrated preferably.
  • CVD method chemical vapor deposition method
  • SPD method spray pyrolysis method
  • pyrosol method etc.
  • the manufacturing method of this invention by a pyrosol method is demonstrated concretely.
  • the indium compound used in the ITO film forming solution a substance that is thermally decomposed to become indium oxide is preferable.
  • indium trisacetylacetonate In (CH 3 COCHCOCH 3 ) 3
  • indium trisbenzoylmethanate In (C 6 H 5 COCHCOC 6 H 5 ) 3
  • indium trichloride InCl 3
  • indium nitrate In (NO 3 ) 3
  • tin compound those which are thermally decomposed to become stannic oxide can be preferably used.
  • stannic chloride dimethyltin dichloride, dibutyltin dichloride, tetrabutyltin, stannic octoate ( Sn (OCOC 7 H 15 ) 2 ), dibutyltin maleate, dibutylzuzuacetate, dibutyltin bisacetylacetonate and the like.
  • a periodic table group 2 element such as Mg, Ca, Sr and Ba, a group 3 element such as Sc and Y, La, Ce, Nd, Lanthanoids such as Sm and Gd, Group 4 elements such as Ti, Zr and Hf, Group 5 elements such as V, Nb and Ta, Group 6 elements such as Cr, Mo and W, Group 7 elements such as Mn Group elements such as Co, Co, Group 10 elements such as Ni, Pd, and Pt, Group 11 elements such as Cu and Ag, Group 12 elements such as Zn and Cd, and Group 13 elements such as B, Al, and Ga
  • An ITO film can be formed by adding a simple substance such as a group element, a group 14 element such as Si, Ge or Pb, a group 15 element such as P, As or Sb, a group 16 element such as Se or Te, or a compound thereof. It can also be formed.
  • fluorine compound used in the FTO film forming solution examples include hydrogen fluoride, sodium fluoride, trifluoroacetic acid, difluoroethane, bromotrifluoromethane, and the like.
  • tin compound the tin compound used for manufacture of the said ITO film
  • the above compound is dissolved in an organic solvent such as alcohols such as methanol and ethanol, and ketones such as acetone, methyl butyl ketone and acetylacetone to prepare FTO film forming solution and FTO film forming solution.
  • organic solvent such as alcohols such as methanol and ethanol
  • ketones such as acetone, methyl butyl ketone and acetylacetone
  • the following process is performed.
  • a plurality of conveyor-type film-forming furnaces heated in advance to 400 to 750 ° C., preferably 400 to 550 ° C., are connected, and the substrate is put into the furnace.
  • a film is produced by contacting the surface of the material and thermally decomposing it.
  • the film thickness can be adjusted by changing the speed of the conveyor.
  • By connecting three or more film forming furnaces at least one of the ITO film and the FTO film can be a multilayer film.
  • another inorganic oxide film such as a SiO 2 film can be formed as the first substrate.
  • Example 1 Glass / SiO 2 / ITO / FTO Laminate (Continuous Film Formation) Three conveyor furnaces heated to 500 ° C. (furnace (1) to (3)) were connected, and a soda lime glass substrate (320 ⁇ 420 ⁇ 0.7 mm) was put into the conveyor furnace.
  • SiO 2 film forming solution (tetraethoxysilane (solution I)), in the second group, ITO film forming solution (acetylacetone solution (solution II) containing 0.2 mol / L of indium acetylacetone containing 5 mol% of stannous chloride)
  • ITO film forming solution acetylacetone solution (solution II) containing 0.2 mol / L of indium acetylacetone containing 5 mol% of stannous chloride
  • an FTO film forming solution ethanol solution containing 0.5 mol / L of dibutyltin diacetate containing 150 mol% of fluorine (solution III)
  • a laminate was continuously produced by blowing it into a conveyor furnace as a carrier gas and bringing it into thermal contact with the surface of the glass substrate.
  • the obtained laminate was glass / SiO 2 film (40 nm) / ITO film (40 nm) / FTO film (13 nm).
  • Comparative Example 1 Glass / SiO 2 / ITO / FTO Laminate (Discontinuous Film Formation Method)
  • the glass substrate is once taken out, and then the glass substrate is again put into the film forming furnace, and the FTO film is formed on the ITO film.
  • a laminated body having a film thickness almost the same as that of the example was formed by film formation.
  • two conveyor furnaces heated to 500 ° C. furnace (1) to (2)
  • a soda lime glass substrate (320 ⁇ 420 ⁇ 0.7 mm) is put into the conveyor furnace.
  • the SiO 2 film forming solution tetraethoxysilane (solution I)
  • the ITO film forming solution indium acetylacetone containing 5 mol% of stannic chloride is 0.2 mol / L
  • the laminated body was produced by the same method as Example 1 except having used each acetylacetone solution (solution II)).
  • the obtained laminate was glass / SiO 2 film (40 nm) / ITO film (40 nm).
  • one conveyor furnace heated to 500 ° C. was used, and the glass / SiO 2 / ITO laminate obtained in the first time was put into the conveyor furnace to prepare an FTO film forming solution (150 mol% fluorine).
  • a laminate was prepared in the same manner as in Example 1 except that an ethanol solution (solution III) containing 0.5 mol / L of dibutyltin diacetate was used.
  • the obtained laminate was glass / SiO 2 film (40 nm) / ITO film (40 nm) / FTO film (17 nm).
  • Comparative Example 2 Glass / SiO 2 / ITO / FTO Laminate
  • the first film formation was performed by the same method as Comparative Example 1.
  • the obtained laminate was glass / SiO 2 film (40 nm) / ITO film (40 nm).
  • a laminate was produced by the same method except that the conveyance speed was slower than that of Comparative Example 1.
  • the obtained laminate was glass / SiO 2 film (40 nm) / ITO film (40 nm) / FTO film (54 nm).
  • Example 1 Comparative Example 1 and Comparative Example 2
  • the film thickness, the sheet resistance value before and after heating at 350 ° C. for 1 hour, the rate of change, the visible light transmittance, the FTO film crystal system, and the cross-sectional structure are evaluated.
  • the results are shown in Table 1 and FIG.
  • the film thickness was measured using an ellipsometer (SE800 manufactured by Eimec), the sheet resistance value was measured using a four-terminal method, the visible light transmittance (550 nm) was measured using a spectrophotometer (Hitachi U4000), and the crystal system was used for thin film evaluation.
  • SE800 manufactured by Eimec
  • the sheet resistance value was measured using a four-terminal method
  • the visible light transmittance (550 nm) was measured using a spectrophotometer (Hitachi U4000)
  • the crystal system was used for thin film evaluation.

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Abstract

　本発明は、基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の表面の結晶構造の一部又は全部が斜方晶であることを特徴とする透明導電膜、及び基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の膜厚が５ｎｍ～２０ｎｍであり、かつＦＴＯ膜が連続膜であることを特徴とする透明導電膜を提供する。また、本発明は、パイロゾル法によりＩＴＯ膜を基材上に成膜した後、連続的にＩＴＯ膜上にＦＴＯ膜を成膜することを特徴とする上記透明導電膜の製造方法を提供する。

Description

ＦＴＯ／ＩＴＯ積層体を有する透明導電膜
　本発明は、透明電極板等に使用される透明導電膜に関し、特に色素増感太陽電池の透明電極などに好適なＦＴＯ／ＩＴＯ積層膜に関する。
　本願は、２００８年６月２４日に、日本に出願された特願２００８－１６４４１７号に基づき優先権を主張し、その内容をここに援用する。
　色素増感太陽電池は、太陽光を吸収する色素が光を吸収して電子を放出することにより発電する方式の太陽電池のことである。１９９１年、スイスEcole Polytechnique Federale de Lausanne （ＥＰＦＬ）のMichael Gratzel氏が発表した論文を契機に研究が進んできた。その機構は、電池に光が当たると電池中の色素が励起状態となり、電子を放出する。この電子は酸化チタン（ＴｉＯ２）を経由して透明電極に達し、外部に流れる。一方、電子を放出して陽イオンになった色素は、もう片方の電極から供給される電子を、電解液中のヨウ素（Ｉ）を経由して受け取り、元の状態に戻るというものである。
　このような太陽電池に用いられる透明電極に必要な条件として、低抵抗、熱安定性、化学的安定性、高透過性、耐湿性、低コストなどが挙げられる。このような条件を満たす電極用の透明導電性膜としては、一般にスズをドープした酸化インジウム膜（ＩＴＯ膜）より、熱、化学的条件に強いフッ素をドープした酸化スズ膜（ＦＴＯ膜）が好ましい。
　しかしながら、ＩＴＯ膜は透明性、導電性に優れていることから、液晶表示素子や太陽電池に広く使用されていることもあるため、ＩＴＯ膜の上にＦＴＯ膜を積層した膜も開発されている。その一例として、特許文献１がある。
　特許文献１には、ＩＴＯ膜の膜厚が１００ｎｍ～１０００ｎｍ、ＦＴＯ膜の膜厚は少なくとも３０ｎｍ～３５０ｎｍが良いこと、及び、ＦＴＯ膜がこの膜厚であると、温度２５０～７００℃での１時間の加熱によっても導電性は低下しないことが記載されている。また、ＦＴＯ膜の成膜はＩＴＯ膜の成膜後に連続して行う必要があることが記載されている。そのため、ＩＴＯ膜を形成した直後の、いまだ４００～５００℃程度にある硝子板に直ちにＦＴＯ膜となる原料化合物溶液を噴霧して、ＩＴＯ膜が劣化する前にスプレー熱分解法（ＳＰＤ法）によってＦＴＯ膜を成膜する必要があると記載されている。
　しかしながら、上記方法では、膜全体が厚いためにコスト上の課題があること、ＦＴＯ膜の膜厚が厚いためにＩＴＯの有するメリットが十分生かせないなどの点で十分ではなかった。
特開２００３－３２３８１８号公報
　そこで、太陽電池の透明電極板等、特に色素増感太陽電池の透明電極などに使用できて、ＦＴＯ及びＩＴＯの有するメリットを生かせ、コスト的に見合うＦＴＯ／ＩＴＯ積層膜を有する透明導電膜を作製することが課題であった。
　上本発明者らは、鋭意検討を重ねた結果、パイロゾル法によりガラス基材上にＦＴＯ／ＩＴＯ積層膜を作製する場合に、成膜炉の中で、ガラス板をコンベアで移動させる間に連続してＩＴＯ膜とＦＴＯ膜を積層することにより、ＦＴＯ膜の表面が斜方晶を有する膜となり、ＦＴＯ膜の膜厚が２０ｎｍ以下と薄い場合でも、耐熱性に優れた積層膜が得られることを見出し、発明を完成した。
　すなわち、本発明は、
（１）基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の表面の結晶構造の一部又は全部が斜方晶であることを特徴とする透明導電膜、
（２）３５０℃で１時間加熱後のシート抵抗値の変化率が１．５倍以下であることを特徴とする（１）記載の透明導電膜、
（３）シート抵抗値が３００Ω／□以下であることを特徴とする（１）または(２)に記載の透明導電膜に関する。
　また、本発明は、
（４）パイロゾル法によりＩＴＯ膜を基材上に成膜した後、連続的にＩＴＯ膜上にＦＴＯ膜を成膜することを特徴とする（１）から（３）のいずれかに記載の透明導電膜の製造方法に関する。
　また、本発明は、
（５）基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の膜厚が５ｎｍ～２０ｎｍであり、かつＦＴＯ膜が連続膜であることを特徴とする透明導電膜、
（６）３５０℃で１時間加熱後のシート抵抗値の変化率が１．５倍以下であることを特徴とする（５）記載の透明導電膜、
（７）シート抵抗値が３００Ω／□以下であることを特徴とする（５）または(６)に記載の透明導電膜に関する。
　また、本発明は、
（８）パイロゾル法によりＩＴＯ膜を基材上に成膜した後、連続的にＩＴＯ膜上にＦＴＯ膜を成膜することを特徴とする（５）から（７）のいずれかに記載の透明導電膜の製造方法に関する。
　本発明のＦＴＯ／ＩＴＯ積層膜からなる透明導電膜はＦＴＯ膜表面の一部又は全部が斜方晶の結晶構造を有することから、膜厚が５ｎｍ～２０ｎｍと薄い場合でも、耐熱性に優れ、３５０℃で１時間加熱後のシート抵抗値の変化率が１．５倍以下という好結果が得られた。そのため、液晶表示素子や太陽電池などの透明電極板等に使用可能であることはもちろんのこと、特に、色素増感太陽電池の透明電極としても使用可能であることが本発明の優れた点である。
実施例、比較例１及び比較例２の薄膜表面のＸ線回折結果を示す図である。 実施例の積層体の断面ＴＥＭ法による断面構造観察結果を示す図である。 比較例１の積層体の断面ＴＥＭ法による断面構造観察結果を示す図である。
　（透明導電膜）
　本発明の透明導電膜は、基材側にＩＴＯ膜が設けられ、その上にＦＴＯ膜が積層されている。ＦＴＯ膜の表面の一部又は全部が斜方晶の結晶構造を有している。
　本発明において、表面の一部が斜方晶とは、少なくとも、シート抵抗値の変化率が１．５倍以下となるために必要な量だけ斜方晶が含まれている状態をいう。結晶構造の一部が斜方晶を有している場合、残りは正方晶又はその他の結晶系であり、通常、混晶状態となる。
　斜方晶とは、結晶学の分野で一般に用いられている７つの結晶系（立方晶、六方晶、菱面体晶、正方晶、斜方晶、単斜晶、三斜晶）のうち、軸長の関係がａ≠ｂ≠ｃであり、軸角の関係がα＝β＝γ＝９０°であるものをいう。結晶系の同定は、単結晶および粉末のＸ線回折、中性子線回折、電子線回折等により行われる。
　斜方晶の結晶構造を生成させるためには、特にパイロゾル法により成膜する場合、後述するように、複数の成膜炉を連結した成膜炉内においてベルト上を移送される基材上にＩＴＯ膜の成膜後に、連結した成膜炉内で引き続き連続的にＦＴＯ膜を成膜することが必要である。ここで、連続膜とは、結晶が隙間なく並んでいる膜をいう。成膜炉でＩＴＯ膜を成膜後、一旦成膜炉外に出した後、再度成膜炉でＦＴＯ膜を成膜すると、ＦＴＯ膜の表面構造は正方晶になるとともに、シート抵抗値の変化率は１．５倍を超える。
　また、ＩＴＯ膜及びＦＴＯ膜の膜厚は、液晶表示素子や太陽電池などの透明電極板等として使用可能である限り制限はないが、ＦＴＯ、ＩＴＯの有するメリットを生かすことができ、かつコストなどの点からＦＴＯ膜の膜厚は、５ｎｍ～２０ｎｍが好ましく、１０ｎｍ～２０ｎｍがより好ましい。一方、ＩＴＯ膜の膜厚は２０ｎｍ～６０ｎｍが好ましく、３０ｎｍ～５０ｎｍがより好ましい。
　ＦＴＯ膜及びＩＴＯ膜は各々、少なくとも１層からなり、前記膜厚を越えない限り、多層に積層できる。
　前記特許文献１に記載されたＩＴＯ膜とＦＴＯ膜の積層膜は、ＩＴＯ膜の膜厚が１００ｎｍ～１０００ｎｍ、ＦＴＯ膜の膜厚は３０ｎｍ～３５０ｎｍである。同文献では、ＦＴＯ膜の膜厚はＩＴＯの保護のために少なくとも３０ｎｍ必要とされているに比べて、本発明の透明導電膜は膜厚がＩＴＯ膜、ＦＴＯ膜共に薄くすることもできることが特徴である。
　本発明の透明導電膜は、ＦＴＯ膜が５ｎｍ～２０ｎｍと薄い場合でも３５０℃以上の温度に対する耐熱性が優れており、３５０℃の温度で１時間の加熱後のシート抵抗値の変化率が１．５倍以下、好ましくは、１．２倍以下である。また、シート抵抗値は、特に色素増感太陽電池の透明電極として使用する場合は３００Ω／□以下であることが要求されているが、膜厚を調整することにより３００Ω／□以下とすることが可能である。
（透明電極用基材）
　本発明の透明導電膜は基材上に積層される。基材は、通常、透明基材が使用されるが、透明でなくてもよい。
　透明基材は、具体的には、アルカリガラス、石英ガラス等のガラス、ポリカーボネート、ポリエチレンテレフタレート、ポリアリレート等のポリエステル、ポリエーテルスルホン系樹脂、アモルファスポリオレフィン、ポリスチレン、アクリル樹脂等が挙げられる。これらの材質は、最終的に用いる製品の用途に応じて最適なものが適宜選択される。
　基材と透明導電膜との間には必要に応じて透明導電膜にアルカリ成分等が侵入するのを防止するために無機酸化物膜を形成することができる。無機酸化物膜として具体的には、ケイ素酸化物（ＳｉＯＸ），アルミニウム酸化物（Ａｌ２ＯＸ），チタン酸化物（ＴｉＯＸ），ジルコニウム酸化物（ＺｒＯＸ），イットリウム酸化物（Ｙ２ＯＸ），イッテルビウム酸化物（Ｙｂ２ＯＸ），マグネシウム酸化物（ＭｇＯＸ），タンタル酸化物（Ｔａ２ＯＸ），セリウム酸化物（ＣｅＯＸ）またはハフニウム酸化物（ＨｆＯＸ）、有機ポリシラン化合物から形成されるポリシラン膜、ＭｇＦ２膜、ＣａＦ２膜、ＳｉＯＸとＴｉＯＸの複合酸化物等からなる膜を例示することができる。
（透明導電膜の製法）
　透明導電膜の製造方法としては、本発明の目的とする物性値を有する膜を成膜できる方法であればよく、具体的には、スパッター法、電子ビーム法、イオンプレーテイング法、スクリーン印刷法又は化学的気相成長法（ＣＶＤ法）、スプレー熱分解法（ＳＰＤ法）、パイロゾル法等を例示することができるが、特にパイロゾル法を好ましく例示することができる。
　以下に、パイロゾル法による本発明の製法について具体的に説明する。
　ＩＴＯ膜形成溶液に用いられるインジウム化合物としては、熱分解して酸化インジウムになる物質が好ましく、具体的には、インジウムトリスアセチルアセトナート（Ｉｎ（ＣＨ３ＣＯＣＨＣＯＣＨ３）３）、インジウムトリスベンゾイルメタネート（Ｉｎ（Ｃ６Ｈ５ＣＯＣＨＣＯＣ６Ｈ５）３）、三塩化インジウム（ＩｎＣｌ３）、硝酸インジウム（Ｉｎ（ＮＯ３）３）、インジウムトリイソプロポキシド（Ｉｎ（ＯＰｒ－ｉ）３）等を例示することができる。
　また、スズ化合物としては、熱分解して酸化第２スズになるものを好ましく用いることができ、具体的には、塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート（Ｓｎ（ＯＣＯＣ７Ｈ１５）２）、ジブチルスズマレエート、ジブチルズズアセテート、ジブチルスズビスアセチルアセトナート等を挙げることができる。
　なお、前記インジウム化合物及びスズ化合物に加えて、第３成分として、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の周期律表第２族元素、Ｓｃ、Ｙ等の第３族元素、Ｌａ、Ｃｅ、Ｎｄ、Ｓｍ、Ｇｄ等のランタノイド、Ｔｉ、Ｚｒ、Ｈｆ等の第４族元素、Ｖ、Ｎｂ、Ｔａ等の第５族元素、Ｃｒ、Ｍｏ、Ｗ等の第６族元素、Ｍｎ等の第７族元素、Ｃｏ等の第９族元素、Ｎｉ、Ｐｄ、Ｐｔ等の第１０族元素、Ｃｕ、Ａｇ等の第１１族元素、Ｚｎ、Ｃｄ等の第１２族元素、Ｂ、Ａｌ、Ｇａ等の第１３族元素、Ｓｉ、Ｇｅ、Ｐｂ等の第１４族元素、Ｐ、Ａｓ、Ｓｂ等の第１５族元素、Ｓｅ、Ｔｅ等の第１６族元素等の単体若しくはこれらの化合物を添加してＩＴＯ膜を形成することもできる。
　ＦＴＯ膜形成溶液に用いられるフッ素化合物としては、フッ化水素、フッ化ナトリウム、トリフルオロ酢酸、ジフルオロエタン、ブロモトリフルオロメタンなどを挙げることができる。また、スズ化合物としては、上記ＩＴＯ膜の製造に用いられるスズ化合物を用いることができる。
　上記化合物を、メタノール、エタノール等のアルコール類、アセトン、メチルブチルケトン、アセチルアセトン等のケトン類等の有機溶媒に溶解して、ＦＴＯ膜形成溶液及びＦＴＯ膜形成溶液を調製する。
　パイロゾル法により透明基材上にＩＴＯ膜及びＦＴＯ膜を成膜するには、以下のようにして行う。
　予め４００～７５０℃、好ましくは４００～５５０℃に加熱したコンベア式成膜炉を複数基連結し、基材を炉内に投入する。第１基目の炉内でＩＴＯ膜形成溶液を、第２基目の炉内でＦＴＯ膜形成溶液を、それぞれ超音波で霧滴状にして空気をキャリアガスとしてコンベア炉の中に吹き込み、基材の表面に接触させて熱分解させることにより、膜を作製する。膜厚はコンベアの速度を変えることにより調整することができる。
　成膜炉を３基以上連結することにより、ＩＴＯ膜、ＦＴＯ膜の少なくともいずれかを多層膜とすることもできる。また、第１基目でＳｉＯ２膜などの他の無機酸化物膜を成膜することもできる。　
　以下に、実施例について示すが、本発明の技術的範囲は、これに限定されるものではない。
（実施例１）　　ガラス／ＳｉＯ２／ＩＴＯ／ＦＴＯ積層体　（連続成膜）
　５００℃に加熱したコンベアー炉を３基（炉（１）～（３））連結し、ソーダライムガラス基材（３２０×４２０×０．７ｍｍ）をコンベアー炉内に投入し、第１基においてはＳｉＯ２膜形成溶液（テトラエトキシシラン（溶液Ｉ））、第２基においてはＩＴＯ膜形成溶液（塩化第２スズを５モル％含むインジウムアセチルアセトンを０．２モル／Ｌ含むアセチルアセトン溶液（溶液ＩＩ））、第３基においてはＦＴＯ膜形成溶液（フッ素を１５０モル％含むジブチルスズジアセテートを０．５モル／Ｌ含むエタノール溶液（溶液ＩＩＩ））をそれぞれ用い、超音波で霧滴状にして空気をキャリアガスとしてコンベアー炉の中に吹き込み、ガラス基材の表面に接触させて熱分解させることにより、積層体を連続的に作製した。得られた積層体は、ガラス／ＳｉＯ２膜（４０ｎｍ）／ＩＴＯ膜（４０ｎｍ）／ＦＴＯ膜（１３ｎｍ）であった。
（比較例１）　　　ガラス／ＳｉＯ２／ＩＴＯ／ＦＴＯ積層体　（非連続成膜法）
　比較のために、実施例と同じ組成のＩＴＯ膜をガラス基材に成膜後、一旦ガラス基材を取り出し、その後再度成膜炉にガラス基材を投入してＩＴＯ膜の上にＦＴＯ膜を成膜して実施例とほぼ同じ膜厚の積層体を作製した。
　１回目の成膜では、５００℃に加熱したコンベアー炉を２基（炉（１）～（２））連結し、ソーダライムガラス基材（３２０×４２０×０．７ｍｍ）をコンベアー炉内に投入し、第１基においてはＳｉＯ２膜形成溶液（テトラエトキシシラン（溶液Ｉ））、第２基においてはＩＴＯ膜形成溶液（塩化第２スズを５モル％含むインジウムアセチルアセトンを０．２モル／Ｌ含むアセチルアセトン溶液（溶液ＩＩ））をそれぞれ用いた以外は実施例１と同じ方法で積層体を作製した。得られた積層体は、ガラス／ＳｉＯ２膜（４０ｎｍ）／ＩＴＯ膜（４０ｎｍ）であった。
　２回目の成膜では５００℃に過熱したコンベアー炉１基を使用し、１回目で得られたガラス／ＳｉＯ２／ＩＴＯ積層体をコンベアー炉に投入し、ＦＴＯ膜形成溶液（フッ素を１５０モル％含むジブチルスズジアセテートを０．５モル／Ｌ含むエタノール溶液（溶液ＩＩＩ））を用いた以外は実施例１と同じ方法で積層体を作製した。得られた積層体は、ガラス／ＳｉＯ２膜（４０ｎｍ）／ＩＴＯ膜（４０ｎｍ）／ＦＴＯ膜（１７ｎｍ）であった。
（比較例２）　ガラス／ＳｉＯ２／ＩＴＯ／ＦＴＯ積層体
　１回目の成膜は、比較例１と同じ方法で積層体を作製した。得られた積層体は、ガラス／ＳｉＯ２膜（４０ｎｍ）／ＩＴＯ膜（４０ｎｍ）であった。
　２回目の成膜は、搬送速度を比較例１よりも遅くした以外は同じ方法で積層体を作製した。得られた積層体は、ガラス／ＳｉＯ２膜（４０ｎｍ）／ＩＴＯ膜（４０ｎｍ）／ＦＴＯ膜（５４ｎｍ）であった。
　上記実施例１、比較例１及び比較例２につき、膜厚、３５０℃で１時間加熱前後のシート抵抗値、変化率、可視光透過率、ＦＴＯ膜の結晶系、断面構造の評価を行ない、結果を表１及び図１に示す。
　尚、膜厚はエリプソメータ（アイメック社製ＳＥ８００）を用い、シート抵抗値は４端子法により、可視光透過率（５５０ｎｍ）は分光光度計（日立社製Ｕ４０００）を用い、結晶系は薄膜評価用試料水平型Ｘ線回折装置（リガク社製SmartLab）を用い、断面構造は断面ＴＥＭ法によりそれぞれ評価した。
　その結果、本発明品は、従来品と比較して、ＦＴＯ膜厚が薄いにも関わらず耐熱性が向上していることがわかった（表１）。
　また、本発明品のＦＴＯ膜の結晶系は斜方晶となり、従来品のＦＴＯ膜の結晶系（正方晶）とは異なることがわかった（図１）。さらに本発明品のＦＴＯ膜の表面は、微細凹凸はあるものの、表面平坦性が良好であったが（図２）、従来品のＦＴＯ膜の表面は、表面凹凸があり、表面平坦性が良くないことがわかった（図３）。
Figure JPOXMLDOC01-appb-T000001

Claims (8)

  1. 　基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の表面の結晶構造の一部又は全部が斜方晶であることを特徴とする透明導電膜。
  2. 　３５０℃で１時間加熱後のシート抵抗値の変化率が１．５倍以下であることを特徴とする請求項１記載の透明導電膜。
  3. 　シート抵抗値が３００Ω／□以下であることを特徴とする請求項１又は２記載の透明導電膜。
  4. 　パイロゾル法によりＩＴＯ膜を基材上に成膜した後、連続的にＩＴＯ膜上にＦＴＯ膜を成膜することを特徴とする請求項１から３のいずれかに記載の透明導電膜の製造方法。　
  5. 　基材上に積層するためのＩＴＯ膜及びＦＴＯ膜からなる透明導電膜であって、ＦＴＯ膜の膜厚が５ｎｍ～２０ｎｍであり、かつＦＴＯ膜が連続膜であることを特徴とする透明導電膜。
  6. 　３５０℃で１時間加熱後のシート抵抗値の変化率が１．５倍以下であることを特徴とする請求項５記載の透明導電膜。
  7. 　シート抵抗値が３００Ω／□以下であることを特徴とする請求項５又は６記載の透明導電膜。
  8. 　パイロゾル法によりＩＴＯ膜を基材上に成膜した後、連続的にＩＴＯ膜上にＦＴＯ膜を成膜することを特徴とする請求項５から７のいずれかに記載の透明導電膜の製造方法。
PCT/JP2009/002844 2008-06-24 2009-06-22 Ｆｔｏ／ｉｔｏ積層体を有する透明導電膜 Ceased WO2009157177A1 (ja)

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US13/000,206 US8557404B2 (en) 2008-06-24 2009-06-22 Transparent conductive film having FTO/ITO laminate
CN2009801235213A CN102067243B (zh) 2008-06-24 2009-06-22 具有fto/ito层叠体的透明导电膜
KR1020137016698A KR20130088886A (ko) 2008-06-24 2009-06-22 Ｆｔｏ／ｉｔｏ 적층체를 갖는 투명 도전막
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