WO2010064719A1 - 透明導電膜の製造方法及び透明導電膜、透明導電基板並びにそれを用いたデバイス - Google Patents
透明導電膜の製造方法及び透明導電膜、透明導電基板並びにそれを用いたデバイス Download PDFInfo
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- WO2010064719A1 WO2010064719A1 PCT/JP2009/070442 JP2009070442W WO2010064719A1 WO 2010064719 A1 WO2010064719 A1 WO 2010064719A1 JP 2009070442 W JP2009070442 W JP 2009070442W WO 2010064719 A1 WO2010064719 A1 WO 2010064719A1
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- Prior art keywords
- transparent conductive
- compound
- conductive film
- organic
- oxide
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- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 description 1
- SBFKENUEAOCRNR-UHFFFAOYSA-K indium(3+);triformate Chemical compound [In+3].[O-]C=O.[O-]C=O.[O-]C=O SBFKENUEAOCRNR-UHFFFAOYSA-K 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 description 1
- PPFNAOBWGRMDLL-UHFFFAOYSA-N methyl 2-ethoxyacetate Chemical compound CCOCC(=O)OC PPFNAOBWGRMDLL-UHFFFAOYSA-N 0.000 description 1
- YVWPDYFVVMNWDT-UHFFFAOYSA-N methyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OC YVWPDYFVVMNWDT-UHFFFAOYSA-N 0.000 description 1
- AKWHOGIYEOZALP-UHFFFAOYSA-N methyl 2-methoxy-2-methylpropanoate Chemical compound COC(=O)C(C)(C)OC AKWHOGIYEOZALP-UHFFFAOYSA-N 0.000 description 1
- XPIWVCAMONZQCP-UHFFFAOYSA-N methyl 2-oxobutanoate Chemical compound CCC(=O)C(=O)OC XPIWVCAMONZQCP-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- AYHLARGFMBMSSU-UHFFFAOYSA-N pentane-2,4-dione;tantalum Chemical compound [Ta].CC(=O)CC(C)=O AYHLARGFMBMSSU-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XEABSBMNTNXEJM-UHFFFAOYSA-N propagermanium Chemical compound OC(=O)CC[Ge](=O)O[Ge](=O)CCC(O)=O XEABSBMNTNXEJM-UHFFFAOYSA-N 0.000 description 1
- KWUQLGUXYUKOKE-UHFFFAOYSA-N propan-2-ol;tantalum Chemical compound [Ta].CC(C)O.CC(C)O.CC(C)O.CC(C)O.CC(C)O KWUQLGUXYUKOKE-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- CYIRLFJPTCUCJB-UHFFFAOYSA-N propyl 2-methoxypropanoate Chemical compound CCCOC(=O)C(C)OC CYIRLFJPTCUCJB-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- HDVLQIDIYKIVRE-UHFFFAOYSA-N tetrabutylgermane Chemical compound CCCC[Ge](CCCC)(CCCC)CCCC HDVLQIDIYKIVRE-UHFFFAOYSA-N 0.000 description 1
- QQXSEZVCKAEYQJ-UHFFFAOYSA-N tetraethylgermanium Chemical compound CC[Ge](CC)(CC)CC QQXSEZVCKAEYQJ-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UMRPCNGKANTZSN-UHFFFAOYSA-N tributylgermanium Chemical compound CCCC[Ge](CCCC)CCCC UMRPCNGKANTZSN-UHFFFAOYSA-N 0.000 description 1
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
-
- 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
- C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
-
- 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
- C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- 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
Definitions
- the present invention relates to a transparent conductive film and a method for producing the transparent conductive film. Specifically, a transparent conductive film formed on a heat-resistant substrate such as glass or ceramics, having both transparency and conductivity, and excellent in film strength, and a transparent conductive film obtained by the transparent conductive film manufacturing method.
- the present invention relates to a film, and further to a transparent conductive substrate using the transparent conductive film and a device using the transparent conductive substrate.
- Transparent electrode for display element such as liquid crystal display, electroluminescence, plasma display, transparent electrode for touch panel, solar cell, etc., forming material for transparent conductive film used for functional coating such as heat ray reflection, electromagnetic wave shielding, antistatic, antifogging etc.
- ITO Indium Tin Oxide
- the ITO transparent conductive film As a method for producing the ITO transparent conductive film, physical methods such as vacuum vapor deposition, sputtering, and chemical vapor deposition are widely used. These methods can form a uniform ITO transparent conductive film excellent in transparency and conductivity on a substrate.
- the film forming apparatus used for this is very expensive because it is based on a vacuum vessel, and the component gas pressure in the manufacturing apparatus must be precisely controlled every time the substrate is formed. There is a problem with sex.
- a method of coating on a substrate using a coating solution for forming a transparent conductive film in which an indium compound and a tin compound are dissolved in a solvent (hereinafter sometimes referred to as “coating method”). ) Is being considered.
- this coating method an ITO transparent conductive film is formed by a simple manufacturing process of coating, drying, and firing a coating liquid for forming a transparent conductive film on a substrate.
- coating solutions using nitrates or halides have the problem of corrosive gases such as nitrogen oxides and chlorine being generated during firing, resulting in equipment corrosion and environmental contamination.
- coating solutions using metal alkoxides Since the raw material is easily hydrolyzed, there is a problem in the stability of the coating solution.
- many of the coating liquids using the organometallic compound described in the patent document have a problem that wettability with respect to the substrate is poor and a non-uniform film is easily formed.
- acetylacetone indium (formal name: tris (acetylacetonato) indium: In (C 5 H 7 O 2 ) 3 )
- acetylacetone tin (formal name: di-n-butoxide) bis (2,4-pentanedionato) tin: [Sn (C 4 H 9 ) 2 (C 5 H 7 O 2) 2])
- hydroxypropyl cellulose alkylphenols and / or alkenyl phenols and a dibasic acid ester and /
- the coating liquid for transparent conductive film formation containing a benzyl acetate (for example, refer patent document 9) is disclosed.
- This coating solution improves the wettability of the coating solution to the substrate by containing hydroxypropyl cellulose in a mixed solution of acetylacetone indium and acetylacetone tin, and at the same time, the viscosity of the coating solution is controlled by the content of hydroxypropylcellulose as a viscosity agent. It is possible to adjust and adopt various coating methods such as spin coating, spray coating, dip coating, screen printing, and wire bar coating.
- an improved coating solution for spin coating contains an organic indium compound such as acetylacetone indium and indium octylate, an organic tin such as acetylacetone tin and tin octylate, and an organic solvent, and the organic solvent contains alkylphenol and / or An acetylacetone solution in which alkenylphenol is dissolved, and a coating liquid for forming a transparent conductive film using a solution obtained by diluting an alkylphenol and / or an acetylacetone solution in which alkenylphenol is dissolved with alcohol have been proposed (for example, see Patent Document 10).
- This coating solution has a low viscosity and can be used for spray coating, dip coating as well as spin coating.
- the transparent conductive film formed by applying, drying, and baking such various ITO transparent conductive film forming coating liquids on the substrate the organic indium compound in the coating liquid is thermally decomposed during baking.
- the formed ITO fine particles are difficult to be densified, and the resulting transparent conductive film has problems such as insufficient conductivity and low film strength. It was. Therefore, a transparent conductive film having better conductivity and film strength has been desired for use in transparent electrodes such as displays, touch panels, and solar cells.
- the present invention relates to a transparent conductive film having good transparency and high conductivity formed by using an ink coating method, which is a low-cost and simple method for producing a transparent conductive film, and excellent in film strength, and the transparent conductive film. It aims at providing the manufacturing method of a film
- the inventors have applied a coating solution for forming a transparent conductive film containing, as a main component, one or more organic metal compounds of an organic indium compound, an organic tin compound, and an organic zinc compound on a heat resistant substrate.
- a coating solution for forming a transparent conductive film containing, as a main component, one or more organic metal compounds of an organic indium compound, an organic tin compound, and an organic zinc compound on a heat resistant substrate As a result of intensive research on transparent conductive films mainly composed of at least one of indium oxide, tin oxide, and zinc oxide obtained by coating, drying, and baking, the dew point was increased during the heating process during the baking.
- an air atmosphere having a low water content, ie, a low water vapor content is applied, the crystal growth of the conductive oxide in the initial stage of firing is suppressed, so that the conductive oxide fine particle layer densely filled with the conductive oxide fine particles is formed.
- the first invention of the present invention is a coating process in which a coating liquid for forming a transparent conductive film containing an organometallic compound as a main component is applied on a heat resistant substrate to form a coating film, and the coating film is dried.
- at least the inorganic component is crystallized in an oxygen-containing atmosphere having a dew point of ⁇ 10 ° C. or less in a dry coating film whose main component is an organometallic compound formed in the drying step.
- Conductive baking is performed at a temperature higher than the baking temperature, and the organic components contained in the dried coating film are removed by thermal decomposition or combustion, or thermal decomposition and combustion, so that the conductive oxide fine particles mainly composed of metal oxide are dense.
- Conductive filling A step of forming an oxide fine particle layer, and the organometallic compound is composed of at least one of an organoindium compound, an organotin compound, and an organozinc compound, and the metal oxide is composed of indium oxide, tin oxide, and oxide. It is a manufacturing method of the transparent conductive film which is any one or more of zinc.
- a second invention of the present invention is a coating step of coating a transparent conductive film forming coating solution containing an organometallic compound and a dopant organometallic compound as main components on a heat-resistant substrate to form a coating film,
- Each process of the drying process which dries a coating film and forms a dry coating film, and the baking process which bakes a dry coating film and forms the inorganic film which has the inorganic component which is a metal oxide containing a dopant metal compound as a main component
- the baking step is a dew point of ⁇ 10 ° C.
- a dry coating film mainly comprising the organometallic compound and the organometallic compound for dopant formed in the drying step In the following oxygen-containing atmosphere, firing is performed to raise the temperature to at least the firing temperature at which crystallization of the inorganic component occurs, and the organic component contained in the dry coating film is thermally decomposed or burned, or thermally decomposed and It is a step of forming a conductive oxide fine particle layer densely filled with conductive oxide fine particles containing a metal oxide as a main component and containing a dopant metal compound by removing by firing, and the organometallic compound is organic
- the content ratio of the organometallic compound and the organometallic compound for dopant is 99.9: 0.1 to 66.7 in terms of molar ratio of organometallic compound: organometallic compound for dopant.
- a range of 33.3 is the method for producing a transparent conductive film according to the second invention.
- the organometallic compound is an organoindium compound
- the organometallic compound for dopant is an organotin compound, an organotitanium compound, an organogermanium compound, an organozinc compound, an organotungsten compound, an organic One or more of a zirconium compound, an organic tantalum compound, an organic niobium compound, an organic hafnium compound, and an organic vanadium compound
- the dopant metal compound is tin oxide, titanium oxide, germanium oxide, zinc oxide, tungsten oxide, zirconium oxide
- the method for producing a transparent conductive film according to the second or third invention which is one or more of tantalum oxide, niobium oxide, hafnium oxide, and vanadium oxide.
- the organometallic compound is composed of an organotin compound, and the organometallic compound for dopant is at least one of an organic indium compound, an organic antimony compound, and an organophosphorus compound. It is a manufacturing method of the transparent conductive film as described in this invention.
- the organometallic compound comprises an organozinc compound
- the organometallic compound for dopant is one or more of an organoaluminum compound, an organoindium compound, and an organogallium compound. It is a manufacturing method of the transparent conductive film as described in invention of 3.
- a seventh invention of the present invention is the method for producing a transparent conductive film according to any one of the first to sixth inventions, wherein the organic indium compound is acetylacetone indium.
- an oxygen-containing atmosphere having a dew point of 0 ° C. or higher is obtained in the oxygen-containing atmosphere having a dew point of ⁇ 10 ° C. or lower, followed by firing at least to a firing temperature at which crystallization of the inorganic component occurs.
- the ninth aspect of the present invention following firing at a firing temperature of 300 ° C. or higher in an oxygen-containing atmosphere having a dew point of ⁇ 10 ° C. or lower, a firing temperature of 250 ° C. or higher in a neutral or reducing atmosphere.
- the method for producing a transparent conductive film according to the first or second invention characterized by firing.
- a firing temperature at which the crystallization of the inorganic component occurs is raised to a temperature equal to or higher than the firing temperature.
- the method for producing a transparent conductive film according to the eighth invention is characterized in that firing is performed at a firing temperature of 250 ° C. or higher.
- the neutral atmosphere is at least one of nitrogen gas and inert gas, or the reducing atmosphere is hydrogen gas and at least one of hydrogen gas or organic solvent vapor in the neutral atmosphere.
- the dew point of the oxygen-containing atmosphere in firing in an oxygen-containing atmosphere having a dew point of -10 ° C or lower is -20 ° C or lower. It is a manufacturing method of the transparent conductive film in any one of.
- the coating method for forming the transparent conductive film forming liquid on the heat resistant substrate in the coating step is an inkjet printing method, a screen printing method, a gravure printing method, an offset printing method, or a flexographic printing method.
- 1st or 2nd invention characterized by being one of dispenser printing method, slit coating method, die coating method, doctor blade coating method, wire bar coating method, spin coating method, dip coating method and spray coating method It is a manufacturing method of the transparent conductive film of description.
- the fourteenth invention of the present invention is a transparent conductive film obtained by the method for producing a transparent conductive film according to any one of the first to thirteenth inventions.
- a fifteenth aspect of the present invention is a transparent conductive substrate comprising a transparent conductive film on a heat-resistant substrate, wherein the transparent conductive film is the transparent conductive film according to the fourteenth aspect. It is.
- a sixteenth invention of the present invention is a device comprising a transparent electrode, wherein the transparent electrode is the transparent conductive substrate according to the fifteenth invention.
- a seventeenth aspect of the present invention is the device according to the sixteenth aspect, wherein the device is one selected from a light emitting device, a power generation device, a display device, and an input device.
- a conductive oxide fine particle layer densely filled with conductive oxide fine particles mainly composed of a metal oxide can be formed. It has both high transparency and high conductivity, and excellent film strength. Therefore, a transparent conductive substrate in which this transparent conductive film is formed on a heat resistant substrate is a light emitting device such as an LED element, an electroluminescence lamp (electroluminescence element), a field emission lamp, a power generation device such as a solar cell, a liquid crystal display (liquid crystal display). Element), an electroluminescence display (electroluminescence element), a plasma display, a display device such as an electronic paper element, and an input device such as a touch panel.
- a light emitting device such as an LED element, an electroluminescence lamp (electroluminescence element), a field emission lamp, a power generation device such as a solar cell, a liquid crystal display (liquid crystal display). Element), an electroluminescence display (electroluminescence element), a plasma display, a display device such as
- FIG. 2 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Example 1.
- FIG. 2 is a scanning electron micrograph (SEM image) of a cross section of a transparent conductive film according to Example 1.
- FIG. 4 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Example 2.
- FIG. 4 is a scanning electron micrograph (SEM image) of a cross section of a transparent conductive film according to Example 2.
- FIG. 6 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Example 4.
- FIG. 10 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Example 6.
- FIG. 2 It is a scanning electron micrograph (SEM image) of the cross section of the transparent conductive film which concerns on Example 7.
- FIG. 4 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Comparative Example 1.
- 2 is a scanning electron micrograph (SEM image) of a cross section of a transparent conductive film according to Comparative Example 1.
- 4 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Comparative Example 2.
- 4 is a scanning electron micrograph (SEM image) of a cross section of a transparent conductive film according to Comparative Example 2.
- It is a transmission electron micrograph (TEM image) of the cross section of the transparent conductive film which concerns on the comparative example 3.
- 10 is a transmission electron micrograph (TEM image) of a cross section of a transparent conductive film according to Comparative Example 5.
- It is a scanning electron micrograph (SEM image) of the cross section of the transparent conductive film which concerns on the comparative example 6.
- the present invention relates to a method for producing a transparent conductive film formed by applying a coating liquid for forming a transparent conductive film containing an organometallic compound as a main component onto a heat-resistant substrate, drying, and firing. Since the conductive oxide fine particle crystal growth proceeds and a densely packed conductive oxide fine particle layer is formed, the conductivity of the transparent conductive film and the strength of the film are improved.
- Transparent conductive film structure First, the transparent conductive film structure will be described. In the following, a transparent conductive film made of tin-doped indium oxide (ITO) will be described as an example. However, the same applies to a transparent conductive film containing tin oxide or zinc oxide as a main component other than indium oxide. Can do.
- ITO tin-doped indium oxide
- a transparent conductive film made of ITO is formed using a vapor phase growth method such as a sputtering method
- a polycrystalline ITO film structure which is a film structure in which ITO crystal grains are usually arranged through grain boundaries. Almost no ITO fine particles are observed in the film structure.
- the ITO fine particles are usually used.
- the particle structure of the ITO fine particles and the size of the voids existing between the ITO fine particles differ depending on the firing conditions, etc., but there are not a few ITO fine particles with open pores (open pores). It is known that a transparent conductive film is formed.
- the transparent conductive film in which ITO fine particles formed by this coating method are bonded to each other has a small contact area between the ITO fine particles because the conductive mechanism intervenes the contact portion (bonded portion) of the ITO fine particles.
- Conductivity drop at the contact portion that is thought to occur due to contact conductivity at atmospheric exposure that is thought to occur because oxygen and water vapor in the atmosphere enter the film through open gaps and degrade the contact between ITO particles Deterioration of the film over time, a decrease in film strength, which is considered to occur due to the coarse filling of ITO fine particles, and the like.
- the present invention densely fills the conductive oxide fine particles and at the same time promotes the crystal growth of the conductive oxide fine particles so that the open pores (open pores) are small and dense. And forming a film structure having a conductive oxide fine particle layer mainly composed of at least one of indium oxide, tin oxide, and zinc oxide in which contact between the conductive oxide fine particles is enhanced.
- the conductivity is improved and the film strength is also improved. Furthermore, it is possible to greatly suppress the deterioration of conductivity over time.
- the dense conductive oxide fine particle layer mainly containing at least one of indium oxide, tin oxide, and zinc oxide is applied by using the above-described coating liquid for forming a transparent conductive film.
- the oxygen-containing atmosphere having a low water vapor content that is, a low dew point is applied in the temperature raising process during the firing.
- the packing density of the conductive oxide particles in the transparent conductive film is It can be increased to about 90% of the true specific gravity of the active oxide, and when an oxygen-containing atmosphere containing water vapor is applied, it remains at about 60 to 70% of the true specific gravity.
- an indium oxide, tin oxide, or zinc oxide coating solution is formed by using a coating liquid for forming a transparent conductive film mainly composed of at least one of an organoindium compound, an organotin compound, and an organozinc compound.
- the transparent conductive film which has any one or more as a main component is formed.
- it is desirable that the transparent conductive film has a high conductivity.
- an oxide that is a main component of indium oxide, tin oxide, or zinc oxide is doped with another metal compound, mainly a metal oxide. This improves the conductivity.
- the conductivity of the transparent conductive film is improved. This is because the dopant metal compound functions to increase the concentration of electrons as carriers (carrier density) in the conductive oxide.
- an organic metal compound for dopant is added to a coating liquid for forming a transparent conductive film containing as a main component one or more of an organic indium compound, an organic tin compound, and an organic zinc compound. There is a method of blending a predetermined amount.
- a coating liquid for forming a transparent conductive film containing an organic indium compound as a main component will be described below.
- the organic indium compound used in the present invention include acetylacetone indium (formal name: tris (acetylacetonato) indium) [In (C 5 H 7 O 2 ) 3 ], indium 2-ethylhexanoate, indium formate, indium alkoxide, and the like.
- any organic indium compound may be used as long as it dissolves in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing.
- indium acetylacetone is preferable because it is highly soluble in an organic solvent and is thermally decomposed and burned (oxidized) at a temperature of about 200 to 250 ° C. to form an oxide.
- organometallic compounds for dopants that improve conductivity organic tin compounds, organic titanium compounds, organic germanium compounds, organic zinc compounds, organic tungsten compounds, organic zirconium compounds, organic tantalum compounds, organic niobium compounds, organic hafnium Any one or more of a compound and an organic vanadium compound are preferable.
- the conductivity is low to some extent (high resistance value), so the addition of the organometallic compound for dopant to the coating liquid for forming the transparent conductive film It may be carried out as necessary.
- organotin compound as the organometallic compound for the dopant examples include, for example, acetylacetone tin (formal name: di-n-butoxide bis (2,4-pentane) dionato) tin, [Sn (C 4 H 9 ) 2 (C 5 H 7 O 2) 2], tin octylate, tin 2-ethylhexanoate, tin acetate (II) [Sn (CH 3 COO) 2] , tin acetate (IV) [Sn (CH 3 COO) 4], di -n- butyl tin diacetate [Sn (C 4 H 9) 2 (CH 3 COO) 2], formic acid, tin as tin alkoxide - tert-Butoxide [Sn (C 4 H 9 O) 4 ] can be mentioned, but basically it dissolves in
- organotitanium compound of the organometallic compound for dopant for example, acetylacetone titanium (formal name: titanium di-n-butoxide bis (2,4-pentanedionate) [Ti (C 4 H 9 O) 2 as a titanium acetylacetone complex] 2 (C 5 H 7 O 2 ) 2 ]), titanyl (IV) acetylacetonate [(C 5 H 7 O 2 ) 4 TiO], titanium diisopropoxide bis (2,4-pentanedionate) [C 16 H 36 O 4 Ti] or the like, titanium tetraethoxide [Ti (C 2 H 5 O) 4 ] as titanium alkoxide, titanium (IV) -tert-butoxide [Ti (C 4 H 9 O) 4 ], titanium tetra -n- butoxide [Ti (C 4 H 9 O ) 4], titanium tetraisopropoxide [Ti (C 3 H 7 O )
- any organic titanium compound may be used as long as it dissolves in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing.
- acetylacetone titanium, titanium tetra-n-butoxide, and titanium tetraisoproposide are preferable because they are inexpensive and easily available.
- germanium tetraethoxide [Ge (C 2 H 5 O) 4 ] as germanium alkoxide, germanium tetra-n-butoxide [Ge (C 4 H 9 O) 4 ], Germanium tetraisopropoxide [Ge (C 3 H 7 O) 4 ] and the like, ⁇ -carboxyethyl germanium oxide [(GeCH 2 CH 2 COOH) 2 O 3 ], tetraethyl germanium [Ge (C 2 H 5 ) 4 ], tetrabutyl germanium [Ge (C 4 H 9 ) 4 ], tributyl germanium [Ge (C 4 H 9 ) 3 ], etc., which are basically dissolved in a solvent and chlorine gas during firing.
- germanium tetraethoxide, germanium tetra-n-butoxide, and germanium tetraisopropoxide are preferable because they are relatively inexpensive and easily available.
- the organic zinc compound of the dopant organometallic compound for example, zinc acetylacetonate as a zinc acetylacetone complex (official name: Zinc 2,4-pentanedionate) [Zn (C 5 H 7 O 2) 2], zinc - 2,2,6,6-tetramethyl-3,5-heptanedionate [Zn (C 11 H 19 O 2 ) 2 ] and the like can be mentioned.
- Any organic zinc compound that decomposes into oxide without generating harmful gas such as gas or nitrogen oxide gas may be used.
- zinc acetylacetone is preferable because it is inexpensive and easily available.
- tungsten (V) ethoxide as tungsten alkoxide [W (C 2 H 5 O) 5 ] tungsten (VI) ethoxide [W (C 2 H 5 O) 6
- any organic tungsten compound may be used as long as it is dissolved in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing.
- the organic zirconium compound as the dopant organometallic compound for example, zirconium di -n- butoxide bis as zirconium acetylacetone complex (2,4-pentanedionate) [Zr (C 4 H 9 O) 2 (C 5 H 7 O 2 ) 2 ]), acetylacetone zirconium (formal name: zirconium-2,4-pentanedionate) [Zr (C 5 H 7 O 2 ) 4 ], zirconium ethoxide as a zirconium alkoxide [Zr (C 2 H 5 O) 4], zirconium -n- propoxide [Zr (C 3 H 7 O ) 4], zirconium isopropoxide [Zr (C 3 H 7 O ) 4], zirconium -n- butoxide [Zr (C 4 H 9 O) 4], zirconium -tert- butoxide [Zr (C 4 H 9 O ) 4] Zi
- the organic tantalum compound as the dopant organometallic compound for example, tantalum as tantalum acetylacetone complex (V) tetraethoxide - pentanedionate) [Ta (C 5 H 7 O 2) (OC 2 H 5) 4], Tantalum methoxide [Ta (CH 3 O) 5 ], tantalum ethoxide [Ta (C 2 H 5 O) 5 ], tantalum isopropoxide [Ta (C 3 H 7 O) 5 ], tantalum- n-butoxide [Ta (C 4 H 9 O) 5 ], tetraethoxyacetylacetonato tantalum [Ta (C 2 H 5 O) 4 (C 5 H 7 O 2 )] and the like can be mentioned.
- organic niobium compound of the organometallic compound for dopant for example, niobium ethoxide [Nb (C 2 H 5 O) 5 ] as niobium alkoxide, niobium-n-butoxide [Nb (C 4 H 9 O) 5 ], etc.
- any organic niobium compound that dissolves in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing may be used.
- hafnium di-n-butoxide bis (2,4-pentandionate) [Hf (C 4 H 9 O) 2 (C 5 H 7 as a hafnium acetylacetone complex) O 2 ) 2 ]
- acetylacetone hafnium [formal name: hafnium-2,4-pentanedionate) [Hf (C 5 H 7 O 2 ) 4 ]
- hafnium-n-butoxide hafnium-tert-butoxide [Hf (C 4 H 9 O) 4 ]
- hafnium (VI) isopropoxide monoisopropylate [ Hf (C 3 H 7 O) 4 (C 3 H 7 OH)] and the like.
- hafnium compound Any organic hafnium compound may be used as long as it dissolves in the gas and decomposes into oxides without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing.
- hafnium-n-butoxide is preferable because it is relatively inexpensive and easily available.
- organic vanadium compound of the organometallic compound for the dopant for example, vanadium (IV) oxide bis-2,4-pentanedionate [VO (C 5 H 7 O 2 ) 2 ] as a vanadium acetylacetone complex, acetylacetone vanadium (formal Name: vanadium (III) -2,4-pentanedionate) [V (C 5 H 7 O 2 ) 3 ] and the like, but basically, it is dissolved in a solvent, and chlorine gas or nitrogen is used during firing. Any organic vanadium compound that decomposes into oxide without generating harmful gas such as oxide gas may be used.
- the coating liquid for forming a transparent conductive film containing an organic tin compound as a main component will be described below.
- the organic tin compound used in the present invention the organic tin compound described in the description of the coating liquid for forming a transparent conductive film containing an organic indium compound as a main component can be used. Is preferably at least one of an organic indium compound, an organic antimony compound, and an organic phosphorus compound.
- the organic indium compound as the organometallic compound for dopant the organic indium compound described above in the description of the coating liquid for forming a transparent conductive film containing the organic indium compound as a main component may be used.
- organic antimony compound of the organometallic compound for dopant for example, antimony (III) acetate [Sb (CH 3 COO) 3 ], antimony (III) ethoxide as antimony alkoxide [Sb (C 2 H 5 O) 3 ], Antimony (III) -n-butoxide [Sb (C 4 H 9 O) 3 ] and the like can be mentioned, but basically, it dissolves in a solvent, and harmful gases such as chlorine gas and nitrogen oxide gas are generated during firing. Any organic antimony compound that does not occur and decomposes into an oxide may be used. Among these, antimony (III) -n-butoxide is preferable because it is relatively inexpensive and easily available.
- organophosphorus compound of the organometallic compound for dopant examples include triethyl phosphate [PO (C 2 H 5 O) 3 ] and the like. Basically, it dissolves in a solvent, and chlorine gas or Any organic phosphorus compound that decomposes into oxide without generating harmful gas such as nitrogen oxide gas may be used.
- a coating liquid for forming a transparent conductive film containing an organic zinc compound as a main component will be described below.
- the organic zinc compound used in the present invention the organic zinc compound described in the explanation of the coating liquid for forming a transparent conductive film containing an organic indium compound as a main component can be used. Is preferably at least one of an organic aluminum compound, an organic indium compound, and an organic gallium compound.
- the organic indium compound as the organometallic compound for dopant the organic indium compound described above in the description of the coating liquid for forming a transparent conductive film containing the organic indium compound as a main component may be used.
- acetylacetone aluminum (aluminum-2,4-pentanedionate) [Al (C 5 H 7 O 2 ) 3 ] as an aluminum acetylacetone complex
- aluminum ethoxide as an aluminum alkoxide [Al (C 2 H 5 O ) 3]
- aluminum -n- butoxide [Al (C 4 H 9 O ) 3]
- aluminum -tert- butoxide [Al (C 4 H 9 O ) 3]
- aluminum isopropoxide [Al (C 3 H 7 O) 3 ] and the like can be mentioned, but basically it dissolves in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing.
- Any organic aluminum compound may be used.
- acetylacetone aluminum and aluminum-n-butoxide are preferable because they are relatively inexpensive and easily available.
- Examples of the organic gallium compound of the organometallic compound for dopant include acetylacetone gallium (gallium-2,4-pentanedionate) [Ga (C 5 H 7 O 2 ) 3 ] as a gallium acetylacetone complex, and gallium ethoxide as a gallium alkoxide. [Ga (C 2 H 5 O) 3 ] and the like can be mentioned, but basically, it dissolves in a solvent and decomposes into an oxide without generating harmful gases such as chlorine gas and nitrogen oxide gas during firing. Any organic gallium compound may be used.
- One or more organometallic compounds of the organic indium compound, organotin compound, and organozinc compound in the coating liquid for forming the transparent conductive film, or the organometallic compound and the organometallic compound for the dopant are formed on the substrate. It is a main compound raw material for formation, and the total content thereof is preferably in the range of 1 to 30% by weight, more preferably 5 to 20% by weight. If the total content is less than 1% by weight, only a thin transparent conductive film can be obtained, and sufficient conductivity cannot be obtained.
- the organometallic compound in the coating liquid for forming the transparent conductive film is likely to be precipitated and the stability of the coating liquid is reduced, or the resulting transparent conductive film becomes too thick and cracks are caused. May occur and conductivity may be impaired.
- the content rate of an organometallic compound and the organometallic compound for dopants is an organometallic compound.
- 99.9: 0.1 to 66.7: 33.3 is preferable in terms of molar ratio of the organometallic compound for dopant.
- the coating liquid for forming a transparent conductive film containing an organic indium compound as a main component when an organozinc compound is used as an organometallic compound for doping, it is 95 in terms of a molar ratio of organometallic compound: organometallic compound for dopant. : 5 to 66.7: 33.3, preferably 91: 9 to 71:29.
- the said molar ratio has pointed out the molar ratio of each metal component of an organometallic compound and the organometallic compound for dopants. Therefore, for example, when two metal elements are contained in one molecule of the organometallic compound for dopant, the metal element for dopant is converted as 2 moles with respect to 1 mole of the organometallic compound for dopant.
- the transparent conductive film does not necessarily require high conductivity, and conversely, a high resistance value may be required. In such a case, for the purpose of obtaining a high-resistance transparent conductive film, it can be used without blending the organometallic compound for dopant in the coating liquid for forming a transparent conductive film.
- the carrier density of the transparent conductive film may decrease and the conductivity of the transparent conductive film may deteriorate rapidly.
- the crystal growth of the conductive oxide fine particles is difficult to proceed and the conductivity may be deteriorated.
- a binder may be added to the coating liquid for forming a transparent conductive film, if necessary.
- a binder By adding a binder, the wettability with respect to the substrate is improved, and at the same time, the viscosity of the coating solution can be adjusted.
- the binder is preferably a material that burns or thermally decomposes during firing, and as such a material, a cellulose derivative, an acrylic resin, or the like is effective.
- cellulose derivative used for the binder examples include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxyethyl methyl cellulose, nitrocellulose and the like.
- HPC hydroxypropylcellulose
- HPC high performance polystyrene
- the combustion start temperature of HPC is about 300 ° C.
- burning is performed at a temperature of 300 ° C. or higher, preferably 350 ° C. or higher, so that it does not hinder the growth of the conductive particles produced and has good conductivity.
- a transparent conductive film can be produced.
- the content of HPC is more than 5% by weight, it becomes a gel and tends to remain in the coating solution, forming an extremely porous transparent conductive film, and the transparency and conductivity are significantly impaired.
- the viscosity of the coating solution can be set lower than when HPC is used.
- the acrylic resin is preferably an acrylic resin that burns at a relatively low temperature.
- Solvents used in the coating liquid for forming a transparent conductive film include alkylphenols and / or alkenylphenols and dibasic acid esters or alkylphenols and / or alkenylphenols that can dissolve acetylacetone complexes such as acetylacetone indium, acetylacetone zinc, and acetylacetone vanadium at high concentrations. It is preferable to use benzyl acetate and a mixed solution thereof.
- alkylphenol and alkenylphenol examples include cresols, xylenol, ethylphenol, p-tert-butylphenol, octylphenol, nonylphenol, cashew nut shell liquid [3 pentadecadeseal phenol], and dibasic acid esters (for example, dibasic acid esters).
- dibasic acid esters for example, dibasic acid esters.
- dimethyl acid, diethyl dibasic acid, etc. succinic acid ester, glutaric acid ester, adipic acid ester, malonic acid ester, phthalic acid ester and the like are used.
- an organic indium compound, an organometallic compound for a dopant, a cellulose derivative and / or an acrylic resin As long as it is compatible with the solution in which water is dissolved, water, methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol (DAA) ) Alcohol solvents, acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone (MIBK), ketone solvents such as cyclohexanone, isophorone, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, propion
- the solvents used include methyl ethyl ketone (MEK), cyclohexanone, propylene glycol monomethyl ether (PGM), N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, and the like. preferable.
- the coating liquid for forming a transparent conductive film used in the present invention is any one of the above organic indium compounds, organic tin compounds, and organic zinc compounds, and any of the above-mentioned various organometallic compounds for dopants. It is produced by heating and dissolving a mixture of one or more, and further, if necessary, a binder.
- the melting by heating is usually performed by setting the heating temperature to 60 to 200 ° C. and stirring for 0.5 to 12 hours.
- the heating temperature is lower than 60 ° C.
- the coating does not dissolve sufficiently.
- the heating temperature is lower than 60 ° C.
- the coating solution for forming a transparent conductive film mainly composed of an organic indium compound the deposition and separation of a metal compound such as acetylacetone indium occurs. If the stability of the liquid is lowered and the temperature is higher than 200 ° C., the evaporation of the solvent becomes remarkable and the composition of the coating liquid changes, which is not preferable.
- the viscosity of the coating liquid for forming a transparent conductive film can be adjusted by the molecular weight and content of the binder and the type of solvent, the inkjet printing method, the screen printing method, the gravure printing method, the offset printing method, the flexographic printing method, The viscosity can be adjusted to correspond to each of various coating methods such as dispenser printing, slit coating, die coating, doctor blade coating, wire bar coating, spin coating, and spray coating.
- the coating liquid having a high viscosity (about 5000 to 50000 mPa ⁇ s) can be prepared by containing a high molecular weight binder in an amount of 5% by weight or less, preferably 2 to 4% by weight.
- the low viscosity (about 5 to 500 mPa ⁇ s) is Further, it can be prepared by containing a low molecular weight binder in an amount of 5% by weight or less, preferably 0.1 to 2% by weight, and diluting with a low viscosity diluent.
- a medium viscosity (500 to 5000 mPa ⁇ s) coating solution can be produced by mixing a high viscosity coating solution and a low viscosity coating solution.
- the manufacturing method of the transparent conductive film of this invention is demonstrated in detail.
- the transparent conductive film of the present invention is a coating process in which a coating liquid for forming a transparent conductive film is applied onto a heat resistant substrate to form a coating film, a drying process in which the coating film is dried to form a dry coating film, and the drying It forms through each process of the baking process which bakes a coating film and forms an inorganic film.
- (A) Application process Application of the coating liquid for forming the transparent conductive film on the heat-resistant substrate is performed by inkjet printing, screen printing, gravure printing, offset printing, flexographic printing, dispenser printing, slit coating, The coating is performed using various coating methods such as a die coating method, a doctor blade coating method, a wire bar coating method, a spin coating method, and a spray coating method.
- a heat-resistant substrate an inorganic substrate such as soda lime glass, non-alkali glass, or quartz glass, or a resin substrate (heat-resistant plastic film) such as polyimide (PI) can be used.
- Drying step In this drying step, the substrate coated with the coating liquid for forming a transparent conductive film is kept in the normal atmosphere at 80 to 180 ° C. for 1 to 30 minutes, preferably 2 to 10 minutes to dry the coated film. And a dry coating film is produced. Drying conditions (drying temperature, drying time) can be appropriately selected depending on the type of heat-resistant substrate used, the coating thickness of the coating liquid for forming the transparent conductive film, and the like. However, in consideration of productivity, it is desirable that the drying time is shortened to the minimum necessary so that the quality of the obtained dry coating film is not deteriorated.
- This dry coating film is obtained by volatilizing and removing the above-mentioned organic solvent from the coating liquid for forming a transparent conductive film, and includes one or more organometallic compounds of an organic indium compound, an organic tin compound, and an organic zinc compound, (Organic metal compound for dopant) and organic components such as a binder.
- (C) Firing step In the firing step, the dried coating film obtained in the drying step is heat-treated (baked), and any one or more of an organic indium compound, an organic tin compound, and an organic zinc compound in the dried coating film
- the organic metal compound or the organic metal compound containing the dopant organic metal compound and the organic component such as a binder are thermally decomposed and burned (oxidized) to form an inorganic component (a conductive oxide mainly composed of a metal oxide). ) (A transparent conductive film as a conductive oxide fine particle layer densely filled with conductive oxide fine particles).
- one or more organometallic compounds (organic metal compounds for dopants) of the organic indium compound, organotin compound, and organozinc compound in the dried coating film Is gradually pyrolyzed and burned (oxidized), and is first in an amorphous state (herein, it refers to a state of very fine particles having a crystallite size of less than 3 nm determined by X-ray diffraction) Conversion into a conductive oxide, so-called mineralization occurs.
- the heating temperature rises further, usually exceeding the range of 300 to 330 ° C., or even if the heating temperature is kept within the range of 300 to 330 ° C., the crystallization of the conductive oxide occurs when the heating time is prolonged. It grows to become conductive oxide fine particles and becomes a constituent element of the final transparent conductive film.
- the above-mentioned 300 to 330 ° C. indicates a general temperature range in which mineralization and crystallization are likely to occur.
- the above-described conductive oxide can be used even at about 270 ° C. Since mineralization, crystallization, and crystal growth may occur, the firing temperature in the firing step of the present invention is not limited to 300 ° C. or higher.
- the binder is also thermally decomposed and burned (oxidized) gradually in the temperature rising process of the firing step, but is mainly converted to carbon dioxide (CO 2 ) and volatilized in the atmosphere and disappeared from the film (binder)
- CO 2 carbon dioxide
- the binder it almost disappears at about 300 to 350 ° C.
- a large amount of binder remains until the initial stage of the firing process (a stage where the temperature rises, for example, a stage where heating is performed from room temperature to 300 ° C.), and the binder is uniform between the amorphous conductive oxides. It is considered that the crystallization of the conductive oxide occurs due to the gradual disappearance of the binder component as the firing proceeds further.
- FIG. 1 shows the relationship between the saturated water vapor content (volume%) in air and the dew point (° C.).
- the initial stage of the firing process usually about 300 to 330 ° C. in the present invention
- the film structure has flexibility by the action of the binder which is an organic substance and enables the film to contract (dense) in the direction perpendicular to the substrate.
- the temperature is raised to a temperature at which crystallization of the conductive oxide occurs (usually 300 to 330 ° C. or higher), and firing is performed. Ensuring densification. After the densification of the film, if necessary, the film is then fired while supplying an oxygen-containing atmosphere gas having a dew point of 0 ° C. or higher, thereby promoting the crystal growth of the conductive oxide fine particles. Further, after the above-mentioned film is densified (firing in an oxygen-containing atmosphere gas having a dew point of ⁇ 10 ° C. or lower), or the crystal growth after the densification is promoted (oxygen-containing atmosphere gas having a dew point of 0 ° C. or higher) It is preferable to perform firing while supplying a neutral atmosphere or a reducing atmosphere gas.
- the oxygen-containing atmosphere gas examples include air or a mixed gas of oxygen and a neutral / inert gas (nitrogen, argon, etc.). Air that is inexpensive and easily available is preferable.
- the dew point of the oxygen-containing atmosphere gas having a dew point of ⁇ 10 ° C. or lower is preferably ⁇ 15 ° C. or lower, more preferably ⁇ 20 ° C. or lower, still more preferably ⁇ 30 ° C. or lower, and most preferably ⁇ 40 ° C. or lower. Further, in the firing in which the temperature is raised to a temperature at which crystallization of the conductive oxide occurs in an oxygen-containing atmosphere having a dew point of ⁇ 10 ° C. or lower (usually 300 to 330 ° C.
- the dew point is ⁇ 10 ° C. If exceeded, in the process of forming a conductive oxide fine particle layer composed of conductive oxide fine particles, water vapor is crystallized and grown in a stage where a large amount of binder remains in the initial stage of firing. Since the film structure capable of shrinking in the vertical direction of the film in which the binder is uniformly interposed between the conductive oxides in the amorphous state is destroyed, the conductive oxide fine particles adhere to each other and cannot move. Densification is hindered and the conductivity and film strength of the transparent conductive film are lowered, which is not preferable.
- the dew point of the oxygen-containing atmosphere gas having a dew point of 0 ° C. or higher is preferably 10 More than 20 degreeC, More preferably, it is 20 degreeC or more.
- the dew point is 0 ° C. or more, the crystal growth of the conductive oxide fine particles of the film in which water vapor is densified is promoted, so that both the densification of the film and the crystal growth can be achieved. This is because the strength can be increased.
- Firing at a temperature higher than the temperature at which crystallization of the conductive oxide in an oxygen-containing atmosphere with a dew point of ⁇ 10 ° C. or lower (usually 300 to 330 ° C. or higher in the present invention) is performed.
- (Peak temperature) is 300 ° C. or higher, more preferably 350 ° C. or higher, more preferably 400 ° C. or higher, for 5 to 120 minutes, more preferably 15 to 60 minutes.
- the organic component (organic indium compound, organic metal compound for dopant, organic component contained in binder, etc.) contained in the dried coating film is usually thermally decomposed or Combustion is likely to be insufficient, and these organic components remain in the transparent conductive film, causing no crystallization of the conductive oxide, resulting in insufficient densification of the film, deteriorating the transparency and conductivity of the film. It is not preferable because of fear.
- the baking time is increased to, for example, about 60 minutes or more, or when the final transparent conductive film has a thin film thickness of about 130 nm or less, thermal decomposition or combustion of the organic component proceeds even at about 270 ° C., for example. Therefore, the transparency and conductivity of the film may not deteriorate. Therefore, in general, a firing temperature of 300 ° C. or higher is preferable, but a firing temperature of about 270 ° C. is also applicable depending on the conditions (film thickness, firing time, etc.) of each step.
- the upper limit of the firing temperature is not particularly limited, but it is affected by the type of firing apparatus used in the firing step and the heat resistance of the heat-resistant substrate, and the strain point is about 510 for a cheap and most commonly used soda-lime glass substrate. Since it is 0 degreeC, it is preferable to bake at temperature lower than this temperature. However, if the soda lime glass substrate is baked on a heat-resistant base material having higher heat resistance, the substrate can be relatively distorted, so that baking at about 600 ° C. is also possible. Of course, when a glass substrate having higher heat resistance such as a quartz glass substrate, an alkali-free glass substrate, or a high strain point glass substrate is used, a higher firing temperature can be applied. When a polyimide (PI) film, which is a heat resistant plastic, is used as the heat resistant substrate, it can be baked up to about 400 ° C. depending on the type of polyimide.
- PI polyimide
- Examples of the baking apparatus used in the baking process include, but are not limited to, a hot plate, a hot-air circulating baking furnace, and a far-infrared heating apparatus.
- the firing apparatus is required to be able to control the firing atmosphere.
- the rate of temperature increase up to the temperature at which the crystallization of the conductive oxide occurs in the temperature increasing process of the firing step but it is in the range of 5 to 40 ° C./min, more generally 10 to 30. ° C / min.
- the heating rate is slower than 5 ° C / minute, it takes too much time to raise the temperature and the efficiency is deteriorated. On the other hand, if it is attempted to achieve a heating rate exceeding 40 ° C / minute with the above-mentioned baking apparatus, the heater capacity becomes too large. It is not realistic.
- the firing conditions for firing in an oxygen-containing atmosphere having a dew point of 0 ° C. or higher are also those for raising the temperature above the temperature at which crystallization of the conductive oxide occurs in an oxygen-containing atmosphere having a dew point of ⁇ 10 ° C. or lower. Similar to normal firing conditions (usually 300 to 330 ° C. or more), the firing temperature is 300 ° C. or more, more preferably 350 ° C. or more, and even more preferably 400 ° C. or more for 5 to 120 minutes, more preferably 15 to 60. For minutes.
- the neutral atmosphere is composed of at least one of nitrogen gas and inert gas (argon, helium, etc.), and the reducing atmosphere is hydrogen gas or hydrogen or an organic solvent vapor (organic such as methanol) in the neutral atmosphere. Gas) and the like, as long as the conductive carrier concentration can be increased by depriving oxygen atoms from the finely packed conductive oxide fine particles to form oxygen vacancies. It is not limited. However, if the atmosphere is too reducing, indium oxide may be reduced to metal indium, which is not preferable. If the firing temperature is about 250-450 ° C., the mixed gas of 1-2% hydrogen-99-98% nitrogen will not explode even if it leaks into the atmosphere, and it is difficult to reduce indium oxide to metallic indium. Preferred atmosphere and firing temperature.
- the firing conditions for firing in a neutral atmosphere or a reducing atmosphere are a firing temperature of 250 ° C. or higher, more preferably 350 ° C. or higher for 5 to 120 minutes, and more preferably 15 to 60 minutes. From the viewpoint of further promoting the crystal growth between the conductive oxide fine particles described above, the firing temperature is preferably 350 ° C. or higher, more preferably 450 ° C. or higher. A firing temperature lower than 250 ° C. is not preferable because oxygen vacancies cannot be sufficiently formed in the conductive oxide fine particles, and the conductivity of the transparent conductive film cannot be improved by increasing the carrier concentration.
- the upper limit of the firing temperature is not particularly limited, but the point affected by the type of firing apparatus used in the firing step and the heat resistance of the heat-resistant substrate is the same as in firing in an oxygen-containing atmosphere.
- the conductive oxide constituting the transparent conductive film may be excessively reduced, requiring caution.
- a firing temperature exceeding 600 ° C. when a reducing atmosphere having strong reducing properties such as hydrogen gas is used, the metal oxide as the conductive oxide is reduced to the metal element in a short time. In some cases (for example, indium oxide may be reduced to metal indium), it is necessary to select an appropriate reducing atmosphere and set a reduction time.
- firing in an oxygen-containing atmosphere with a dew point of ⁇ 10 ° C. or lower firing at a temperature higher than the temperature at which crystallization of the conductive oxide occurs, firing in an oxygen-containing atmosphere with a dew point of 0 ° C. or higher, and neutral atmosphere or reducing property Firing in the atmosphere can be performed continuously. That is, in firing a heat-resistant substrate on which a dry coating film is formed, for example, after raising the temperature of the substrate to a firing temperature of 300 ° C. or higher, only the atmosphere is kept at a dew point of ⁇ 10 ° C. or lower while maintaining the temperature.
- the oxygen-containing atmosphere may be switched to an oxygen-containing atmosphere having a dew point of 0 ° C. or higher, or a neutral atmosphere or a reducing atmosphere.
- firing in a neutral atmosphere or a reducing atmosphere is performed by forming a transparent conductive film due to the presence of oxygen vacancies in addition to the function of increasing oxygen concentration by forming oxygen vacancies in the above-described conductive oxide. It also has a function of facilitating crystal growth by facilitating the movement of these constituent elements, and contributes to further improvement in the strength and conductivity of the transparent conductive film.
- Such devices include LED elements, electroluminescence lamps (electroluminescence elements), light emission devices such as field emission lamps, power generation devices such as solar cells, liquid crystal displays (liquid crystal elements), electroluminescence displays (electrons) as described above.
- Luminescence elements display devices such as plasma displays and electronic paper elements, and input devices such as touch panels.
- the transparent conductive film and the transparent conductive substrate of the present invention are suitable for these transparent electrodes.
- the electroluminescence element as the light emitting device includes an organic EL element using an organic light emitting material and an inorganic EL element using an inorganic light emitting material.
- the organic EL element has attracted attention.
- This organic EL element is a self-luminous element unlike a liquid crystal display element, and is expected to be used as a display device such as a display because high luminance can be obtained by driving at a low voltage.
- Organic EL devices also have a low molecular type and a high molecular type.
- a high molecular type structure has a hole injection layer (hole) made of a conductive polymer such as a polythiophene derivative on a transparent conductive film as an anode electrode layer.
- organic light emitting layer (polymer light emitting layer formed by coating), cathode electrode layer [magnesium (Mg), calcium (Ca), aluminum (Al ) And the like, and a gas barrier coating layer (or a sealing treatment with metal or glass) are sequentially formed.
- the gas barrier coating layer is required to prevent the deterioration of the organic EL element, and an oxygen barrier and a water vapor barrier are required.
- the water vapor transmission rate is about 10 ⁇ 5 g / m 2 / day or less. Therefore, the inside of the organic EL element (device) is completely sealed from the outside.
- Solar cells as power generation devices are power generation elements that convert sunlight into electrical energy
- solar cells are silicon solar cells (thin film type, microcrystal type, crystal type), CIS solar cells (copper-indium-selenium thin film).
- CIGS solar cells copper-indium-gallium-selenium thin film
- dye-sensitized solar cells etc., for example, silicon solar cells sequentially have a transparent electrode, a semiconductor power generation layer (silicon), and a metal electrode on a transparent substrate. Formed.
- Liquid crystal elements as display devices are non-light emitting electronic display elements widely used in displays such as mobile phones, PDAs (Personal Digital Assistants), and PCs (Personal Computers). Simple matrix system (passive matrix system) And an active matrix method.
- the active matrix method is superior in terms of image quality and response speed. Its basic structure is a structure in which liquid crystal is sandwiched between transparent electrodes (corresponding to the transparent conductive film of the present invention), and liquid crystal molecules are aligned by voltage driving, and the actual element is a color electrode.
- a filter, a retardation film, a polarizing film, etc. are further laminated and used.
- liquid crystal elements include polymer dispersed liquid crystal elements (hereinafter abbreviated as PDLC elements) and polymer network liquid crystal elements (hereinafter abbreviated as PNLC elements) used for optical shutters such as windows. .
- the liquid crystal layer is sandwiched between electrodes (at least one is a transparent electrode, and the transparent conductive film of the present invention corresponds), and the liquid crystal molecules are aligned by voltage driving.
- the actual element does not require a retardation film or a polarizing film, and has a feature that the structure of the element can be simplified.
- the PDLC element has a structure in which liquid crystal microencapsulated in a polymer resin matrix is dispersed, while the PNLC element has a structure in which liquid crystal is filled in a mesh part of a resin network.
- the PDLC element has a high resin content in the liquid crystal layer, so an AC drive voltage of several tens V or more (for example, about 80 V) is required, whereas the PNLC element that can reduce the resin content in the liquid crystal layer is about several to 15 V.
- the PNLC element that can reduce the resin content in the liquid crystal layer is about several to 15 V.
- it is necessary to prevent water vapor from being mixed into the liquid crystal for example, a water vapor transmission rate of 0.01 g / m 2 / day or less is required, The inside of the liquid crystal element (device) is completely sealed from the outside.
- An electronic paper element as a display device is a non-light-emitting electronic display element that does not emit light by itself, has a memory effect that remains displayed even when the power is turned off, and is expected as a display for displaying characters.
- This display method includes an electrophoresis method in which colored particles are moved in a liquid between electrodes by an electrophoresis method, a twist ball method in which particles having dichroism are colored by rotating in an electric field, for example, a cholesteric liquid crystal is used as a transparent electrode.
- a liquid crystal system that displays images by sandwiching between them, a powder system that displays images by moving colored particles (toner) and electronic powder fluid (Quick Response Liquid Powder) in the air, and color development based on electrochemical oxidation / reduction action
- An electrochromic method, an electrodeposition method in which a metal is deposited and dissolved by electrochemical oxidation / reduction, and display is performed by a color change associated therewith have been developed.
- the display layer has a structure sandwiched between a transparent conductive film (transparent electrode) and a counter electrode.
- water vapor transmission rate 0. 0.01 to 0.1 g / m 2 / day is required, and the inside of the electronic paper element (device) is completely sealed from the outside.
- the touch panel is a position input element, such as a resistance method or a capacitance method.
- a resistance touch panel has a structure in which two transparent conductive substrates as coordinate detection resistance films for detecting coordinates are bonded together via a dot-shaped transparent spacer.
- the transparent conductive substrate is required to have hit point durability, and the transparent conductive film is required to have flexibility so that cracks do not occur.
- further improvement in conductivity of the transparent conductive film is required due to the improvement in resolution.
- any of the above light emitting devices, power generation devices, display devices, input devices, etc. improvement in device characteristics is required, and by applying the transparent conductive film according to the present invention and the transparent conductive substrate to those transparent electrodes. Since the basic characteristics of the device can be further improved, for example, it can greatly contribute to energy saving and downsizing of the device.
- solution A containing indium acetylacetone and hydroxypropylcellulose.
- solution B containing acetylacetone tin and hydroxypropyl cellulose.
- Example 1 a transparent conductive film according to Example 1 containing indium oxide (In 2 O 3 ) containing tin oxide (SnO 2 ) for dopant as a main component was produced.
- the surface resistance of the transparent conductive film was measured using a surface resistance meter Loresta AP (MCP-T400) manufactured by Mitsubishi Chemical Corporation.
- the haze value and visible light transmittance were measured based on JIS K7136 (haze value) and JIS K7361-1 (transmittance) using a Nippon Denshoku Co., Ltd. haze meter (NDH5000).
- the film thickness was measured using a stylus type film thickness meter (Alpha-Step IQ) manufactured by KLA-Tencor Corporation.
- the crystallite size was measured by X-ray diffraction, and the (222) peak of indium oxide (In 2 O 3 ) was determined by the Scherrer method.
- the pencil hardness was measured based on JIS K5400.
- the visible light transmittance and the haze value are values only for the transparent conductive film, and were obtained by the following formulas 1 and 2, respectively.
- Firing using the hot plate in Example 1 was heated to 350 ° C. over 35 minutes (temperature increase rate: 10 ° C./min) in an air atmosphere (supply of 1 liter / min) with a dew point of ⁇ 30 ° C., Baking at 350 ° C. for 15 minutes, changing the atmosphere to 2% hydrogen-98% nitrogen (1 liter / min supply) and baking at 350 ° C. for another 15 minutes.
- a transparent conductive film according to Example 2 containing indium oxide (In 2 O 3 ) containing tin (SnO 2 ) as a main component was produced.
- Example 1 Various characteristics of the produced transparent conductive film were measured in the same manner as in Example 1, and the results are shown in Table 1. Furthermore, the transmission electron micrograph (TEM image) which observed the cross section of the transparent conductive film of Example 2 with the transmission electron microscope, and the scanning electron micrograph (SEM image) are shown in FIG. 4 and FIG. 5, respectively. A conductive oxide fine particle layer densely filled with conductive oxide fine particles has been observed.
- TEM image transmission electron micrograph
- SEM image scanning electron micrograph
- Film formation was performed in the same manner as in Example 1 except that air having a dew point of ⁇ 80 ° C. or lower (cylinder filling air) was used instead of air having a dew point of ⁇ 30 ° C. in baking using the hot plate in Example 1.
- a transparent conductive film according to Example 3 containing indium oxide (In 2 O 3 ) containing tin oxide (SnO 2 ) for dopant as a main component was prepared.
- the coating solution for forming a transparent conductive film used in Example 1 was spin-coated (250 rpm ⁇ 60 sec) on the entire surface of a soda lime glass substrate (10 cm ⁇ 10 cm ⁇ 3 mm thickness) at 25 ° C., and then at 180 ° C. for 20 minutes. Dried, and further heated to 500 ° C. over 50 minutes (temperature increase rate: 10 ° C./min) in an air atmosphere having a dew point of ⁇ 30 ° C. (1 liter / min supply), and calcined at 500 ° C. for 15 minutes, As it is, the atmosphere is switched to an air atmosphere (supply of 1 liter / min) with a dew point of about 20 ° C., and further baked at 500 ° C. for 15 minutes, and indium oxide (In 2 O 3 ) containing tin oxide (SnO 2 ) for dopant is used.
- the transparent conductive film which concerns on Example 4 which has as a main component was produced.
- This coating solution for forming a transparent conductive film was spin coated (200 rpm ⁇ 60 sec) on the entire surface of a 25 ° C. soda lime glass substrate (10 cm ⁇ 10 cm ⁇ thickness 3 mm), then dried at 180 ° C. for 10 minutes, and further ⁇ 16 In an air atmosphere (1 liter / min supply) having various dew points of -19 ° C, -19 ° C, -27 ° C, -34 ° C, -44 ° C, and -80 ° C, the temperature is increased to 500 ° C over 50 minutes (temperature increase rate) : 10 ° C./min), and after baking at 500 ° C.
- Example 5 having indium oxide (In 2 O 3 ) containing tin (SnO 2 ) as a main component were prepared.
- the air atmosphere having various dew points of ⁇ 16 ° C. to ⁇ 80 ° C. is obtained by supplying air having a dew point of 25 ° C. and air having a dew point of ⁇ 80 ° C. at a predetermined flow rate and mixing them well.
- the various transparent conductive films according to Example 5 each have high transparency (haze value: within a range of 0.15-0.3%, visible light transmittance: 92.6-95.5%). Further, in any transparent conductive film, the pencil hardness was excellent at 5H or more. In addition, when the cross section of the various transparent conductive film of Example 5 was observed with the transmission electron microscope, the conductive oxide fine particle layer with which the conductive oxide fine particle was densely packed was observed.
- Example 6 a transparent conductive film according to Example 6 containing tin oxide (SnO 2 ) containing antimony oxide as a dopant as a main component was produced.
- solution D solution containing acetylacetone aluminum and hydroxypropylcellulose was prepared.
- Example 7 a transparent conductive film according to Example 7 containing zinc oxide (ZnO 2 ) containing aluminum oxide (Al 2 O 3 ) for dopant as a main component was produced.
- Example 1 A film was formed in the same manner as in Example 1 except that air having a dew point of 15 ° C. was used instead of air having a dew point of ⁇ 30 ° C. in Example 1, and tin oxide (SnO 2 ) for the dopant was included.
- Example 1 Various characteristics of the produced transparent conductive film were measured in the same manner as in Example 1, and the results are shown in Table 1. Furthermore, the transmission electron micrograph (TEM image) and the scanning electron micrograph (SEM image) which observed the cross section of the transparent conductive film of the comparative example 1 with the transmission electron microscope are shown in FIG. 12 and FIG. 13, respectively. A conductive oxide fine particle layer in which voids are observed between the conductive oxide fine particles has been observed.
- TEM image transmission electron micrograph
- SEM image scanning electron micrograph
- Example 2 A film was formed in the same manner as in Example 2 except that air having a dew point of 15 ° C. was used instead of air having a dew point of ⁇ 30 ° C. in Example 2, and tin oxide (SnO 2 ) for the dopant was included.
- a transparent conductive film according to Comparative Example 2 containing indium oxide (In 2 O 3 ) as a main component was produced.
- Example 1 Various characteristics of the produced transparent conductive film were measured in the same manner as in Example 1, and the results are shown in Table 1. Furthermore, the transmission electron micrograph (TEM image) which observed the cross section of the transparent conductive film of the comparative example 2 with the transmission electron microscope, and the scanning electron micrograph (SEM image) are shown in FIG. 14 and FIG. 15, respectively. A conductive oxide fine particle layer in which voids are observed between the conductive oxide fine particles has been observed.
- Example 3 A film was formed in the same manner as in Example 4 except that air having a dew point of about 20 ° C. was used instead of air having a dew point of ⁇ 30 ° C. (ie, an air atmosphere having a dew point of about 20 ° C.) 1 liter / minute supply), the temperature was raised to 500 ° C. over 50 minutes (temperature increase rate: 10 ° C./minute), and baked as it was at 500 ° C. for 30 minutes to contain tin oxide (SnO 2 ) for dopant.
- a transparent conductive film according to Comparative Example 3 containing indium oxide (In 2 O 3 ) as a main component was produced.
- Example 5 (Comparative Example 4) In Example 5, instead of air having various dew points of ⁇ 16 ° C. to ⁇ 80 ° C., air having various dew points of 25 ° C., 6 ° C., and ⁇ 4 ° C. was used in the same manner as in Example 5.
- Various transparent conductive films according to Comparative Example 4 containing indium oxide (In 2 O 3 ) containing tin oxide (SnO 2 ) as a dopant as a main component were prepared.
- the air atmosphere having various dew points of 25 ° C., 6 ° C., and ⁇ 4 ° C. is obtained by supplying air having a dew point of 25 ° C. and air having a dew point of ⁇ 80 ° C. at a predetermined flow rate and mixing them well.
- the various transparent conductive films according to Comparative Example 4 had high transparency, respectively (haze value: within a range of 0.1 to 0.3%, visible light transmittance: 92.3 to 98.7. %)), The pencil hardness was less than 3H in any transparent conductive film.
- the cross section of the various transparent conductive film of the comparative example 4 was observed with the transmission electron microscope, the conductive oxide fine particle layer by which a space
- Example 5 A film was formed in the same manner as in Example 6 except that air having a dew point of 23 ° C. was used instead of air having a dew point of ⁇ 60 ° C., and tin oxide containing antimony oxide for dopant (SnO The transparent conductive film which concerns on the comparative example 5 which has 2 ) as a main component was produced.
- Example 1 Various characteristics of the produced transparent conductive film were measured in the same manner as in Example 1, and the results are shown in Table 1. Furthermore, the transmission electron microscope photograph (TEM image) which observed the cross section of the transparent conductive film of the comparative example 5 with the transmission electron microscope is shown in FIG. A conductive oxide fine particle layer in which voids are observed between the conductive oxide fine particles has been observed.
- Example 6 A film was formed in the same manner as in Example 7 except that air having a dew point of 23 ° C. was used instead of air having a dew point of ⁇ 60 ° C. in Example 7, and aluminum oxide (Al 2 O 3 ) for dopant was used. A transparent conductive film according to Comparative Example 6 containing zinc oxide (ZnO 2 ) as a main component was produced.
- Example 1 and Example 3 are compared with Comparative Example 1, all are transparent conductive films obtained by firing at 500 ° C. (air atmosphere and 2% hydrogen-98% nitrogen atmosphere).
- the comparative example 1 has a relatively high resistance of 150 ⁇ / ⁇ . Recognize.
- the film thickness of Example 1 and Example 3 is 190 nm
- the film thickness of Comparative Example 1 is about 225 nm and about 18% thick. From this point, the transparent conductive films of Example 1 and Example 3 are It is densified by about 18% than the transparent conductive film of Comparative Example 1.
- Comparing Example 2 and Comparative Example 2 both are transparent conductive films obtained by firing at 350 ° C. (air atmosphere and 2% hydrogen-98% nitrogen atmosphere), but Example 2 is 140 ⁇ / ⁇ . On the other hand, it can be seen that Comparative Example 2 has a high resistance of 440 ⁇ / ⁇ . Further, while the film thickness of Example 2 is 205 nm, the film thickness of Comparative Example 2 is 225 nm, which is about 10% thick. From this point, the transparent conductive film of Example 2 is more transparent than the transparent conductive film of Comparative Example 2. Is densified by about 10%.
- Example 4 and Comparative Example 3 are transparent conductive films obtained by firing at 500 ° C. (air atmosphere), whereas Example 4 has a resistance of 660 ⁇ / ⁇ . It can be seen that Comparative Example 3 has a high resistance of 1540 ⁇ / ⁇ . Further, while the film thickness of Example 4 is 185 nm, the film thickness of Comparative Example 3 is 230 nm, which is about 24% thick. From this point, the transparent conductive film of Example 4 is the transparent conductive film of Comparative Example 3. It is about 24% denser than the film.
- Example 5 and Comparative Example 4 are transparent conductive films obtained by firing at 500 ° C. (air atmosphere). It can be seen that while the following resistance values are obtained, the various transparent conductive films of Comparative Example 4 have a resistance value of 102 ⁇ / ⁇ or more. Moreover, while the film thickness of the various transparent conductive films of Example 5 is 228 nm or less, the film thickness of the various transparent conductive films of Comparative Example 4 is as thick as 246 nm or more. It can be seen that the film is more dense than the various transparent conductive films of Comparative Example 4.
- Example 6 and Comparative Example 5 are transparent conductive films obtained by firing at 500 ° C. (air atmosphere and 1% hydrogen-99% nitrogen atmosphere), but Example 6 is 7500 ⁇ / ⁇ . It can be seen that Comparative Example 5 has an extremely high resistance of 6 ⁇ 10 6 ⁇ / ⁇ . Further, while the film thickness of Example 6 is 105 nm, the film thickness of Comparative Example 5 is 115 nm, which is about 10% thicker. From this point, the transparent conductive film of Example 6 is more transparent than the transparent conductive film of Comparative Example 5. Is densified by about 10%.
- Example 7 and Comparative Example 6 are transparent conductive films obtained by firing at 500 ° C. (air atmosphere and 1% hydrogen-99% nitrogen atmosphere). It can be seen that the resistance of ⁇ / ⁇ is obtained, whereas the comparative example 6 has an extremely high resistance of 8 ⁇ 10 6 ⁇ / ⁇ .
- the film thickness of Example 7 is 240 nm, whereas the film thickness of Comparative Example 6 is 310 nm, which is about 30% thicker. From this point, the transparent conductive film of Example 7 is more transparent than the transparent conductive film of Comparative Example 6. Is about 30% denser.
- the transparent conductive film according to the present invention can be formed on a heat-resistant substrate by using various inexpensive coating methods, and the obtained transparent conductive film has excellent transparency and high conductivity, and film strength. Therefore, a transparent conductive substrate in which this transparent conductive film is formed on a heat-resistant substrate is a light emitting device such as an LED element, an electroluminescence lamp (electroluminescence element), a field emission lamp, a power generation device such as a solar cell, It can be expected to be used for transparent electrodes such as liquid crystal displays, electroluminescent displays (electroluminescent elements), plasma displays, display devices such as electronic paper elements, and input devices such as touch panels.
- a transparent conductive substrate in which this transparent conductive film is formed on a heat-resistant substrate is a light emitting device such as an LED element, an electroluminescence lamp (electroluminescence element), a field emission lamp, a power generation device such as a solar cell. It can be expected to be used for transparent electrodes such as liquid crystal displays, electro
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Abstract
Description
しかしながら、これに使用する膜形成装置は真空容器をベースとするため非常に高価であり、また基板成膜毎に製造装置内の成分ガス圧を精密に制御しなければならないため、製造コストと量産性に問題がある。
この塗布方法では、透明導電膜形成用塗布液の基板上への塗布、乾燥、焼成という簡素な製造工程でITO透明導電膜を形成するもので、その塗布液の基板上への塗布法には、インクジェット印刷法、スクリーン印刷法、グラビア印刷法、オフセット印刷法、フレキソ印刷法、ディスペンサ印刷法、スリットコート法、ダイコート法、ドクターブレードコート法、ワイヤーバーコート法、スピンコート法、ディップコート法、スプレーコート法等が知られている。
これらの従来知られている塗布液の多くはインジウムや錫の硝酸塩、ハロゲン化物からなる有機または無機化合物、あるいは金属アルコキシドなどの有機金属化合物等が用いられている。
この塗布液は、低粘度であり、スピンコートのほかスプレーコート、ディップコートにも使用可能である。
本発明は、有機金属化合物を主成分とする透明導電膜形成用塗布液を、耐熱性基板上に塗布、乾燥、焼成して形成される透明導電膜の製造方法において、金属酸化物を主成分とする導電性酸化物微粒子の結晶成長が進み、かつ緻密に充填した導電性酸化物微粒子層を形成するため、透明導電膜の導電性の向上、及び膜強度の向上が図られる。
先ず、透明導電膜構造を説明する。
以下では、錫をドープした酸化インジウム(ITO)の透明導電膜を例に挙げて説明するが、酸化インジウム以外の、酸化錫や酸化亜鉛を主成分とする透明導電膜に関しても同じように行うことができる。
また、有機インジウム化合物と有機錫化合物を主成分とする透明導電膜形成用塗布液を耐熱性基板上に塗布、乾燥、焼成する塗布法で形成されるITOからなる透明導電膜では、通常ITO微粒子同士が結合した膜構造を有しており、ITO微粒子の粒子径やITO微粒子間に存在する空隙の大きさは、焼成条件などで異なるが、少なからず開空隙(オープンポア)を有するITO微粒子で構成される透明導電膜となることが知られている。
例えば酸化インジウムを主成分とする透明導電膜において、本発明の水蒸気含有量の少ない、すなわち露点が低い酸素含有雰囲気を適用した場合には、透明導電膜における導電性酸化物微粒子の充填密度は導電性酸化物の真比重の約90%程度まで高めることが可能であり、水蒸気を含む酸素含有雰囲気を適用した場合には、真比重の60~70%程度に留まる。
次に、本発明で用いられる透明導電膜形成用塗布液について詳細する。
本発明では、有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上の有機金属化合物を主成分とする透明導電膜形成用塗布液を用いて、酸化インジウム、酸化錫、酸化亜鉛のいずれか一つ以上を主成分とする透明導電膜を形成している。一般に、透明導電膜の導電性は高い方が望ましく、そのような場合には、酸化インジウム、酸化錫、酸化亜鉛という主成分となる酸化物にそれ以外の金属化合物、主として金属酸化物をドーピングすることで導電性を向上させる。即ち、ドーパント金属化合物を含む酸化インジウム、酸化錫、酸化亜鉛を導電性酸化物として用いれば、透明導電膜の導電性が向上する。これは、ドーパント金属化合物が導電性酸化物において、キャリアとしての電子の濃度(キャリア密度)を高める働きがあるからである。
その具体的なドーピングの方法としては、有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上の有機金属化合物を主成分とする透明導電膜形成用塗布液に、ドーパント用有機金属化合物を所定量配合する方法がある。
本発明で用いる有機インジウム化合物には、アセチルアセトンインジウム(正式名称:トリス(アセチルアセトナト)インジウム)[In(C5H7O2)3]、2−エチルヘキサン酸インジウム、蟻酸インジウム、インジウムアルコキシド等が挙げられるが、基本的には、溶剤に溶解し、焼成時において塩素ガスや窒素酸化物ガスなどの有害ガスが発生せずに酸化物に分解する有機インジウム化合物であれば良い。これらの中でもアセチルアセトンインジウムは有機溶剤への溶解性が高く、200~250℃程度の温度で熱分解・燃焼(酸化)して酸化物となるため好ましい。
なお、透明導電膜を適用するデバイスによっては導電性がある程度低い(抵抗値が高い)ことが必要とされる場合もあるため、透明導電膜形成用塗布液へのドーパント用有機金属化合物の添加は、必要に応じて適宜実施すればよい。
本発明で用いる有機錫化合物には、有機インジウム化合物を主成分とする透明導電膜形成用塗布液の説明で述べた有機錫化合物を用いることができ、導電性を向上させるドーパント用有機金属化合物としては、有機インジウム化合物、有機アンチモン化合物、有機リン化合物のいずれか一種以上が好ましい。
ドーパント用有機金属化合物としての有機インジウム化合物には、先に有機インジウム化合物を主成分とする透明導電膜形成用塗布液の説明で述べた有機インジウム化合物を用いれば良い。
本発明で用いる有機亜鉛化合物には、有機インジウム化合物を主成分とする透明導電膜形成用塗布液の説明で述べた有機亜鉛化合物を用いることができ、導電性を向上させるドーパント用有機金属化合物としては、有機アルミニウム化合物、有機インジウム化合物、有機ガリウム化合物のいずれか一種以上が好ましい。
ドーパント用有機金属化合物としての有機インジウム化合物には、先に有機インジウム化合物を主成分とする透明導電膜形成用塗布液の説明で述べた有機インジウム化合物を用いれば良い。
その合計含有量が1重量%未満であると膜厚の薄い透明導電膜しか得られなくなるため十分な導電性が得られない。また、30重量%より多いと透明導電膜形成用塗布液中の有機金属化合物が析出し易くなって塗布液の安定性が低下したり、得られる透明導電膜が厚くなり過ぎて亀裂(クラック)が発生して導電性が損なわれる場合がある。
なお、有機インジウム化合物を主成分とする透明導電膜形成用塗布液において、有機亜鉛化合物をドーピング用有機金属化合物して用いる場合には、有機金属化合物:ドーパント用有機金属化合物のモル比換算で95:5~66.7:33.3が良く、好ましくは91:9~71:29である。
なお、透明導電膜を適用するデバイスによっては、透明導電膜に対して、必ずしも高い導電性を必要とせず、逆に高い抵抗値が要求されることもある。そのような場合には、高抵抗の透明導電膜を得る目的で、あえて上記透明導電膜形成用塗布液にドーパント用有機金属化合物を配合せずに用いることができる。
ここで、セルロース誘導体として、例えばHPCの代わりにエチルセルロースを用いた場合には、HPCを用いた場合よりも塗布液の粘度が低く設定できるが、高粘度塗布液が好適であるスクリーン印刷法等ではパターン印刷性が若干低下する。
また、アクリル樹脂としては、比較的低温で燃焼するアクリル樹脂が好ましい。
本発明の透明導電膜の製造方法について詳細する。
本発明の透明導電膜は、透明導電膜形成用塗布液を耐熱性基板上に塗布して塗布膜を形成する塗布工程、その塗布膜を乾燥して乾燥塗布膜を形成する乾燥工程、その乾燥塗布膜を焼成して無機膜を形成する焼成工程の各工程を経て形成される。
(a)塗布工程
耐熱性基板上への透明導電膜形成用塗布液の塗布は、インクジェット印刷法、スクリーン印刷法、グラビア印刷法、オフセット印刷法、フレキソ印刷法、ディスペンサ印刷法、スリットコート法、ダイコート法、ドクターブレードコート法、ワイヤーバーコート法、スピンコート法、スプレーコート法等の各種塗布法を用いて塗布される。
上記耐熱基板としては、ソーダライムガラス、無アルカリガラス、石英ガラス等の無機基板や、ポリイミド(PI)等の樹脂基板(耐熱性プラスチックフィルム)を用いることができる。
この乾燥工程では、透明導電膜形成用塗布液を塗布した基板を、通常大気中80~180℃で1~30分間、好ましくは2~10分間保持して塗布膜の乾燥を行って、乾燥塗布膜を作製する。乾燥条件(乾燥温度、乾燥時間)は、用いる耐熱性基板の種類や透明導電膜形成用塗布液の塗布厚さ等によって、適宜選択することができる。ただし、生産性を考慮すれば、乾燥時間は、得られる乾燥塗布膜の膜質が悪化しない必要最低限度に短縮することが望ましい。
この乾燥塗布膜は、透明導電膜形成用塗布液から前述の有機溶剤が揮発除去されたものであって、有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上の有機金属化合物、(ドーパント用有機金属化合物)、バインダー等の有機系成分で構成されている。
焼成工程では、上記乾燥工程で得られた乾燥塗布膜を加熱処理(焼成)し、乾燥塗布膜中の有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上の有機金属化合物、あるいはドーパント用有機金属化合物を含んだ上記有機金属化合物、およびバインダー等の有機系成分を熱分解・燃焼(酸化)させて無機成分(金属酸化物を主成分とする導電性酸化物)からなる無機膜(導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層としての透明導電膜)を得ている。すなわち、焼成工程の昇温過程で加熱温度が高くなってくると、乾燥塗布膜中の有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上の有機金属化合物(ドーパント用有機金属化合物を含有する物も含む)は徐々に熱分解・燃焼(酸化)されて、まずアモルファス状態(ここでは、X線回折で求めた結晶子サイズ=3nm未満の非常に微細な粒子の状態を称する)の導電性酸化物への変換、所謂無機化が生じる。その後加熱温度が一層上昇して通常300~330℃の範囲を越えるか、あるいは300~330℃の範囲のままであっても加熱時間が長くなると上記導電性酸化物の結晶化が起き、さらに結晶成長して導電性酸化物微粒子となり最終的な透明導電膜の構成要素となる。
なお、上記300~330℃は上記無機化や結晶化が生じやすい一般的な温度範囲を示すものであって、例えば、加熱時間が長い場合には、270℃程度でも上記記導電性酸化物の無機化、結晶化、結晶成長が生じる場合もあるため、本発明の焼成工程の焼成温度が300℃以上に限定されるものではない。
上記乾燥塗布膜の焼成工程において、先ず露点の低い、即ち水蒸気含有量の少ない酸素含有雰囲気(参考として、図1に、空気中の飽和水蒸気含有量(体積%)と露点(℃)の関係を示す)を昇温過程の雰囲気に適用することで、上記の通り焼成工程の初期段階に生じる導電性酸化物の結晶化、並びに結晶成長が抑制されて、導電性酸化物微粒子が緻密に充填した本発明の導電性酸化物微粒子層の膜構造を得ることができる。なお、導電性酸化物微粒子が緻密に充填するメカニズムに関しては、必ずしも明らかではないが、例えば、以下のように考えることができる。
なお、上述した露点の低い、即ち水蒸気含有量の少ない空気雰囲気下において導電性酸化物の結晶化、並びに結晶成長が抑制される理由は明らかではないが、例えば、空気雰囲気中の水蒸気が、(1)導電性酸化物間に介在しているバインダー成分の熱分解・燃焼(酸化)の促進作用を有する、(2)導電性酸化物自体の結晶化、並びに結晶成長を促進する作用を有する、等が考えられる。
上記露点−10℃以下の酸素含有雰囲気ガスの露点は、好ましくは−15℃以下、より好ましくは−20℃以下、さらに好ましくは−30℃以下、最も好ましくは−40℃以下である。
また、上記露点−10℃以下の酸素含有雰囲気下で導電性酸化物の結晶化が起こる温度以上(本発明では通常300~330℃以上)に昇温する焼成において、その露点が−10℃を越えると、導電性酸化物微粒子からなる導電性酸化物微粒子層の形成過程において、焼成の初期段階でのバインダーがまだ多く残留している段階で水蒸気が導電性酸化物の結晶化、並びに結晶成長を促進して前述のアモルファス状態の導電性酸化物間にバインダーが均一に介在した膜垂直方向に収縮可能な膜構造が破壊されて、導電性酸化物微粒子同士が固着し動けなくなるため、膜の緻密化が阻害され、透明導電膜の導電性や膜強度が低下するため、好ましくない。
なお、耐熱性基板として耐熱性プラスチックであるポリイミド(PI)フィルムを用いた場合は、ポリイミドの種類にもよるが、400℃程度までの焼成が可能である。
なお、焼成工程の昇温過程における導電性酸化物の結晶化が起こる温度以上までの昇温速度については特に制約はないが、5~40℃/分の範囲、より一般的には10~30℃/分である。5℃/分より昇温速度が遅いと昇温に時間がかかりすぎて効率が悪くなり、一方40℃/分を越える昇温速度を上記焼成装置で実現しようとすると、ヒーター容量が大きくなりすぎて現実的でない。
300℃よりも低い焼成温度、特に270℃未満の焼成温度では、前述と同様に、通常、導電性酸化物微粒子同士の結晶化促進効果が不十分となり易く、導電性や膜強度の大幅な向上が期待しにくいため好ましいとは言えない。
なお、この中性雰囲気または還元性雰囲気下での焼成は、膜中に形成された酸素空孔が導電性酸化物微粒子の成分元素(インジウム、酸素等)を拡散しやすくするため、上記露点0℃以上の酸素含有雰囲気ガス中の焼成による導電性酸化物微粒子同士の結晶成長促進よりも、より強い促進効果を有しており、上記透明導電膜の導電性向上だけでなく、導電性の安定化(経時変化抑制)にも有効である点からも好ましい。
焼成温度が250~450℃程度であれば、1~2%水素−99~98%窒素の混合ガスは、大気に漏洩しても爆発の恐れがなく、酸化インジウムを金属インジウムまで還元し難いため好ましい雰囲気、焼成温度である。
250℃よりも低い焼成温度では、導電性酸化物微粒子に酸素空孔が十分に形成できず、キャリア濃度の増加による透明導電膜の導電性向上が期待できないため好ましくない。
このようなデバイスとしては、上述したようにLED素子、エレクトロルミネッセンスランプ(エレクトロルミネッセンス素子)、フィールドエミッションランプ等の発光デバイス、太陽電池等の発電デバイス、液晶ディスプレイ(液晶素子)、エレクトロルミネッセンスディスプレイ(エレクトロルミネッセンス素子)、プラズマディスプレイ、電子ペーパー素子等の表示デバイス、及びタッチパネル等の入力デバイス等が挙げられ、本発明の透明導電膜、透明導電基板はこれらの透明電極に好適である。
以下、幾つかのデバイスについて説明する。
この有機EL素子は、液晶表示素子と違って自発光素子であり、低電圧駆動で高輝度が得られるためディスプレイ等の表示装置として期待されている。有機EL素子にも低分子型と高分子型があり、例えば高分子型の構造は、アノード電極層としての透明導電膜上に、ポリチオフェン誘導体等の導電性高分子から成る正孔注入層(ホール注入層)、有機発光層(塗布により形成される高分子発光層)、カソード電極層[発光層への電子注入性の良い、仕事関数の低いマグネシウム(Mg)、カルシウム(Ca)、アルミニウム(Al)等の金属層]、ガスバリアコーティング層(あるいは金属やガラスでの封止処理)を順次形成したものである。上記ガスバリアコーティング層は、有機EL素子の劣化を防止するために必要とされ、酸素バリア及び水蒸気バリアが求められるが、例えば、水蒸気に関しては、水蒸気透過率=10−5g/m2/day程度以下の非常に高いバリア性能が要求されており、有機EL素子(デバイス)内部は外部から完全に封止された構造となっている。
なお、上記液晶素子の表示安定性を確保するためには、液晶への水蒸気の混入を防止する必要があり、例えば、水蒸気透過率=0.01g/m2/day以下が要求されており、液晶素子(デバイス)内部は外部から完全に封止された構造となっている。
この表示方式には、電気泳動法により着色粒子を電極間の液体中を移動させる電気泳動方式、二色性を有する粒子を電場で回転させることにより着色させるツイストボール方式、例えばコレステリック液晶を透明電極で挟み込んで表示を行う液晶方式、着色粒子(トナー)や電子粉流体(Quick Response Liquid Powder)を空気中を移動させて表示を行う粉体系方式、電気化学的な酸化・還元作用に基づき発色を行うエレクトロクロミック方式、電気化学的な酸化・還元により金属を析出・溶解させ、これに伴う色の変化で表示を行うエレクトロデポジション方式等が開発されている。これらいずれの方式においても、表示層が透明導電膜(透明電極)と対向電極とではさみ込まれた構造を有している。
例えば、抵抗方式タッチパネルでは、座標を検出するための座標検出用抵抗膜としての2枚の透明導電基板がドット状の透明スペーサーを介して貼り合わされている構造を有している。透明導電基板には打点耐久性が必要とされ、透明導電膜はクラックが生じないようなフレキシビリティが求められる。また、静電容量方式では解像度のアップにより、透明導電膜の一層の導電性向上が求められている。
アセチルアセトンインジウム(正式名称:トリス(アセチルアセトナト)インジウム)[In(C5H7O2)3](分子量=412.15)40g、p−tert−ブチルフェノール42g、二塩基酸エステル(デュポンジャパン製)14g、ヒドロキシプロピルセルロース(HPC)4gを混合し、130℃に加温して90分間攪拌して溶解させ、次に、得られた溶解液25g、シクロヘキサノン25g、プロピレングリコールモノメチルエーテル(PGM)10g、メチルエチルケトン(MEK)40gを混合して均一になるまで良く攪拌し、アセチルアセトンインジウムとヒドロキシプロピルセルロースを含有する溶解液(A液)を作製した。
アセチルアセトン錫(正式名称:ジ−n−ブトキシド ビス(2,4−ペンタンジオナト)錫[Sn(C4H9)2(C5H7O2)2](分子量=431.14)40g、p−tert−ブチルフェノール42g、二塩基酸エステル(デュポンジャパン製)14g、ヒドロキシプロピルセルロース(HPC)4gを混合し、130℃に加温して90分間攪拌して溶解させ、得られた溶解液25g、シクロヘキサノン25g、プロピレングリコールモノメチルエーテル(PGM)10g、メチルエチルケトン(MEK)40gを混合して均一になるまで良く攪拌し、アセチルアセトン錫とヒドロキシプロピルセルロースを含有する溶解液(B液)を作製した。
作製したA液9.6gとB液0.4gを均一になるまで良く攪拌し、アセチルアセトンインジウムとアセチルアセトン錫を合計で10重量%、ヒドロキシプロピルセルロースを1重量%含有する透明導電膜形成用塗布液を作製した。
この透明導電膜形成用塗布液を、25℃のソーダライムガラス基板(10cm×10cm×厚み3mm;ヘイズ値=0.26%、可視光透過率=91.1%)上の全面にスピンコーティング(250rpm×60sec)した後、熱風乾燥機を用いて180℃で20分間乾燥し、さらにホットプレートを用いて露点が−30℃の空気雰囲気(1リッター/分供給)において、500℃まで50分かけて昇温(昇温速度:10℃/分)し、500℃で15分間焼成し、そのまま雰囲気を2%水素−98%窒素(1リッター/分供給)に切替えて500℃でさらに15分間焼成してドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする実施例1に係る透明導電膜を作製した。
さらに、実施例1の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)、及び走査電子顕微鏡写真(SEM像)を、それぞれ図2、及び図3に示す。導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
ヘイズ値と可視光透過率は、日本電色(株)社製のヘイズメーター(NDH5000)を用いJIS K7136(ヘイズ値)、JISK7361−1(透過率)に基づいて測定した。
膜厚は、KLA−TencorCorporation製触針式膜厚計(Alpha−StepIQ)を用いて測定した。
結晶子サイズは、X線回折測定を行い、酸化インジウム(In2O3)の(222)ピークについて、Scherrer法により求めた。
鉛筆硬度は、JIS K5400に基づいて測定した。
なお、可視光透過率及びヘイズ値は、透明導電膜だけの値であり、それぞれ下記数1及び数2により求めた。
さらに、実施例2の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)、及び走査電子顕微鏡写真(SEM像)を、それぞれ図4、及び図5に示す。導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
さらに、実施例3の透明導電膜の断面を透過電子顕微鏡で観察したところ、導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
さらに、実施例4の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)を図6に示す。導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
実施例1のA液9.1gとB液0.9gを均一になるまで良く攪拌し、アセチルアセトンインジウムとアセチルアセトン錫を合計で10重量%、ヒドロキシプロピルセルロースを1重量%含有する透明導電膜形成用塗布液を作製した。
この透明導電膜形成用塗布液を、25℃のソーダライムガラス基板(10cm×10cm×厚み3mm)上の全面にスピンコーティング(200rpm×60sec)した後、180℃で10分間乾燥し、さらに−16℃、−19℃、−27℃、−34℃、−44℃、−80℃の各種露点を有する空気雰囲気(1リッター/分供給)において、500℃まで50分かけて昇温(昇温速度:10℃/分)し、500℃で15分間焼成後、そのまま雰囲気を1%水素−99%窒素(1リッター/分供給)に切替えて500℃でさらに15分間焼成して、ドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする実施例5に係る各種透明導電膜を作製した。
なお、上記−16℃~−80℃の各種露点を有する空気雰囲気は、露点25℃の空気と露点−80℃の空気を、それぞれ所定の流量で供給し、よく混合して得ている。
実施例5に係る上記各種透明導電膜は、それぞれ高い透明性を有しており(ヘイズ値:0.15~0.3%の範囲内、可視光透過率:92.6~95.5%の範囲内)、さらにいずれの透明導電膜においても鉛筆硬度は5H以上と優れていた。
なお、実施例5の各種透明導電膜の断面を透過電子顕微鏡で観察したところ、導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
アセチルアセトン錫(正式名称:ジ−n−ブトキシド ビス(2,4−ペンタンジオナト)錫[Sn(C4H9)2(C5H7O2)2](分子量=431.14)9.9g、アンチモン(III)−n−ブトキシド[Sb(C4H9O)3](分子量=341.08)0.1g、p−tert−ブチルフェノール10.5g、二塩基酸エステル(デュポンジャパン製)3.5g、ヒドロキシプロピルセルロース(HPC)1g、アセチルアセトン75gを混合し、120℃に加温しながら120分間攪拌して均一になるまで良く溶解し、アセチルアセトン錫とアンチモン(III)−n−ブトキシドを合計で10重量%、ヒドロキシプロピルセルロースを1重量%含有する透明導電膜形成用塗布液を作製した。
この透明導電膜形成用塗布液を、25℃のソーダライムガラス基板(10cm×10cm×厚み3mm;ヘイズ値=0.26%、可視光透過率=91.1%)上の全面にスピンコーティング(250rpm×60sec)した後、熱風乾燥機を用いて180℃で10分間乾燥し、さらにホットプレートを用いて露点が−60℃の空気雰囲気(1リッター/分供給)において、500℃まで50分かけて昇温(昇温速度:10℃/分)し、500℃で15分間焼成し、そのまま雰囲気を1%水素−99%窒素(1リッター/分供給)に切替えて500℃でさらに15分間焼成して、ドーパント用の酸化アンチモンを含んだ酸化錫(SnO2)を主成分とする実施例6に係る透明導電膜を作製した。
さらに、実施例6の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)を図10に示す。導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
アセチルアセトン亜鉛(正式名称:亜鉛−2,4−ペンタンジオネート)[Zn(C5H7O2)2](分子量=263.59)10g、γ−ブチロラクトン49.99g、アセチルアセトン38g、ヒドロキシプロピルセルロース(HPC)2g、界面活性剤0.01gを混合し、120℃に加温しながら90分間攪拌して均一になるまで良く溶解し、アセチルアセトン亜鉛とヒドロキシプロピルセルロースを含有する溶解液(C液)を作製した。
アセチルアセトンアルミニウム(正式名称:アルミニウム−2,4−ペンタンジオネート)[Al(C5H7O2)3](分子量=324.29)10g、p−tert−ブチルフェノール28.5g、二塩基酸エステル(デュポンジャパン製)9.5g、アセチルアセトン49.99g、ヒドロキシプロピルセルロース(HPC)2g、界面活性剤0.01gを混合し、120℃に加温しながら90分間攪拌して均一になるまで良く溶解し、アセチルアセトンアルミニウムとヒドロキシプロピルセルロースを含有する溶解液(D液)を作製した。
作製したC液9.5gとD液0.5gを均一になるまで良く攪拌し、アセチルアセトン亜鉛とアセチルアセトンアルミニウムを合計で10重量%、ヒドロキシプロピルセルロースを2重量%含有する透明導電膜形成用塗布液を作製した。
この透明導電膜形成用塗布液を、25℃のソーダライムガラス基板(10cm×10cm×厚み3mm;ヘイズ値=0.26%、可視光透過率=91.1%)上の全面にスピンコーティング(250rpm×60sec)した後、熱風乾燥機を用いて180℃で10分間乾燥し、さらにホットプレートを用いて露点が−60℃の空気雰囲気(1リッター/分供給)において、500℃まで50分かけて昇温(昇温速度:10℃/分)し、500℃で15分間焼成し、そのまま雰囲気を1%水素−99%窒素(1リッター/分供給)に切替えて500℃でさらに15分間焼成して、ドーパント用の酸化アルミニウム(Al2O3)を含んだ酸化亜鉛(ZnO2)を主成分とする実施例7に係る透明導電膜を作製した。
さらに、実施例7の透明導電膜の断面を透過電子顕微鏡で観察した走査電子顕微鏡写真(SEM像)を図11に示す。導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層が観察されている。
実施例1で露点が−30℃の空気の代わりに、露点が15℃の空気を用いた以外は実施例1と同様にして成膜を行い、ドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする比較例1に係る透明導電膜を作製した。
さらに、比較例1の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)、及び走査電子顕微鏡写真(SEM像)を、それぞれ図12、及び図13に示す。導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
実施例2で露点が−30℃の空気の代わりに、露点が15℃の空気を用いた以外は実施例2と同様にして成膜を行い、ドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする比較例2に係る透明導電膜を作製した。
さらに、比較例2の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)、及び走査電子顕微鏡写真(SEM像)を、それぞれ図14、及び図15に示す。導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
実施例4で露点が−30℃の空気の代わりに、露点が約20℃の空気を用いた以外は実施例4と同様にして成膜を行い(すなわち、露点が約20℃の空気雰囲気(1リッター/分供給)において、500℃まで50分かけて昇温(昇温速度:10℃/分)し、そのまま500℃で30分間焼成して、ドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする比較例3に係る透明導電膜を作製した。
さらに、比較例3の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)を図16に示す。導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
実施例5で、−16℃~−80℃の各種露点を有する空気の代わりに、25℃、6℃、−4℃の各種露点を有する空気を用いた以外は実施例5と同様にして成膜を行い、ドーパント用の酸化錫(SnO2)を含んだ酸化インジウム(In2O3)を主成分とする比較例4に係る各種透明導電膜を作製した。
なお、上記25℃、6℃、−4℃の各種露点を有する空気雰囲気は、露点25℃の空気と露点−80℃の空気をそれぞれ所定の流量で供給し、よく混合して得ている。
比較例4に係る上記各種透明導電膜は、それぞれ高い透明性を有していたものの(ヘイズ値:0.1~0.3%の範囲内、可視光透過率:92.3~98.7%の範囲内)、いずれの透明導電膜においても鉛筆硬度は3H未満と不十分だった。
なお、比較例4の各種透明導電膜の断面を透過電子顕微鏡で観察したところ、導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
実施例6で露点が−60℃の空気の代わりに、露点が23℃の空気を用いた以外は実施例6と同様にして成膜を行い、ドーパント用の酸化アンチモンを含んだ酸化錫(SnO2)を主成分とする比較例5に係る透明導電膜を作製した。
さらに、比較例5の透明導電膜の断面を透過電子顕微鏡で観察した透過電子顕微鏡写真(TEM像)を図17に示す。導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
実施例7で露点が−60℃の空気の代わりに、露点が23℃の空気を用いた以外は実施例7と同様にして成膜を行い、ドーパント用の酸化アルミニウム(Al2O3)を含んだ酸化亜鉛(ZnO2)を主成分とする比較例6に係る透明導電膜を作製した。
さらに、比較例6の透明導電膜の断面を透過電子顕微鏡で観察した走査電子顕微鏡写真(SEM像)を図18に示す。導電性酸化物微粒子間に空隙が見られる導電性酸化物微粒子層が観察されている。
また、実施例1及び実施例3の膜厚が190nmであるのに対し、比較例1の膜厚は225nmと約18%程度厚く、この点から実施例1及び実施例3の透明導電膜は比較例1の透明導電膜よりも約18%程度緻密化している。
また、実施例2の膜厚が205nmであるのに対し、比較例2の膜厚は225nmと約10%程度厚く、この点から実施例2の透明導電膜は比較例2の透明導電膜よりも約10%程度緻密化している。
また、実施例4の膜厚が185nmであるのに対し、比較例3の膜厚は230nmと約24%程度厚く、この点からも実施例4の透明導電膜は、比較例3の透明導電膜よりも約24%程度緻密化している。
また、実施例5の各種透明導電膜の膜厚が228nm以下であるのに対し、比較例4の各種透明導電膜の膜厚は246nm以上と厚く、この点からも実施例5の各種透明導電膜は、比較例4の各種透明導電膜よりも緻密化していることがわかる。
また、実施例6の膜厚が105nmであるのに対し、比較例5の膜厚は115nmと約10%程度厚く、この点から実施例6の透明導電膜は比較例5の透明導電膜よりも約10%程度緻密化している。
また、実施例7の膜厚が240nmであるのに対し、比較例6の膜厚は310nmと約30%程度厚く、この点から実施例7の透明導電膜は比較例6の透明導電膜よりも約30%程度緻密化している。
Claims (17)
- 主成分として有機金属化合物を含有する透明導電膜形成用塗布液を、耐熱性基板上に塗布して塗布膜を形成する塗布工程、前記塗布膜を乾燥して乾燥塗布膜を形成する乾燥工程、前記乾燥塗布膜を焼成して、金属酸化物である無機成分を主成分とする無機膜を形成する焼成工程の各工程を経て形成される、透明導電膜の製造方法であって、
前記焼成工程が、前記乾燥工程で形成された有機金属化合物を主成分とする前記乾燥塗布膜を、露点−10℃以下の酸素含有雰囲気下で、少なくとも前記無機成分の結晶化が起こる焼成温度以上まで昇温する焼成を行い、前記乾燥塗布膜に含まれる有機成分を熱分解または燃焼、或いは熱分解並びに燃焼により除去することで金属酸化物を主成分とする導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層を形成する工程で、
前記有機金属化合物が、有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上からなり、前記金属酸化物が、酸化インジウム、酸化錫、酸化亜鉛のいずれか一つ以上であること、
を特徴とする透明導電膜の製造方法。 - 主成分として有機金属化合物及びドーパント用有機金属化合物を含有する透明導電膜形成用塗布液を、耐熱性基板上に塗布して塗布膜を形成する塗布工程、前記塗布膜を乾燥して乾燥塗布膜を形成する乾燥工程、前記乾燥塗布膜を焼成して、ドーパント金属化合物を含む金属酸化物である無機成分を主成分とする無機膜を形成する焼成工程の各工程を経て形成される、透明導電膜の製造方法であって、
前記焼成工程が、前記乾燥工程で形成された有機金属化合物及びドーパント用有機金属化合物を主成分とする前記乾燥塗布膜を、露点−10℃以下の酸素含有雰囲気下で、少なくとも前記無機成分の結晶化が起こる焼成温度以上まで昇温する焼成を行い、前記乾燥塗布膜に含まれる有機成分を熱分解または燃焼、或いは熱分解並びに燃焼により除去することでドーパント金属化合物を含み金属酸化物を主成分とする導電性酸化物微粒子が緻密に充填した導電性酸化物微粒子層を形成する工程で、
前記有機金属化合物が、有機インジウム化合物、有機錫化合物、有機亜鉛化合物のいずれか一つ以上からなり、前記金属酸化物が、酸化インジウム、酸化錫、酸化亜鉛のいずれか一つ以上であること、
を特徴とする透明導電膜の製造方法。 - 前記有機金属化合物及びドーパント用有機金属化合物の含有割合が、有機金属化合物:ドーパント用有機金属化合物のモル比換算で、99.9:0.1~66.7:33.3の範囲であることを特徴とする請求項2記載の透明導電膜の製造方法。
- 前記有機金属化合物が、有機インジウム化合物からなり、
前記ドーパント用有機金属化合物が、有機錫化合物、有機チタン化合物、有機ゲルマニウム化合物、有機亜鉛化合物、有機タングステン化合物、有機ジルコニウム化合物、有機タンタル化合物、有機ニオブ化合物、有機ハフニウム化合物、有機バナジウム化合物のいずれか一種以上であり、前記ドーパント金属化合物が、酸化錫、酸化チタン、酸化ゲルマニウム、酸化亜鉛、酸化タングステン、酸化ジルコニウム、酸化タンタル、酸化ニオブ、酸化ハフニウム、酸化バナジウムのいずれか一種以上であることを特徴とする請求項2または3記載の透明導電膜の製造方法。 - 前記有機金属化合物が、有機錫化合物からなり、
前記ドーパント用有機金属化合物が、有機インジウム化合物、有機アンチモン化合物、有機リン化合物のいずれか一種以上であることを特徴とする請求項2または3記載の透明導電膜の製造方法。 - 前記有機金属化合物が有機亜鉛化合物からなり、
前記ドーパント用有機金属化合物が、有機アルミニウム化合物、有機インジウム化合物、有機ガリウム化合物のいずれか一種以上であることを特徴とする請求項2または3記載の透明導電膜の製造方法。 - 前記有機インジウム化合物が、アセチルアセトンインジウムであることを特徴とする請求項1~6のいずれか1項に記載の透明導電膜の製造方法。
- 前記露点−10℃以下の酸素含有雰囲気下で、少なくとも前記無機成分の結晶化が起こる焼成温度以上まで昇温する焼成に続いて、露点0℃以上の酸素含有雰囲気下での300℃以上の焼成温度で焼成することを特徴とする請求項1または2記載の透明導電膜の製造方法。
- 前記露点−10℃以下の酸素含有雰囲気下で、300℃以上の焼成温度による焼成に続いて、中性雰囲気または還元性雰囲気下で、250℃以上の焼成温度で焼成することを特徴とする請求項1または2記載の透明導電膜の製造方法。
- 前記露点0℃以上の酸素含有雰囲気下で、少なくとも前記無機成分の結晶化が起こる焼成温度以上まで昇温する焼成に続いて、中性雰囲気または還元性雰囲気下での250℃以上の焼成温度で焼成することを特徴とする請求項8記載の透明導電膜の製造方法。
- 前記中性雰囲気が、窒素ガス、不活性ガスのいずれか一種以上、または前記還元性雰囲気が、水素ガス若しくは前記中性雰囲気に水素ガス或いは有機溶剤蒸気の少なくとも一種以上が含まれた雰囲気であることを特徴とする請求項9または10記載の透明導電膜の製造方法。
- 前記露点−10℃以下の酸素含有雰囲気下での焼成における前記酸素含有雰囲気の露点が、−20℃以下であることを特徴とする請求項1~11のいずれか1項に記載の透明導電膜の製造方法。
- 前記塗布工程における透明導電膜形成用塗布液の耐熱性基板上への塗布方法が、インクジェット印刷法、スクリーン印刷法、グラビア印刷法、オフセット印刷法、フレキソ印刷法、ディスペンサ印刷法、スリットコート法、ダイコート法、ドクターブレードコート法、ワイヤーバーコート法、スピンコート法、ディップコート法、スプレーコート法のいずれかであることを特徴とする請求項1または2記載の透明導電膜の製造方法。
- 請求項1~13のいずれか1項に記載の透明導電膜の製造方法で得られたことを特徴とする透明導電膜。
- 耐熱性基板上に透明導電膜を備える透明導電基板において、
前記透明導電膜が、請求項14記載の透明導電膜であることを特徴とする透明導電基板。 - 透明電極を備えるデバイスにおいて、
前記透明電極が、請求項15記載の透明導電基板であることを特徴とするデバイス。 - 前記デバイスが、発光デバイス、発電デバイス、表示デバイス、入力デバイスから選ばれた1種であることを特徴とする請求項16記載のデバイス。
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