WO2005083722A1 - 透明導電膜及びそれを用いた透明導電性基材 - Google Patents
透明導電膜及びそれを用いた透明導電性基材 Download PDFInfo
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- WO2005083722A1 WO2005083722A1 PCT/JP2004/019595 JP2004019595W WO2005083722A1 WO 2005083722 A1 WO2005083722 A1 WO 2005083722A1 JP 2004019595 W JP2004019595 W JP 2004019595W WO 2005083722 A1 WO2005083722 A1 WO 2005083722A1
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- Prior art keywords
- film
- transparent conductive
- thin film
- oxygen
- indium
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 9
- 239000010408 film Substances 0.000 claims abstract description 213
- 239000010409 thin film Substances 0.000 claims abstract description 90
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 43
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052738 indium Inorganic materials 0.000 claims abstract description 34
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 229920001230 polyarylate Polymers 0.000 claims description 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 4
- 238000005401 electroluminescence Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
- H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
Definitions
- the present invention relates to a transparent conductive film used for an organic electroluminescence (EL) element and the like, and a transparent conductive substrate using the same.
- EL organic electroluminescence
- the transparent conductive film high conductivity (e.g., less resistivity 1 X 10- 3 ⁇ cm), because they have a high transmittance in the visible light area, solar cells, liquid crystal display elements, In addition, it is used as an electrode for various light-receiving elements, etc. It is also used as a window glass for automobiles and architectural windows, a heat ray reflective film, various antistatic films, and a transparent anti-fog film for frozen showcases. It is also used as a heating element.
- the transparent conductive film includes an oxidized tin (SnO 2) film doped with antimony or fluorine, aluminum
- Oxidized zinc (ZnO) films doped with palladium and gallium, tin-doped indium oxide (In O) films, and the like are widely used.
- ITO Indium Tin Oxide
- the ITO film is also used as an electrode of an organic EL device.
- Organic EL devices have a drastically reduced driving voltage and can be easily miniaturized. Therefore, research on practical use as a next-generation display device has been actively conducted.
- the configuration of the organic EL element is based on a stack of anode / light-emitting layer / cathode, and usually employs a configuration in which the ITO film is formed as a transparent anode on a substrate using a glass plate or the like. Since holes are injected from the anode, the work function of the anode is preferably higher. In this case, the work function requires a force of at least 4.4 eV or more, and preferably a force of 5. OeV or more. However, it is generally known that the work function of an ITO film is about 4.4 eV, and the work function is not sufficient for use as an anode of an organic EL device.
- Patent Document 1 discloses an organic electroluminescent device in which an organic layer including an organic light-emitting layer is sandwiched between an anode and a cathode. a conductive film, sequentially together are laminated comprising at resistivity 1 X 10- 5 ⁇ cm or less of the metal thin film, an organic elect port Ruminesse Nsu element transparent thin film layer on the outside of the cathode is formed is proposed.
- the transparent thin film layer is made of indium (In), zinc (Zn), an amorphous transparent conductive film using an oxide that also has oxygen (O) power, V, a so-called IZO film.
- the IZO film is a stable amorphous film that does not contain microcrystals that has only a low specific resistance, and thus is useful as an electrode film of an organic EL.
- the work function of the IZO film is about 4.8-4.9 eV, which is not high enough to be used as an organic EL anode. As with ITO films, it is necessary to increase the work function by surface treatment.
- Patent Document 1 Japanese Patent Application Laid-Open No. 7-182924
- Non-Patent Document 1 "New Development of Transparent Conductive Film II", CMC Publishing, First Edition, P203 Invention Disclosure
- An object of the present invention is to provide a transparent conductive film having a low surface resistance and a high work function, which is formed by laminating transparent conductive thin films, and a transparent conductive substrate using the same.
- the present inventors have proposed an amorphous oxide film having Ga, In, and O forces, which is a transparent oxide film containing Ga in an amount of 49.1 at.% Or more and 65 at.
- the conductive film has the characteristic that the 1S work function is as high as 5.leV or more, so that the conductivity is still not sufficiently satisfied in order to be used as the transparent electrode of the organic EL.
- the characteristic having the function at least two or more transparent conductive films were sequentially laminated on the substrate.
- a laminated film is formed, and the first transparent conductive film on the uppermost surface is an amorphous oxide thin film composed of gallium, indium, and oxygen.
- the present inventors have found that a transparent conductive film having a work function of 5. leV or more and a surface resistance of a laminated film of 100 ⁇ / square or less can be obtained by using a transparent conductive film containing at most atomic%. .
- the first transparent conductive thin film as the uppermost layer is formed of a glass.
- the surface resistance is 50 ⁇ 50 or less.
- the other transparent conductive thin film on the substrate side than the first transparent conductive thin film is made of indium, tin and an amorphous silicon oxide thin film having oxygen power, indium, Misalignment of an amorphous oxide thin film composed of zinc and oxygen, an amorphous oxide thin film composed of indium, tungsten and oxygen, or an amorphous oxide thin film composed of indium, tungsten, zinc and oxygen Or more than one kind.
- the thickness of the first transparent conductive thin film is 5 nm or more, and the total thickness of the laminated transparent conductive thin films is 300 nm or less.
- the arithmetic mean height (Ra) of the surface of the first transparent conductive thin film is 2.0 nm or less.
- the transparent conductive substrate according to the present invention includes a glass plate, a quartz plate, a resin plate or a resin film in which one or both surfaces are covered with a gas barrier film, or a gas noria film inserted therein. And / or a transparent substrate selected from a resin plate or a resin film, and the transparent conductive film formed on one or both surfaces of the transparent substrate.
- the gas nolia film is at least one selected from an oxidized silicon film, an oxidized silicon nitride film, a magnesium aluminate film, a tin oxide-based film, and a diamond-like carbon film. It is.
- the transparent conductive film of the present invention is composed of a laminated film in which at least two or more transparent conductive thin films are sequentially laminated on a substrate, and the uppermost transparent conductive thin film is formed of gallium, indium and oxygen.
- a work film with a work function of 5. leV which could not be obtained conventionally by using a transparent conductive film containing gallium in a content of 49.1 at% to 65 at% based on all metal atoms.
- a transparent conductive film having a surface resistance of 100 ⁇ square or less can be obtained.
- the transparent conductive film of the present invention when used as an anode of an organic EL device or the like, holes are easily injected. As a result, the transparent conductive film of the present invention can improve the luminous efficiency of an organic EL device or the like and is useful.
- the transparent conductive substrate of the present invention may be a gas-barrier film, if necessary, on a resin substrate having no heat resistance, such as a glass substrate or a quartz substrate, or a flexible resin film substrate. After formation, it is obtained by forming the transparent conductive film of the present invention. Therefore, it can be used as a base material for a flexible transparent organic EL device using a resin film substrate for any device shape and form, and is extremely valuable industrially.
- FIG. 1 is a cross-sectional view showing a basic configuration of a transparent conductive substrate in which a transparent conductive film is formed on a substrate.
- FIG. 2 is a cross-sectional view showing a basic configuration of a transparent conductive base material in which a gas noria film is formed on a base material and a transparent conductive film is formed thereon.
- the transparent conductive film according to the present invention comprises a laminated film in which at least two or more transparent conductive thin films are sequentially laminated on a substrate, and the uppermost transparent conductive thin film is composed of gallium, indium and oxygen.
- An amorphous silicon oxide thin film that is also strong and contains 49.1 atomic% to 65 atomic% of gallium based on all metal atoms, has a work function of 5. leV or more, It is characterized in that the sheet resistance is less than 100 ⁇ per square.
- Gallium content is 49.1 atoms %, The work function decreases, and when the gallium content exceeds 65 atomic%, sufficient conductivity as a conductive film cannot be obtained! / ⁇ .
- the other transparent conductive thin film laminated on the substrate side from the uppermost transparent conductive thin film of the laminated film is indium, tin and an amorphous oxide thin film which also has oxygen power, indium, At least one force of an amorphous oxide thin film composed of zinc and oxygen, an amorphous oxide thin film composed of indium, tungsten, and oxygen, or an amorphous oxide thin film composed of indium, tungsten, zinc, and oxygen Preferably, it is a thin film.
- the amorphous thin film exhibiting 10- 4 Omega in cm stand a low specific resistance can be easily obtained.
- an amorphous oxide film composed of indium, zinc and oxygen, an amorphous oxide film composed of indium, tungsten and oxygen, and an amorphous oxide film composed of indium, tungsten, zinc and oxygen Since the dangling thin film is an almost completely amorphous film in which microcrystals are hardly seen, it is still more preferable as an electrode of an organic EL which does not like surface irregularities due to the existence of microcrystals.
- the uppermost transparent conductive thin film has a thickness of 5 nm or more and 50 nm or less, and the total thickness of the laminated film is 300 nm or less. If the thickness of the uppermost transparent conductive thin film is less than 5 nm, a stable high work function cannot be obtained. On the other hand, when the film thickness exceeds 50 nm, when the first layer (top layer) is laminated on the second and subsequent transparent conductive thin films, the ratio of the top layer thickness to the total thickness of the laminated film is reduced. And the resistance increases.
- the total thickness of the laminated film exceeds 300 nm, when the first layer (the uppermost layer) is laminated on the second and subsequent transparent conductive thin films, the second and subsequent transparent conductive thin films become too thick. Coloring occurs, and a sufficient transmittance cannot be obtained. Further, when the total thickness of the laminated film is less than 100 nm, the surface resistance of the laminated film is increased. Therefore, the total thickness is more preferably 100 nm or more.
- the arithmetic average height (Ra) of the surface of the first layer of the transparent conductive thin film is preferably 2.Onm or less. More preferably, the height is 1. Onm or less. If the arithmetic average height (Ra) of the surface of the transparent conductive thin film of the first layer exceeds 2. Onm, for example, when used as an electrode of an organic EL, leakage occurs at a convex portion of the electrode, so that the Problems such as generation of a large number of dark spots in the EL are not preferred.
- the transparent conductive substrate of the present invention is formed by forming the transparent conductive film of the present invention on the surface of a transparent substrate.
- the transparent substrate examples include a glass plate, a quartz plate, a resin plate or a resin film having one or both surfaces covered with a gas barrier film, or a resin plate or a resin film having a gas noria film inserted therein. Used.
- a resin plate or resin film has higher gas permeability than a glass plate.
- the light-emitting layer of organic EL elements and inorganic EL elements, and the liquid crystal layer of LCD etc. are inferior to moisture and oxygen. Therefore, when a resin plate or a resin film is used as a substrate for these display elements, it is preferable to provide a gas noria film for suppressing gas passage.
- the gas barrier film is formed on one side of the resin plate or the resin film, or on both sides, the gas barrier property is further improved.
- a gas barrier film is formed on one side of a resin plate or a resin film, and a resin plate or a resin film is laminated on the gas resin film to insert a gas barrier film therein.
- the obtained configuration can be obtained. Further, a structure in which lamination is repeated a plurality of times may be employed.
- the resin plate or resin film is made of polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate (PAR), polycarbonate (PC), or the surface of these materials is made of acrylic resin. It is a laminated structure covered with organic matter.
- the thickness of the resin film V is selected appropriately according to the following specific applications.
- the gas barrier film is at least one selected from an oxidized silicon film, a silicon oxynitride (SiON) film, a magnesium aluminum oxide film, a tin oxide-based film, and a diamond-like carbon (DLC) film.
- SiON silicon oxynitride
- DLC diamond-like carbon
- the tin oxide-based film has a composition in which tin oxide contains, for example, at least one or more additional elements selected from the group consisting of Si, Ce, and Ge. With these added elements, the tin oxide layer is made amorphous to form a dense film.
- At least one gas nolia film selected from an oxidized silicon film, an oxidized silicon nitride film, a magnesium aluminum oxide film, a tin oxide-based film, and a diamond-like carbon film, and an organic or polymer film.
- a configuration in which the transparent conductive film is provided on a substrate having a structure in which the surface is repeatedly and alternately laminated on a resin substrate or a resin film may be used.
- FIG. 1 is a cross-sectional view showing a basic configuration of a transparent conductive substrate used in Examples 1 to 6.
- the transparent conductive films 10 and 20 were formed by a DC magnetron sputtering method using a special SPF-530H nottering device manufactured by ANELVA.
- the transparent conductive thin films 10 and 20 have a predetermined thickness at a power of 200 W using a mixed gas of argon and oxygen at a gas pressure of 0.5 Pa and an oxygen flow rate of 1.5 to 2.5%.
- the film was formed by adjusting the time as described above.
- FIG. 2 is a cross-sectional view showing a basic configuration of the transparent conductive substrate used as Example 7.
- a silicon oxide nitride film having a thickness of 100 nm is formed in advance as a gas noria film 30 on a substrate 51 made of a PES film having a thickness of 200 m, and the same transparent conductive film as in Examples 1 to 6 is formed on the gas noria film 30. Film 1 was formed.
- the work function of the obtained transparent conductive film 1 was measured with an atmospheric photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.).
- the surface resistance of the film was measured by a four-probe method using a resistivity meter Loresta EP (Model MCP-T360 manufactured by Dia Instruments Co., Ltd.).
- the surface roughness of the film was measured by an atomic force microscope (NS-IIU D5000 system, manufactured by Digital Instruments).
- the light transmittance including the substrate 51 was measured with a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).
- the transparent conductive film 20 was formed using a 150 nm thick In 2 O 3 -wt% WO amorphous film.
- the transparent conductive film 10 was a 10-nm-thick amorphous film having gallium, indium and oxygen power.
- the transparent conductive thin film 10 was an amorphous film made of gallium, indium, and oxygen having a film thickness of 10 nm and a gallium content of 50 atomic%. 150nm thick In O 10wt% Sn
- One of the ZnO amorphous films was selected and combined.
- the transparent conductive thin film 10 was set to a thickness of 5 nm, the gallium content was set to 50 atomic%, and the transparent conductive thin film 20 was formed of a 150 nm thick In 2 O 3 -lwt% WO As a crystalline film
- Table 1 shows work functions and surface resistance values of the transparent conductive films 1 of Examples 1 to 8.
- the transparent conductive thin film 10 was an amorphous film having a film thickness of lOnm, which also had gallium, indium, and oxygen power, and was composed of three types of gallium contents of 49.150 and 65 atomic% with respect to all metal atoms, respectively.
- the transparent conductive thin film 20 is a 150 nm thick InO-lwt% WO
- the gallium content of the transparent conductive thin film 10 is in the range of 49.1 to 65 atomic%, the work function is 5.leV or more, and the surface resistance is 50 ⁇ or less.
- the transparent conductive film 1 is obtained.
- the transparent conductive thin film 10 is an amorphous film having a film thickness of lOnm, which also has gallium, indium and oxygen power, and has a composition of only one kind having a gallium content of 50 atomic% with respect to all metal atoms.
- the transparent conductive thin film 20 is a 150 nm thick InO 10 wt% SnO amorphous film, InOlOw
- a transparent conductive thin film 10 having a thickness of 10 nm and a gallium content of 50 atomic% and a transparent conductive thin film 20 having a thickness of 150 nm were formed of InO-10 wt% SnO amorphous.
- the transparent conductive thin film 10 was a 5 nm-thick amorphous film having gallium, indium and oxygen power, and the composition was such that the gallium content was 50 atomic% based on all metal atoms.
- the transparent conductive thin film 20 was an In 2 O-lwt% WO amorphous film having a thickness of 150 nm.
- Example 7 even when the thickness of the transparent conductive thin film 10 is reduced to 5 nm, a transparent conductive film 1 having a work function of 5. leV or more and a surface resistance of 50 ⁇ or less can be obtained.
- the transparent conductive thin film 10 was an amorphous film having a film thickness of lOnm, which also had gallium, indium, and oxygen power, and had a gallium content of only 50 atomic% based on all metal atoms.
- the transparent conductive thin film 20 was an In 2 O 1 -wt% WO amorphous film having a thickness of 290 nm.
- Example 8 even when the total film thickness is increased to 300 nm, a transparent conductive film 1 having a work function of 5. leV or more and a surface resistance of 50 ⁇ or less can be obtained.
- the average light transmittance in the visible range was also over 80%, and there was no problem with coloring at the visual level.
- a silicon oxynitride film having a thickness of 100 nm was formed as a gas nolia film in advance, and a transparent conductive film 1 having the same structure as that of Example 2 was formed on the gas noria film.
- Example 9 It can be seen from Example 9 that the transparent conductive film 1 having a work function of 5. leV or more and a surface resistance of 50 ⁇ or less was obtained even when a resin film in which the gas nolia film 30 was formed in advance on the substrate was used. Puru.
- a transparent conductive substrate having the same configuration as in Examples 1 to 6 was produced.
- Comparative Examples 1 to 3 were prepared by transforming the transparent conductive thin film 20 into a 150 nm thick InO-lwt% WO amorphous.
- the gallium content of the transparent conductive thin film 10 having a thickness of 10 nm was changed.
- Comparative Examples 4 and 5 when the transparent conductive thin film 10 was 3 nm in film thickness and the gallium content was 50 atomic%, and the transparent conductive thin film 20 was a 150 nm thick In 2 O-lwt% WO amorphous film, You
- the transparent conductive thin film 10 had a thickness of 10 nm and a gallium content of 50 atomic%, and the transparent conductive thin film 20 had a thickness of 300 nm and an InO 10 wt% SnO amorphous film. Comparative Example 1
- Table 2 shows the work functions and surface resistance values of the No. 5 to No. 5 transparent conductive films 1. [0040] Table 2
- the transparent conductive thin film 10 was an amorphous film made of gallium, indium, and oxygen having a film thickness of lOnm, and had a gallium content of 30 45 and a gallium content of 30 Three types of 70 atomic% were used.
- the transparent conductive thin film 20 was an In 2 O 3 -lwt% WO amorphous film having a thickness of 150 nm.
- the transparent conductive thin film 10 was an amorphous film made of gallium, indium and oxygen having a thickness of 5 nm, and the composition was such that the gallium content relative to all metal atoms was only 50 atomic%.
- the transparent conductive thin film 20 is a 150 nm thick InO-lwt% WO amorphous film.
- the transparent conductive thin film 10 was an amorphous film made of gallium, indium and oxygen having a film thickness of 50 nm, and the composition was such that the gallium content was 50 atomic% based on all metal atoms. .
- the transparent conductive thin film 20 is a 300 nm thick InO-10 wt% SnO amorphous film.
- the transparent conductive film of the present invention When the transparent conductive film of the present invention is used particularly as an anode of an organic EL device or the like, holes can be easily injected, and as a result, the luminous efficiency of the organic EL device or the like can be improved, which is useful. It is.
- the transparent conductive substrate of the present invention may be obtained by forming a gas barrier film on a resin substrate having no heat resistance, such as a glass substrate or a quartz substrate alone, or a flexible resin film substrate, if necessary. And the transparent conductive film of the present invention. Therefore, it can be used as a base material for a flexible transparent organic EL device using a resin film substrate for any device shape and form, and is extremely valuable industrially.
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Claims
Priority Applications (5)
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KR1020067006407A KR101081871B1 (ko) | 2004-02-27 | 2004-12-28 | 투명도전막 및 그것을 이용한 투명 도전성 기재 |
DE602004027166T DE602004027166D1 (de) | 2004-02-27 | 2004-12-28 | Transparenter leitfähiger film und transparentes leitfähiges basismaterial damit |
JP2006510377A JP4730300B2 (ja) | 2004-02-27 | 2004-12-28 | 透明導電膜及びそれを用いた透明導電性基材 |
EP04807950A EP1720175B1 (en) | 2004-02-27 | 2004-12-28 | Transparent conductive film and transparent conductive base material utilizing the same |
US10/575,471 US7563514B2 (en) | 2004-02-27 | 2004-12-28 | Transparent conductive film and transparent conductive base material utilizing the same |
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JP2004-054816 | 2004-02-27 | ||
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JP2004-363269 | 2004-12-15 |
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US (1) | US7563514B2 (ja) |
EP (1) | EP1720175B1 (ja) |
JP (1) | JP4730300B2 (ja) |
KR (1) | KR101081871B1 (ja) |
DE (1) | DE602004027166D1 (ja) |
WO (1) | WO2005083722A1 (ja) |
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- 2004-12-28 JP JP2006510377A patent/JP4730300B2/ja not_active Expired - Fee Related
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WO2007141994A1 (ja) * | 2006-06-08 | 2007-12-13 | Sumitomo Metal Mining Co., Ltd. | 酸化物焼結体、ターゲット、およびそれを用いて得られる透明導電膜、並びに透明導電性基材 |
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JP2011184284A (ja) * | 2009-09-18 | 2011-09-22 | Nippon Electric Glass Co Ltd | ガラスフィルムの製造方法及びガラスフィルムの処理方法並びにガラスフィルム積層体 |
JP2011195963A (ja) * | 2011-06-24 | 2011-10-06 | Sumitomo Metal Mining Co Ltd | 透明導電膜製造用焼結体ターゲット |
Also Published As
Publication number | Publication date |
---|---|
KR101081871B1 (ko) | 2011-11-09 |
KR20060117911A (ko) | 2006-11-17 |
US7563514B2 (en) | 2009-07-21 |
US20070051926A1 (en) | 2007-03-08 |
EP1720175A1 (en) | 2006-11-08 |
DE602004027166D1 (de) | 2010-06-24 |
JPWO2005083722A1 (ja) | 2008-01-17 |
JP4730300B2 (ja) | 2011-07-20 |
EP1720175A4 (en) | 2008-05-28 |
EP1720175B1 (en) | 2010-05-12 |
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