WO2010026899A1 - 透明電極付き基板および透明電極付き基板の製造方法 - Google Patents
透明電極付き基板および透明電極付き基板の製造方法 Download PDFInfo
- Publication number
- WO2010026899A1 WO2010026899A1 PCT/JP2009/064863 JP2009064863W WO2010026899A1 WO 2010026899 A1 WO2010026899 A1 WO 2010026899A1 JP 2009064863 W JP2009064863 W JP 2009064863W WO 2010026899 A1 WO2010026899 A1 WO 2010026899A1
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- WIPO (PCT)
- Prior art keywords
- substrate
- transparent electrode
- oxide
- transparent conductive
- zinc oxide
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 115
- 239000011787 zinc oxide Substances 0.000 claims description 57
- 235000014692 zinc oxide Nutrition 0.000 claims description 56
- 238000004544 sputter deposition Methods 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 13
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 11
- 238000001069 Raman spectroscopy Methods 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005477 sputtering target Methods 0.000 claims description 5
- 230000014509 gene expression Effects 0.000 claims description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 abstract description 7
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 73
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- 230000000052 comparative effect Effects 0.000 description 18
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- 238000005259 measurement Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007779 soft material Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 229910052796 boron Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
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- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 239000011810 insulating material Substances 0.000 description 1
- 230000005596 ionic collisions Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
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- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03921—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic Table
-
- 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
-
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
-
- 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 is mainly applied to a touch panel, a plasma display panel (PDP), a liquid crystal display (LCD), an electroluminescence (EL) display, a transparent electrode and a back electrode of a solar cell, a transparent intermediate layer of a hybrid solar cell, and a compound semiconductor high-speed device.
- PDP plasma display panel
- LCD liquid crystal display
- EL electroluminescence
- the present invention relates to a substrate with a transparent electrode that can achieve high environmental variability (durability) in a photoacoustic material, a high-temperature heater material, and the like, and a method for manufacturing the same.
- ITO indium tin oxide
- tin oxide zinc oxide, etc.
- Such a transparent conductive layer is formed by a physical vapor deposition method (PVD method) such as a magnetron sputtering method or a molecular beam epitaxy method, or a chemical vapor deposition method (CVD method) such as thermal CVD or plasma CVD.
- PVD method physical vapor deposition method
- CVD method chemical vapor deposition method
- thermal CVD or plasma CVD vapor deposition method
- ITO is an excellent material as a transparent conductive material, and is currently widely used for transparent conductive layers.
- indium as a raw material may be depleted, and there is an urgent need to search for a material that can replace ITO in terms of resources and cost.
- ZnO zinc oxide
- Patent Documents 1 and 2 describe that a transparent electrode using a group III or group IV atom together with ZnO in addition to chromium or cobalt has good etching characteristics.
- Patent Document 3 discloses a transparent conductor obtained by laminating a hard coat layer on a plastic substrate and further laminating a transparent conductive layer made of zinc oxide doped with 4 to 6 atomic% of silicon on the hard coat layer.
- the durability of the sheet resistance is good (the resistance change amount in the reliability test is small).
- the transparent conductor described in Patent Document 3 contains about 5 atomic% of silicon, the conductivity is lowered.
- the silicon content is reduced in order to improve the conductivity, the durability is deteriorated.
- a method of treating the surface of a zinc oxide transparent conductive oxide with an aqueous solution containing a trivalent cation has been reported as an improvement in chemical stability by a protective film. (Patent Document 4)
- Zinc oxide is a compound with strong ion binding properties, and among thin film materials, it is weak against water and chemicals.
- a method of blocking moisture by providing a coating layer on the surface of the zinc oxide transparent thin film can be considered.
- Such a moisture barrier material is generally a material such as a metal material or polyolefin, and is often not suitable for a material for a substrate with a transparent electrode, such as an opaque or insulating material.
- it is conceivable to impart stability to zinc oxide by doping and Patent Documents 1 to 3 describe that stability is improved by doping cobalt, chromium, or silicon.
- Patent Document 5 describes a method of forming a transparent conductive layer by sputtering in an atmosphere containing a gas containing carbon atoms such as carbon dioxide using a metal target. It has been. However, in this case, metallic zinc is used as the metallic target, and metallic zinc is easily oxidized and the composition of the target is not stable.
- Patent Document 6 Japanese Patent Application Laid-Open No. 62-154411 reports a transparent conductive film containing zinc oxide as a main component and a group IV element such as silicon.
- Patent Document 6 is the same application as “Japanese Patent Publication No. 5-6766” described in paragraph [0004] of Patent Document 3.
- the transparent conductive film according to Patent Document 6 is left at high temperature and high humidity, the electrical resistance value changes with time and the conductivity is lowered. This is as described in paragraphs [0005] to [0007] of Patent Document 3.
- Patent Document 7 reports zinc oxide doped with aluminum, gallium, boron, or indium in addition to silicon for a light-transmitting conductive film used for a photoelectric conversion element. ing.
- the translucent conductive film is formed by sputtering, the target used contains three or more elements in addition to oxygen. Such a target can be uniformly kneaded or sintered. This process is very difficult, it becomes difficult to increase the area of the target, and there is a problem in productivity.
- Non-patent Document 2 Amorphous zinc oxide transparent conductive oxide is the extent to which IZO containing indium oxide has been reported (Non-patent Document 2). This also has a zinc oxide content of about 10 atomic%, and the main component is Indium oxide. Thus, no amorphous zinc oxide transparent conductive oxide based on zinc oxide, which is abundant as a resource, has been found so far.
- Non-patent documents 3 and 4 are generally related to sputtering.
- the present invention has an object to be solved to improve durability when a zinc oxide transparent conductive oxide is left in a high temperature and high humidity environment.
- the present inventors contain a small amount of silicon atoms in the zinc oxide in the zinc oxide transparent conductive layer, thereby suppressing the decrease in conductivity and improving the environmental variability. I found that it was possible.
- one aspect of the present invention is as follows.
- LO Longitudinal vibration
- the vibration mode parallel to the laser light is the longitudinal wave (LO) mode (Longitudinal Optical Mode), and the vibration mode perpendicular to the laser light is the transverse wave vibration. (TO) mode (Transverse Optical Mode).
- LO longitudinal wave
- TO Transverse Optical Mode
- the sheet resistance is good at high temperature and high humidity.
- the peak intensity ratio I LO / I TO is less than 0.40, the high temperature and high humidity durability is lowered. Even if the content of silicon dioxide is less than 0.50% by weight, the durability is lowered. When the content of silicon dioxide exceeds 2.75% by weight, the conductivity is lowered.
- the peak intensity ratio I LO / I TO is preferably 1.80 or less. If this value is exceeded, it becomes difficult to manufacture. Moreover, even if the peak intensity ratio is too large, the durability may be reduced.
- the sheet resistance (R1) of the substrate surface after leaving the substrate for 10 days in an 85 ° C./85% relative humidity environment is preferably 0.75 to 1.5.
- This aspect can also be displayed as follows.
- Such a transparent conductive film can be formed by making the power density during film formation higher than a predetermined value.
- a predetermined value Conventionally, when sputtering film formation is performed with the power density increased, it has been thought that the film quality deteriorates due to selective resputtering (etching) of the film after the film formation by O ⁇ ions generated in the vicinity of the target ( Non-patent documents 3 and 4).
- the present inventors have found that a film having excellent durability is produced by increasing the power density at the time of forming the zinc oxide transparent conductive oxide.
- the reason why the film is excellent in durability is that the vicinity of the crystal grain boundary is close to an amorphous structure, so that the adhesion of oxygen and moisture to the crystal grain boundary is suppressed, and electrical conduction is not hindered.
- the manufacturing method of the substrate with a transparent electrode of the present invention is as follows.
- substrate with a transparent electrode characterized by making the power density applied to the said target at the time of sputtering film forming into 3.5 W / cm ⁇ 2 > or more using the mixture containing.
- the peak intensity ratio I LO / I TO becomes small and the durability is lowered.
- the power density is preferably 18 W / cm 2 or less in order to prevent inconvenience (described later) that is expected due to excessively high power density.
- the present invention has the following configuration as an aspect different from the above.
- the transparent conductive oxide layer is one of gallium oxide, aluminum oxide, and boron oxide.
- Longitudinal vibration (LO) mode near 570 to 575 cm -1
- transverse wave which is a mixed oxide of oxides and zinc oxide selected from more than one kind, and is detected by laser Raman spectroscopy.
- LO Longitudinal vibration
- I TO peak intensity in vibration
- the peak intensity ratio I LO / I TO is 1.40 or more, the high temperature and high humidity durability of the sheet resistance is good. If the peak intensity ratio is less than 1.40, the high temperature and high humidity durability is lowered.
- the peak intensity ratio I LO / I TO is preferably 2.20 or less. If this value is exceeded, it becomes difficult to manufacture. Moreover, even if the peak intensity ratio is too large, the durability may be reduced.
- This aspect can also be displayed as follows.
- the transparent conductive oxide layer is one kind of gallium oxide, aluminum oxide, and boron oxide. It is a mixed oxide of the oxide selected above and zinc oxide, the film thickness of the transparent conductive oxide layer is D (nm), the in-plane average roughness measured with an atomic force microscope is Sa (nm), A substrate with a transparent electrode, wherein the following two expressions are satisfied simultaneously when the number density on the top of the protrusion is Sds ( ⁇ m ⁇ 2 ). Sa ⁇ 0.01 ⁇ D + 4.0 Sds ⁇ ⁇ 0.55 ⁇ D + 420
- the sheet resistance of the substrate surface immediately after the formation of the substrate with a transparent electrode based on the sheet resistance (R0) of the substrate surface immediately after the formation of the substrate with a transparent electrode, the sheet resistance of the substrate surface after leaving the substrate in an environment of 85 ° C./85% relative humidity for 10 days.
- the ratio (R1 / R0) of (R1) is preferably 2.0 or less.
- the manufacturing method of the substrate with a transparent electrode according to this aspect is as follows.
- the peak intensity ratio I LO / I TO becomes small and the durability is lowered.
- the power density is preferably 18 W / cm 2 or less in order to prevent inconvenience (described later) that is expected due to excessively high power density.
- the durability of a transparent conductive oxide mainly composed of zinc oxide is improved, and “conductivity” and “environmental variability” which are particularly important factors in a touch panel, an electroluminescence electrode substrate, a solar cell, etc. It becomes possible to form a substrate with a transparent electrode exhibiting good characteristics.
- the present invention it is possible to use a transparent conductive oxide mainly containing zinc oxide which does not contain indium other than impurities, and it is possible to use abundant zinc oxide as a resource.
- FIG. 1 is a schematic cross-sectional view of a substrate with a transparent electrode according to the present invention.
- a zinc oxide transparent conductive oxide layer 2 is formed on the substrate 1 (FIG. 1).
- a zinc oxide transparent conductive oxide containing zinc oxide as a main component and containing indium other than impurities is used.
- the material of the substrate 1 can be selected depending on the application, but when used as a substrate for a transparent electrode, the hard or soft material is not particularly limited as long as it is a substrate that is transparent at least in the visible light region.
- Glass or sapphire can be used as the hard material. Specific examples of the glass include alkali glass, borosilicate glass, and non-alkali glass.
- the thickness of the base material using glass or sapphire can be arbitrarily selected depending on the purpose of use, but 0.5 to 4.5 mm can be exemplified as a preferable range in consideration of the balance between handling and weight. If it is too thin, the strength will be insufficient and it will be easily broken by impact. On the other hand, if the thickness is too large, the weight becomes heavy and the thickness of the device is affected. Therefore, it is difficult to use the portable device, and it is not preferable in terms of transparency and cost.
- examples of the soft material include a thermoplastic resin and a thermosetting resin.
- examples of the thermoplastic resin include acrylic resin, polyester, polycarbonate resin, polyolefin, and cycloolefin polymer, and examples of the thermosetting resin include polyurethane.
- a substrate mainly composed of a cycloolefin polymer (COP) having excellent optical isotropy and water vapor barrier properties is preferable.
- COP examples include norbornene polymers, copolymers of norbornene and olefins, and polymers of unsaturated alicyclic hydrocarbons such as cyclopentadiene. From the viewpoint of water vapor barrier properties, it is preferable that the main chain and side chain of the constituent molecules do not contain a functional group having a large polarity, such as a carbonyl group or a hydroxyl group.
- PEN polyethylene naphthalate
- PES polyethersulfone
- the thickness can be arbitrarily selected depending on the purpose of use, but handling is easy if it is about 0.03 mm to 3.0 mm. If it is too thin, handling is difficult and the strength is insufficient. On the other hand, if it is too thick, there are problems in transparency and cost, and the thickness of the device increases. Therefore, it is difficult to use it in a portable device.
- a film or sheet shape having a thickness of 0.03 mm to 1.0 mm, more preferably 0.035 mm to 0.5 mm is preferable.
- the substrate film When using a film as the substrate 1, the substrate film can be stretched to give a phase difference.
- a phase difference By providing a phase difference, it is possible to produce a low reflection panel by combining with a polarizing plate, and it is expected that the visibility of an image is greatly improved.
- the phase difference can be given by using a known method. For example, it is possible by stretching or orientation treatment such as uniaxial stretching or biaxial stretching. At this time, the orientation of the polymer skeleton can be promoted by applying a temperature close to the glass transition temperature to the film.
- the preferable range of the retardation value varies depending on the target function, but when providing the antireflection function, it is preferable to select the retardation value within the range of 50 to 300 nm. The vicinity of 137 nm, which is 1/4, is more preferable.
- the zinc oxide transparent conductive oxide of the present invention can be formed on the photoelectric conversion layer or the light emitting layer as a base material.
- the photoelectric conversion layer may be a layer made of amorphous or crystalline silicon or a multi-component compound semiconductor.
- an organic metal complex having aluminum or rare earth atom as a metal center can be used.
- the zinc oxide transparent conductive oxide layer 2 in the present invention is roughly divided into an aspect in which silicon dioxide is added and an aspect in which gallium oxide, aluminum oxide, or boron oxide is added. These will be described sequentially.
- the zinc oxide transparent conductive oxide layer 2 is characterized in that the content of silicon dioxide is 0.50 to 2.75% by weight with respect to zinc oxide, and is further preferably 0.2% by weight.
- the content is preferably 8 to 2.2% by weight, particularly 0.8 to 2.1% by weight.
- silicon dioxide is unevenly distributed in the vicinity of the crystal grain boundary of zinc oxide so as not to lower the conductivity, and due to electrolysis generated by oxygen and water adhering to the vicinity of the crystal grain boundary It is presumed that carrier scattering is suppressed.
- the zinc oxide transparent conductive oxide layer of this embodiment substantially contains no dopant other than silicon such as aluminum, gallium, boron, and indium.
- the transparent conductive oxide layer 2 according to the present invention can be formed by magnetron sputtering.
- a target material used for magnetron sputtering can be manufactured by sintering a mixture of oxide mainly composed of zinc oxide and silicon dioxide and bonding the resultant to a backing plate by hot pressing or the like.
- the amount of silicon dioxide mixed with zinc oxide is preferably 0.50 to 2.75% by weight, more preferably 0.8 to 2.2% by weight.
- a direct current power source or a high frequency power source (RF, VHF) or the like can be used as a power source for magnetron sputtering.
- Power density was 3.5 W / cm 2 or more, further it is possible to manufacture the substrate of the present invention by 4W / cm 2 or more.
- the power density is more preferably 4W / cm 2 ⁇ 18W / cm 2, in particular is 4.5W / cm 2 ⁇ 15W / cm 2, is preferably Among them 5W / cm 2 ⁇ 13W / cm 2 .
- a transparent conductive oxide layer exhibiting the above peak intensity ratio can be formed by using such a power density region.
- the power density is lower than this, the film forming speed is not improved, and it is presumed to be a problem of crystallinity, but the reliability in a high temperature and high humidity environment may not be good.
- the transparent conductive oxide layer is re-sputtered by oxygen ions generated in the plasma, which may result in a substrate with a transparent electrode with poor transparency and conductivity. This is not preferable.
- the optimum conditions can be determined by appropriately controlling the target / substrate distance and the substrate temperature.
- Laser Raman measurement is performed using a helium-neon laser having a wavelength of 632.8 nm as excitation light.
- Zinc oxide in response to the vibration of the LO and TO modes A1 symmetric vibration peaks respectively 570 ⁇ 575cm -1 and the 380 ⁇ 385cm -1 near is detected. In some cases, these peak positions may deviate. In this case, the value of the maximum peak position in the vicinity of this position may be adopted.
- the peak intensity ratio I LO / I TO shows a value of 0.40 to 1.80. Further, it is preferably 0.45 to 1.65.
- the power density at the time of film is 3.5 W / cm 2 or more, for example, 4.5W / cm 2 ⁇ 15W / cm 2, even more in the case of 5W / cm 2 ⁇ 13W / cm 2 is A transparent conductive film having an I LO / I TO of 0.65 to 1.80, more preferably 0.70 to 1.65 is obtained, and the rate of change in sheet resistance is small, which is preferable.
- the peak of the Raman spectrum can be easily calculated by fitting the measured spectrum as a combination of a plurality of peaks using a Gaussian function. For example, when a film is formed on an alkali-free glass substrate, since a peak derived from the glass substrate is detected in the vicinity of 490 cm ⁇ 1 , the peak ratio can be obtained by fitting from a combination of a total of three Gauss functions. .
- a hydrogen plasma treatment may be performed on the substrate with a transparent electrode after the transparent conductive oxide layer 2 is formed.
- oxygen defects that greatly contribute to the conductivity of the zinc oxide transparent conductive oxide are formed, and the conductivity is improved.
- an excellent substrate with a transparent electrode can be produced by flowing hydrogen at a pressure of about 50 to 200 Pa and discharging at 0.02 to 3.00 W / cm 2 using an RF power source. If the power in the hydrogen plasma treatment is too low, the effect is small, and if it is too high, the transparent conductive oxide is etched, which is not preferable.
- a substrate with a transparent electrode formed on a glass substrate or a soft material having a high softening (melting) temperature can be annealed to increase conductivity and light transmittance.
- the annealing atmosphere is preferably a vacuum or an inert gas stream such as nitrogen. Annealing in an oxygen atmosphere is not preferable because the transparent conductive oxide is thermally oxidized and the conductivity is lowered.
- the annealing temperature is not less than the temperature at which the crystallinity of zinc oxide is improved, and is preferably not more than the melting temperature of the substrate.
- a favorable substrate with a transparent electrode can be produced by annealing at about 200 to 450 ° C.
- the film thickness of the transparent conductive oxide layer 2 is preferably 15 to 500 nm, more preferably 20 to 200 nm.
- a transparent conductive oxide layer having a thickness in this range a substrate with a transparent electrode having both high transparency and conductivity can be produced.
- the film thickness is reduced, the film formation by magnetron sputtering is not preferable because the transparent conductive oxide has a stripe-like growth and does not become a film.
- the film thickness is increased, light absorption by the transparent conductive oxide is increased, the transmittance is decreased, and cracks are easily generated in the transparent conductive oxide layer due to stress, which is not preferable.
- the method for detecting the doping amount contained in the transparent conductive oxide layer 2 may be any method as long as it is a method usually used for elemental analysis.
- an element such as atomic absorption analysis or fluorescent X-ray analysis is used.
- Analytical means spectroscopic techniques such as X-ray photoelectron spectroscopy, Auger electron spectroscopy, and electron beam microanalyzer, and techniques such as secondary ion mass spectrometry can be used.
- EDX energy dispersive X-ray fluorescence analysis
- SEM scanning electron microscope
- TEM transmission electron microscope
- the doping amount can be easily calculated by the following equation by relative comparison with zinc.
- (Doping amount) (Number of atoms of doping agent) ⁇ (Number of atoms of doping agent) + (Number of atoms of zinc)) ⁇ 100.
- the sheet resistance of the surface of the substrate with a transparent electrode to be produced varies depending on the application, but for example, it is preferably about 10 to 20 ⁇ / ⁇ in the case of a solar cell or an EL element, and 200 to 2000 ⁇ / ⁇ in the case of a touch panel. The degree is preferred.
- an optical design layer may be provided between the substrate 1 and the transparent conductive oxide layer 2 or on the surface of the transparent conductive oxide layer 2 for the purpose of improving the light transmittance.
- a high refractive index layer such as titanium oxide, hafnium oxide, niobium oxide and a low refractive index layer such as silicon dioxide are provided between the substrate 1 and the transparent conductive oxide layer 2 as “substrate 1 / high.
- the optical design layer is provided on the transparent conductive oxide layer 2
- a layer having a lower refractive index than that of the transparent conductive oxide layer is formed, the effect of suppressing light reflection is large.
- PES polystyrene sulfonate
- a conductive porous carbon material can also be used.
- the zinc oxide transparent conductive oxide layer is doped for the purpose of imparting conductivity and improving durability.
- these doping agents one selected from gallium, aluminum, and boron is used. These are doped into zinc oxide in the form of oxides such as gallium oxide, aluminum oxide and boron oxide.
- the doping amount is preferably such that each element is 1.0 to 4.0% by weight with respect to zinc. If the doping amount is too large or too small, the conductivity tends to decrease. The reason is that if the amount is too large, the oxide of the dopant is segregated in the vicinity of the crystal grain boundary, causing the grain boundary scattering of the conductive carrier. On the other hand, if the amount is too small, the number of carriers contributing to conductivity is reduced, and conductivity cannot be obtained.
- the Raman spectrum of the transparent conductive oxide layer 2 When the Raman spectrum of the transparent conductive oxide layer 2 is measured, the ratio (I LO / I TO ) between the LO (longitudinal wave) mode and the TO (transverse wave) peak intensity of the A1 symmetric vibration is 1.40-2. 20 is one of the main points of the present invention.
- the Raman spectrum measurement is the result of using a 632.8 nm helium neon laser. Position of the peaks of A1 symmetry LO mode and TO mode of the zinc oxide is detected at around 570 ⁇ 575cm -1 and 380 ⁇ 385cm -1, respectively. The peak position may vary depending on the amount of dopant added.
- these peaks in a Raman spectrum are peaks that selectively appear due to crystallinity, and the crystal structure of the transparent conductive oxide layer can be determined by analyzing the ratio of these peak intensities.
- the LO / TO mode is presumed to be related to the growth direction of the film and the orientation of the crystal.
- the present inventors have found that when the ratio of the LO / TO peak intensity is 1.40 to 2.20, the substrate with a transparent electrode is excellent in durability under a high temperature and high humidity environment. Even if the ratio of the peak intensity of LO / TO is larger or smaller than this range, a substrate with a transparent electrode having sufficient durability cannot be obtained. This is considered to be because there is an optimum value for the mixing ratio of different crystalline zinc oxides, and if the balance is lost, the durability in a high temperature and high humidity environment is lowered.
- the surface of the transparent conductive oxide layer 2 is observed with an atomic force microscope (AFM), and the average surface roughness in the surface is Sa (nm) with respect to the data obtained by analysis.
- AFM atomic force microscope
- Sds ( ⁇ m ⁇ 2 ) and the transparent conductive oxide layer thickness is D (nm): .
- the surface roughness tends to increase as the film thickness increases. This is because the crystal grain size in the layer increases.
- the present inventors have found that durability in a high-temperature and high-humidity environment can be improved by setting the surface roughness to a region represented by the above formula. It is presumed that this is because the surface roughness of the transparent conductive oxide layer is made as small as possible by reducing the surface roughness, and the contact area with water or oxygen is made small.
- Sds can also be interpreted as the number of crystal grains per unit area, and an increase in Sds can be explained as an increase in the number of crystal grains, that is, an increase in crystal density. For this reason, it is presumed that the crystal grain boundary has a dense structure, and the penetration and adhesion of water and oxygen can be suppressed.
- the transparent conductive oxide layer 2 As a method for forming the transparent conductive oxide layer 2, a magnetron sputtering method is used.
- the power density during sputtering 3.5 ⁇ 18W / cm 2, more preferably, be a film of a transparent conductive oxide layer of the present embodiment by a 6.0 ⁇ 11.0W / cm 2 Can do.
- An excessively high power density is not preferable because it not only causes damage to the target, but also causes ion species in the plasma to reach the substrate and damage the transparent conductive oxide layer adhering to the base material.
- the transparent conductive oxide layer which shows the above Raman spectra and surface roughness characteristics can be formed into a film. This is because the ion collision energy to the target is increased, the size of atoms or ionic species leaving the target is reduced, and the atoms or ionic species that reach the substrate can be densely attached. It is estimated to be.
- the crystal orientation depends on the power density at the time of film formation, and these results are considered to determine the performance of the transparent conductive oxide layer.
- the optimum conditions can be determined by appropriately controlling the target / substrate distance and the substrate temperature.
- the transparent conductive oxide layer 2 of this embodiment can also be subjected to hydrogen plasma treatment or annealing treatment for the purpose of further improving the conductivity. These treatments have the effect of increasing the particle size in the removal of interstitial atoms and the solid phase reaction of crystals, leading to improved conductivity.
- a hydrogen plasma condition an excellent substrate with a transparent electrode can be produced by flowing hydrogen at a pressure of about 50 to 200 Pa and discharging at 0.02 to 3.00 W / cm 2 using an RF power source. If the power in the hydrogen plasma treatment is too low, the effect is small, and if it is too high, the transparent conductive oxide is etched, which is not preferable.
- the annealing process is preferably performed in a vacuum or a nitrogen atmosphere. Annealing in an atmosphere containing oxygen is not preferable because the conductivity of the transparent conductive oxide decreases due to thermal oxidation.
- the annealing temperature may be about 150 to 450 ° C.
- a scanning electron microscope JSM-6390-LA manufactured by JEOL Ltd.
- the doping amount is converted into a substance amount ratio (molar ratio), where the ratio of the detected amounts of silicon and zinc elements is the number of atoms, and the ratio of silicon dioxide (molecular weight 60 g / mol) to zinc oxide (molecular weight 81 g / mol).
- the film thickness of the transparent conductive oxide layer was a spectroscopic ellipsometer VASE (manufactured by JA Woollam). Fitting was performed using the Chaucy model.
- a laser Raman spectrometer NR-1000 manufactured by JASCO Corporation was used for laser Raman spectroscopy.
- a helium-neon laser with an excitation wavelength of 632.8 nm was used. In the range of 300 cm -1 ⁇ 650 cm -1 of the spectrum after measurement, it represents a total of three peaks of the two peaks and glass LO mode ⁇ TO mode each Gaussian function, and fitting the combination of three Gaussian functions . For fitting, the three elements of peak height, half-value width, and peak wave number were used as variables.
- the value of the reliability test result indicates the quality stability related to the environmental variability of the substrate with a transparent electrode, and this value is most widely 0.50 to 2.0, more preferably 0.75 to It is preferably 1.50, more preferably 0.75 to 1.40. In particular, 0.8 to 1.2 is preferable.
- the resistance is unstable, which tends to lead to deterioration of the image for display materials, deterioration of conversion efficiency for materials such as solar cells, and deterioration of accuracy for materials such as touch panels.
- Example 1 A transparent conductive oxide layer was magnetron-sputtered on an alkali-free glass substrate (trade name OA-10, manufactured by Nippon Electric Glass Co., Ltd., film thickness 0.7 mm).
- alkali-free glass substrate trade name OA-10, manufactured by Nippon Electric Glass Co., Ltd., film thickness 0.7 mm.
- Zinc oxide Zinc oxide (Comparative Example 1) was used, and the pressure was adjusted to 0.2 Pa while flowing argon gas at a rate of 20 cubic centimeters per minute in terms of standard conditions, and a power density of 8 W / cm 2 was applied to form a 50 nm film Thickness was formed.
- a high frequency power source (frequency: 13.56 MHz) was used as the power source.
- the target size was 4 inches (101.6 mm) in diameter, the target-substrate distance was 80 mm, and the substrate temperature was 80 ° C.
- the reliability test was implemented after measuring a film thickness, the transmittance
- silicon dioxide contained in the transparent electrode produced this time was 1.0 wt% (Example 1) and 2.0 wt% (Example 2).
- Example 3 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 1 except that the sputtering power density was 4 W / cm 2 .
- Example 4 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 2 except that the sputtering power density was 12 W / cm 2 .
- Example 5 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 2 except that the sputtering power density was 4 W / cm 2 .
- Example 2 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 1 except that the sputtering power density was 2 W / cm 2 .
- the Raman spectra of Examples 1 and 2 and Comparative Example 2 are shown in FIGS.
- the horizontal axis is the wave number (cm ⁇ 1 ), and the vertical axis is the Raman intensity.
- symbol 3 shows measurement data.
- the graphs with reference numerals 4, 5, and 6 indicate peaks derived from the TO mode, the LO mode, and the glass substrate, respectively.
- the graph of reference numeral 7 is the sum of the graphs of reference numerals 4, 5, and 6, and corresponds to a smoothed version of the graph of reference numeral 3.
- Table 1 shows the examination results of the above examples and comparative examples. Further, Table 2 shows the power density of each example and comparative example, the ILO / ITO ratio of the Raman spectrum, and the sheet resistance change degree under a high temperature and high humidity environment.
- Examples 6 to 10, Comparative Examples 3 to 5 On an alkali-free glass substrate (trade name OA-10, manufactured by Nippon Electric Glass Co., Ltd., film thickness: 0.7 mm), zinc oxide (GZO) added with 2.0% by weight of gallium oxide was formed by magnetron sputtering.
- the film thickness was 30 nm only in Example 10, and 45 nm in all of Examples 6 to 9 and the comparative example.
- the film forming conditions are as follows as in Examples 1 to 5.
- Target size 4 inches in diameter (101.6mm)
- Carrier gas / pressure Argon gas / 0.2 Pa
- Power supply High frequency (13.56 MHz) power supply
- Target-to-board distance 80 mm
- Substrate temperature 80 ° C
- Raman spectroscopic measurement was performed using NR-1000 manufactured by JASCO Corporation, and sheet resistance measurement was performed using Loresta GP MCT-610 manufactured by Mitsubishi Chemical Corporation.
- the film thickness was fitted by a cauchy model using a spectroscopic ellipsometer VASE manufactured by JA Woollam.
- Example 6 A substrate with a transparent electrode was prepared with a sputtering power density of 9.87 W / cm 2 and evaluated.
- Example 7 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 8.64 W / cm 2 .
- Example 8 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 6.79 W / cm 2 .
- Example 9 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 6.20 W / cm 2 .
- Example 10 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 9 except that the film thickness was 30 nm.
- Example 3 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 4.94 W / cm 2 .
- Example 4 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 3.09 W / cm 2 .
- Example 5 A substrate with a transparent electrode was prepared and evaluated in the same manner as in Example 6 except that the sputtering power density was 1.23 W / cm 2 .
- Tables 3 to 5 show the results of Raman spectrum / AFM / reliability tests of the substrates with transparent electrodes in the examples and comparative examples.
- all the examples satisfy the conditions of Sa ⁇ Sao and Sds ⁇ Sdso.
- Sds ⁇ Sdso In the comparative example.
- Comparative Examples 3 to 5 are examples in which the power density is too low, which corresponds to an example in which the I LO / I TO ratio is too small and an example in which Sds is too small. These are too large in sheet resistance change. In other words, the durability under a high temperature and high humidity environment is low. From these results, it is possible to improve the durability under high temperature and high humidity environment by depositing GZO doped with gallium oxide or the like at a power density within the proper range, which is related to the results of Raman spectrum and AFM. I found out that
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Abstract
Description
Sa≦0.01×D+4.0
Sds≧-0.55×D+420
本発明の一態様における酸化亜鉛透明導電性酸化物層2は、二酸化珪素の含有量は酸化亜鉛に対して0.50~2.75重量%であることが特徴であるが、さらには0.8~2.2重量%、特には0.8~2.1重量%含有していることが好ましい。二酸化珪素が果たす役割については明確でないが、二酸化珪素が、酸化亜鉛の結晶粒界付近に導電性を低下させない程度に偏在し、結晶粒界近傍に酸素や水が付着することで発生する電解によるキャリアの散乱を抑制していると推定される。本態様の酸化亜鉛透明導電性酸化物層は、実質的にアルミニウム、ガリウム、ホウ素、インジウム等の珪素以外のドーパントを含まないことが好ましい。
(ドーピング量)=(ドーピング剤の原子数)÷((ドーピング剤の原子数)+(亜鉛の原子数))×100。
酸化亜鉛透明導電性酸化物層には、導電性の付与や耐久性の向上を目的としてドーピングを施す。これらのドーピング剤にはガリウム・アルミニウム・ホウ素から1種類以上選択されるものを用いる。これらは、酸化ガリウム・酸化アルミニウム・酸化ホウ素のような酸化物の状態で酸化亜鉛中にドーピングされる。ドーピング量は、各々の元素が亜鉛に対して1.0~4.0重量%となるように施されることが好ましい。ドーピング量は多すぎても少なすぎても導電性が低下する傾向がある。この理由は、多すぎるとドーパントの酸化物が結晶粒界近傍に偏析するようになり導電キャリアの粒界散乱の原因となる。一方、少なすぎると導電性に寄与するキャリアが減少し、導電性が得られない。
Sa≦0.01×D+4.0
Sds≧-0.55×D+420
後記の各実施例において、ドーピング量測定にはEDX測定機能を搭載した走査電子顕微鏡JSM-6390-LA(日本電子社製)を用いた。ドーピング量は、珪素と亜鉛の元素の検出量の比を原子数として、それぞれ物質量比(モル比)に変換し、二酸化珪素(分子量60g/mol)と酸化亜鉛(分子量81g/mol)の比として計算した。透明導電性酸化物層の膜厚は分光エリプソメーターVASE(J.A・ウーラム社製)を使用した。フィッティングはChaucyモデルにより行った。レーザーラマン分光測定にはレーザーラマン分光測定装置NR-1000(日本分光工業社製)を使用した。
いずれの透明電極付き基板についても、該基板形成直後の該基板表面のシート抵抗(R0)を基準とする、該基板を85℃/85%RH環境下で10日間放置した後の該基板表面のシート抵抗(R1)の比(R1/R0)を信頼性試験結果とした。シート抵抗測定には、抵抗率計ロレスタGP MCT-610(三菱化学社製)を用いた。
(信頼性試験結果)=(10日後のシート抵抗)÷(製膜直後のシート抵抗)
無アルカリガラス基材(商品名OA-10、日本電気硝子社製、膜厚0.7mm)に、透明導電性酸化物層をマグネトロンスパッタリング製膜した。スパッタターゲットとしては、1.0重量%の二酸化珪素が添加された酸化亜鉛(実施例1)、2.0重量%の二酸化珪素が添加された酸化亜鉛(実施例2)、二酸化珪素が添加されていない酸化亜鉛(比較例1)を使用し、アルゴンガスを標準状態換算で毎分20立方cm流しながら、圧力を0.2Paに調整し、8W/cm2のパワー密度をかけて50nmの膜厚を製膜した。電源は高周波電源(周波数:13.56MHz)を使用した。
ターゲットサイズは直径4インチ(101.6mm)、ターゲット-基板間距離は80mm、基板温度は80℃とした。
作製された透明電極付き基板について、膜厚・透過率・シート抵抗を測定後に信頼性試験を実施した。
EDX測定による組成分析を行った結果、今回作製された透明電極に含まれる二酸化珪素は1.0重量%(実施例1)、2.0重量%(実施例2)であった。
スパッタパワー密度を4W/cm2とした以外は実施例1と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を12W/cm2とした以外は実施例2と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を4W/cm2とした以外は実施例2と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を2W/cm2とした以外は実施例1と同様にして透明電極付き基板を作製し、評価を実施した。
無アルカリガラス基材(商品名OA-10、日本電気硝子社製、膜厚0.7mm)上に、2.0重量%酸化ガリウムを添加した酸化亜鉛(GZO)をマグネトロンスパッタリング製膜した。膜厚は、実施例10のみ30nmとし、実施例6~9及び比較例はすべて45nmとした。
製膜条件は、実施例1~5と同様、下記のとおりである。
ターゲットサイズ:直径4インチ(101.6mm)
キャリアガス・圧力:アルゴンガス・0.2Pa
電源:高周波(13.56MHz)電源
ターゲット-基板間距離:80mm
基板温度:80℃
AFM(原子間力顕微鏡)測定はPacific Nanotechnology社製Nano-Rを使用した。他の測定装置については実施例1~5と同様で、ラマンスペクトル分光測定は日本分光製NR-1000、シート抵抗測定は三菱化学社製ロレスタGP MCT-610を使用した。膜厚はJ・A・ウーラム社製分光エリプソメーターVASEを使用し、cauchyモデルによりフィッティングした。
スパッタパワー密度を9.87W/cm2として透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を8.64W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を6.79W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を6.20W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
膜厚を30nmとした以外は実施例9と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を4.94W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を3.09W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
スパッタパワー密度を1.23W/cm2とした以外は実施例6と同様にして透明電極付き基板を作製し、評価を実施した。
Claims (12)
- 基材上に少なくとも1層からなる酸化亜鉛を主成分とする透明導電性酸化物層を有する透明電極付き基板であって、該透明導電性酸化物層を構成する酸化亜鉛透明導電性酸化物が二酸化珪素を酸化亜鉛に対して0.50~2.75重量%含んでおり、且つレーザーラマン分光測定により検出されるA1対称の光学振動モードである縦波振動モードと横波振動モードのピーク強度をそれぞれILO、ITOとしたとき、ピーク強度比ILO/ITOが0.40以上であることを特徴とする透明電極付き基板。
- 上記ピーク強度比ILO/ITOが1.80以下であることを特徴とする請求項1記載の透明電極付き基板。
- 透明電極付き基板形成直後の該基板表面のシート抵抗を基準とする、該基板を85℃/85%相対湿度環境下で10日間放置した後の該基板表面のシート抵抗の比が、0.75~1.5であることを特徴とする、請求項1又は2記載の透明電極付き基板。
- 基材上に少なくとも1層からなる酸化亜鉛を主成分とする透明導電性酸化物層を有する透明電極付き基板であって、該透明導電性酸化物層を構成する酸化亜鉛透明導電性酸化物が二酸化珪素を酸化亜鉛に対して0.50~2.75重量%含有し、かつ、透明電極付き基板形成直後の該基板表面のシート抵抗を基準とする、該基板を85℃/85%相対湿度環境下で10日間放置した後の該基板表面のシート抵抗の比が、0.75~1.5であることを特徴とする、透明電極付き基板。
- 請求項1~4のいずれかに記載の透明電極付き基板の製造方法であって、透明導電性酸化物層をマグネトロンスパッタリング法により製膜し、スパッタターゲットとして二酸化珪素を酸化亜鉛に対して0.50~2.75重量%含む混合物を用い、スパッタリング製膜時に上記ターゲットに印加されるパワー密度を3.5W/cm2以上とすることを特徴とする、透明電極付き基板の製造方法。
- 上記パワー密度を18W/cm2以下とすることを特徴とする、請求項5に記載の透明電極付き基板の製造方法。
- 基材上に酸化亜鉛を主成分とする透明導電性酸化物層が製膜されてなる透明電極付き基板において、上記透明導電性酸化物層が、酸化ガリウム、酸化アルミニウム、酸化ホウ素の中から1種類以上選択された酸化物と酸化亜鉛の混合酸化物であり、レーザーラマン分光測定により検出されるA1対称の光学振動モードである縦波振動モードと横波振動モードのピーク強度をそれぞれILO、ITOとしたとき、ピーク強度比ILO/ITOが1.40以上であることを特徴とする透明電極付き基板。
- 上記ピーク強度比ILO/ITOが2.20以下であることを特徴とする請求項7記載の透明電極付き基板。
- 基材上に酸化亜鉛を主成分とする透明導電性酸化物層が製膜されてなる透明電極付き基板において、上記透明導電性酸化物層が酸化ガリウム、酸化アルミニウム、酸化ホウ素の中から1種類以上選択された酸化物と酸化亜鉛の混合酸化物であり、透明導電性酸化物層の膜厚をD(nm)、原子間力顕微鏡で測定した、面内平均粗さをSa(nm)、突起頂上の個数密度をSds(μm-2)としたときに、下記2つの式を同時に満たすことを特徴とする透明電極付き基板。
Sa≦0.01×D+4.0
Sds≧-0.55×D+420 - 透明電極付き基板形成直後の該基板表面のシート抵抗を基準とする、該基板を85℃/85%相対湿度環境下で10日間放置した後の該基板表面のシート抵抗の比が、2.0以下であることを特徴とする、請求項7~9のいずれかに記載の透明電極付き基板。
- 請求項7~10のいずれかに記載の透明電極付き基板の製造方法であって、透明導電性酸化物をマグネトロンスパッタリング法により製膜し、スパッタターゲットとして酸化ガリウム、酸化アルミニウム、酸化ホウ素の中から1種類以上選択された酸化物と酸化亜鉛の混合酸化物を用い、スパッタリング製膜時に上記ターゲットに印加されるパワー密度を6.0W/cm2以上とすることを特徴とする、透明電極付き基板の製造方法。
- 上記パワー密度を18W/cm2以下とすることを特徴とする、請求項11に記載の透明電極付き基板の製造方法。
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US8895427B2 (en) | 2014-11-25 |
US20110163448A1 (en) | 2011-07-07 |
JP5697449B2 (ja) | 2015-04-08 |
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