WO2007015342A1 - 電極基板および光電変換素子 - Google Patents
電極基板および光電変換素子 Download PDFInfo
- Publication number
- WO2007015342A1 WO2007015342A1 PCT/JP2006/312548 JP2006312548W WO2007015342A1 WO 2007015342 A1 WO2007015342 A1 WO 2007015342A1 JP 2006312548 W JP2006312548 W JP 2006312548W WO 2007015342 A1 WO2007015342 A1 WO 2007015342A1
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- WIPO (PCT)
- Prior art keywords
- layer
- electrode substrate
- transparent conductive
- metal wiring
- experimental example
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 claims abstract description 77
- 239000002184 metal Substances 0.000 claims abstract description 77
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- 238000000034 method Methods 0.000 description 33
- 239000004065 semiconductor Substances 0.000 description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 17
- 229910052740 iodine Inorganic materials 0.000 description 17
- 239000011630 iodine Substances 0.000 description 17
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- 238000002474 experimental method Methods 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 229940006461 iodide ion Drugs 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
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- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- LTNAYKNIZNSHQA-UHFFFAOYSA-L 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);dithiocyanate Chemical compound N#CS[Ru]SC#N.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 LTNAYKNIZNSHQA-UHFFFAOYSA-L 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- VFLYBWGSQGMWHP-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;iodide Chemical compound [I-].C[N+]=1C=CNC=1 VFLYBWGSQGMWHP-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
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- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 description 1
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- 229910000464 lead oxide Inorganic materials 0.000 description 1
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
-
- 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
-
- 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
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Definitions
- the present invention relates to an electrode substrate suitably used for a photoelectric conversion element such as a dye-sensitized solar cell, and more particularly to a metal wiring layer and a transparent conductive layer.
- the present invention relates to an electrode substrate that can suppress deterioration of characteristics due to electric leakage or corrosion of a metal wiring layer.
- Dye-sensitized solar cells were developed by Gretzell et al. In Switzerland and have advantages such as high photoelectric conversion efficiency and low manufacturing costs. (For example, see Patent Document 1 and Non-Patent Document 1).
- a dye-sensitized solar cell includes a working electrode having an oxide semiconductor porous film in which a photosensitizing dye composed of oxide semiconductor fine particles is supported on an electrode substrate, and a counter electrode provided facing the working electrode. And an electrolyte layer formed by filling an electrolyte between the working electrode and the counter electrode.
- oxide semiconductor particles are sensitized by a photosensitizing dye that absorbs incident light such as sunlight, and an electromotive force is generated between the working electrode and the redox couple in the electrolyte.
- a photosensitizing dye that absorbs incident light such as sunlight
- an electromotive force is generated between the working electrode and the redox couple in the electrolyte.
- it functions as a photoelectric conversion element that converts light energy into electric power (see, for example, Patent Document 1 and Non-Patent Document 1).
- Patent Document 1 Japanese Patent Application Publication No. 01-220380
- Non-Patent Document 1 Michael 'M. Graetzel et al., Nature, (UK), 1991, No. 353, p. 737
- the transparent electrode substrate used in the dye-sensitized solar cell as described above includes a tin-added acid.
- a transparent conductive film such as indium (ITO) or fluorine-added tin oxide (FTO) is deposited on the surface of the substrate.
- ITO indium
- FTO fluorine-added tin oxide
- the specific resistance of ⁇ and FTO is about 10 4 ⁇ 10 " 3 ⁇ 'cm, which is about 100 times the specific resistance of metals such as silver and gold.
- the cell has a large area, it will cause a decrease in photoelectric conversion efficiency
- As a technique to reduce the resistance of the transparent electrode substrate it is considered to increase the formation thickness of the transparent conductive film (ITO, FTO, etc.).
- the film is formed with a thickness that sufficiently reduces the resistance value, the light absorption by the transparent conductive layer will increase, and the transmission efficiency of incident light will be significantly reduced. Decline is likely to occur.
- the shielding layer made of glass is easily cracked when a shielding layer that is vulnerable to deformation is formed or due to a volume change accompanying heat treatment after the shielding layer is formed. If a crack generated in the shielding layer reaches the metal wiring, the function of the cell may be impaired due to electric leakage from the metal wiring to the electrolyte or corrosion of the metal wiring by the electrolyte.
- the present invention has been made in view of the above circumstances, and can reduce the resistance of the electrode substrate. In addition, leakage of the metal wiring from the metal wiring to the electrolyte and the metal wiring layer can be prevented. It is an object of the present invention to provide an electrode substrate capable of suppressing deterioration of characteristics due to corrosion and a photoelectric conversion element suitably used for a solar cell.
- An electrode substrate according to the present invention is provided on a base material, on a transparent conductive layer and on the transparent conductive layer.
- ⁇ > ⁇ is satisfied. It is characterized by that.
- the electrode substrate according to the present invention is characterized in that the thickness of the transparent conductive layer is 0.05 to 5 / ⁇ ⁇ .
- the electrode substrate according to the present invention is characterized in that the insulating layer is made of a low melting glass glass.
- the electrode substrate according to the invention is characterized in that the base material is made of a high strain point glass glass.
- a photoelectric conversion element according to the present invention is characterized by having any one of the electrode substrates described above.
- the dye-sensitized solar cell according to the present invention is characterized by having the above-described photoelectric conversion element force.
- the electrode substrate of the present invention it is possible to reduce the resistance of the electrode substrate, and it is possible to suppress deterioration of characteristics due to leakage from the metal wiring to the electrolyte and corrosion of the metal wiring layer. it can.
- FIG. 1 is a cross-sectional view showing a first example of an electrode substrate according to the present invention.
- FIG. 2 is a partial plan view showing an example of a planar shape of a metal wiring layer.
- FIG. 3 is a cross-sectional view showing a second example of the electrode substrate of the present invention.
- FIG. 4 is a cross-sectional view showing an embodiment of the photoelectric conversion element of the present invention.
- FIG. 5 (b) shows a metal wiring layer 1 in which a part of the electrode substrate 1 of Experimental Example 2 and Experimental Example 3 is enlarged.
- FIG. 5 is a cross-sectional view in the width direction
- FIG. 5B is a cross-sectional view in the width direction of the metal wiring layer 12 in which a part of the electrode substrate 1 of Experimental Example 5 is enlarged.
- Electrode substrate 2 ... Oxide semiconductor porous film, 3 ... Working electrode, 4 ... Counter electrode, 5 ... Charge transfer layer, 6 ... Photoelectric conversion element, 10 ... Base material, 11 ... Transparent conductive layer, 12 ... metal wiring layer, 13 ... shielding layer, 14 ... insulating layer, 21 ... crack, 31 ... corrosion BEST MODE FOR CARRYING OUT THE INVENTION
- FIG. 1 is a cross-sectional view showing an example of the electrode substrate 1 of the present invention.
- An electrode substrate 1 shown in FIG. 1 includes a transparent conductive layer 11 on a base material 10, a metal wiring layer 12 formed on the transparent conductive layer 11, and an insulating layer covering the surface of the metal wiring layer 12. 14 is defined, and the thermal expansion coefficient of the substrate 10 is defined and the thermal expansion coefficient of the insulating layer 14 is defined as j8, it is assumed that ⁇ > ⁇ is satisfied.
- the material of the base material 10 is not particularly limited as long as it has a light transmittance that has a thermal expansion coefficient larger than that of the insulating layer 14, but it should have as high a light transmittance as possible for use. Is preferred.
- borosilicate glass, soda lime glass, and high strain point glass can be used. High strain point glass is preferred because it has excellent heat resistance with little deformation by heat treatment.
- the Houkei silicate glass for example, can be the thermal expansion coefficient is present use those 72 X 10_ 7, as the soda lime glass, for example, thermal expansion coefficient can be used those 86 chi 10_ 7, high the strain point glass, for example, leave in that the thermal expansion coefficient is present use those 85 X 10_ 7.
- the transparent conductive layer 11 is formed on the substrate 10 over a region wider than the region where the metal wiring layer 12 is formed.
- the transparent conductive layer 11 can be a single layer or a plurality of layers.
- a material having a thermal expansion coefficient larger than that of the insulating layer 14 and smaller than that of the substrate 10 can be selected according to the intended use in consideration of desired light transmittance, conductivity, and the like.
- the thickness of the transparent conductive layer 11 is preferably 0.05 to 5 / ⁇ ⁇ . If the thickness of the transparent conductive layer 1 1 is less than 0.05 ⁇ m, the sheet resistance may be larger than that of the transparent conductive layer 11 having a thickness of 0.05 to 5 ⁇ m, leading to a decrease in photoelectric conversion efficiency. Occurs. On the other hand, if the thickness of the transparent conductive layer 11 exceeds 5 ⁇ m, the light transmittance is remarkably lowered, leading to a decrease in photoelectric conversion efficiency.
- the transparent conductive layer 11 includes conductive metal oxides such as tin-doped indium oxide (ITO), indium oxide, tin oxide (SnO), and fluorine-added tin oxide (FTO).
- ITO tin-doped indium oxide
- SnO tin oxide
- FTO fluorine-added tin oxide
- Tin-doped indium oxide is 72 X 10 _7, thermal expansion coefficient of Sn O is 35 X 10_ 7.
- Tin-doped indium oxide is a fluorine-added acid Compared with Ti ⁇ tin (FTO), it has excellent light transmission and electrical conductivity. It is inferior in heat resistance.
- fluorine-added tin oxide is inferior in power transmissivity and conductivity, which is superior in heat resistance, as compared with tin-added indium oxide (ITO).
- the transparent conductive layer 11 is a composite film of fluorine-added tin oxide (FTO) and tin-added indium oxide (ITO), the disadvantages of the two are offset and the excellent transparent conductive layer 11 that combines the advantages of both become.
- FTO fluorine-added tin oxide
- ITO tin-added indium oxide
- a known appropriate method according to the material of the transparent conductive layer 11 may be used. Examples thereof include a sputtering method, a vapor deposition method, an SPD method, and a CVD method.
- the metal wiring layer 12 is formed by wiring a metal such as gold, silver, platinum, aluminum, nickel, titanium, etc., and is electrically connected to the transparent conductive layer 11 and insulated by the insulating layer 14. It is covered.
- the wiring pattern of the metal wiring layer 12 is not particularly limited, and may be a lattice pattern as shown in FIG. 2, or may be a stripe pattern, a strip pattern, a comb pattern, or the like.
- each wiring of the metal wiring layer 12 is not particularly limited, but is preferably 0.1 to 50 m.
- a method of forming the metal wiring layer 12 for example, a metal powder that becomes conductive particles and a binder such as glass fine particles are blended to form a paste, and this is screen printing, metal mask, ink jet
- a method may be used in which a coating is formed so as to form a predetermined pattern using a printing method, and the conductive particles are fused by heating and baking.
- the firing temperature is preferably 600 ° C. or lower, more preferably 550 ° C. or lower.
- a forming method such as a sputtering method, a vapor deposition method, or a plating method can also be used.
- the surface of the metal wiring layer 12 is preferably smooth, but priority is given to having high conductivity over this, and there may be some undulations and irregularities.
- Specific resistance of the metal wiring layer 12 is at least 9 X 10_ 5 ⁇ 'cm or less, more preferably, 5 X 1 0 "5 ⁇ ' is desirably cm or less.
- the insulating layer 14 is made of an amorphous or crystalline, and further a composite low melting point glass layer.
- the insulating layer 14 is a low-layer containing lead oxide such as PbO-PO-SnF or PbO-SiO-BO.
- the insulating layer 14 is composed of a plurality of layers, it can be formed of, for example, two or more kinds of low melting glass having different melting temperatures.
- a low melting point glass layer having a thermal expansion coefficient smaller than that of the substrate 10 is used as a material for the insulating layer 14. Thermal expansion of the low-melting-point glass layer can be used which is adjusted to, for example, 65 X 10 about one 7 ⁇ 69 X 10_ 7.
- the thickness is the largest and the thermal expansion coefficient of the layer is smaller than that of the substrate 10.
- the resistance of the electrode substrate 1 can be reduced.
- the thermal expansion coefficient of the substrate 10 is defined as a and the thermal expansion coefficient of the insulating layer 14 is defined as ⁇
- ⁇ > ⁇ is satisfied and the thickness of the transparent conductive layer 11 is 0. Because it is said to be 5 to 5 ⁇ m, it suppresses deterioration of characteristics due to leakage from metal wiring to electrolyte and corrosion of metal wiring layer, which are difficult to crack due to volume change due to heat treatment be able to.
- the insulating layer 14 is a low-melting-point glass layer, the electrode substrate 1 of the present embodiment can cover the metal wiring layer 12 densely and has excellent chemical resistance against the electrolyte solution constituting the electrolyte layer. It becomes.
- the electrode substrate shown in FIG. 3 is different from the electrode substrate shown in FIG. 1 in that a shielding layer 13 is provided on the transparent conductive layer 11.
- the problem is small compared to the metal wiring layer 12, but since leakage from the transparent conductive layer 11 has been pointed out, it is higher by providing the shielding layer 13 to cover the transparent conductive layer 11. A shielding effect can be obtained.
- a compound having a low electron transfer reaction rate with an electrolytic solution containing a redox species and having a high light transmittance and a high photoelectron transfer ability is selected.
- oxide semiconductors such as zinc oxide (ZnO), nickel niobium (Nb 2 O 3), and tin oxide (SnO 2) Indicated.
- the shielding layer 13 does not hinder electron transfer to the transparent conductive layer 11! It is necessary to form a thin film as thin as /, and it is preferable to have a thickness of about 1 to: LOOOnm.
- the method for forming the shielding layer 13 is not particularly limited.
- an oxide semiconductor as a target compound or a precursor thereof is produced by a dry method (vapor phase method) such as sputtering, vapor deposition, or CVD.
- a method of forming a film is mentioned.
- the shielding layer 13 can be obtained by oxidizing by heat treatment or chemical treatment.
- a liquid containing the target compound or its precursor is applied by a method such as spin coating, destaining or blade coating, and then chemically changed to the target compound by heat treatment or chemical treatment.
- the shielding layer 13 can be obtained.
- the precursor examples include salts and complexes having a constituent metal element of the target compound.
- a solution is preferable to a dispersion.
- the base material 10 having the transparent conductive layer 11 is heated and becomes a precursor of the shielding layer 13 toward the base material 10. It is possible to use a method of forming the shielding layer 13 by spraying a substance, thermally decomposing it, and changing it to the target oxide semiconductor.
- the shielding layer 13 for shielding the transparent conductive layer 11 in this way, the leakage of the transparent conductive layer 11 force can be suppressed, and thus a photoelectric conversion element with higher photoelectric conversion efficiency is manufactured. be able to.
- FIG. 4 shows an example of the photoelectric conversion element constituting the dye-sensitized solar cell.
- This photoelectric conversion element 6 includes a working electrode 3 having an oxide semiconductor porous film 2 on an electrode substrate 1 shown in FIG. 1 and a counter electrode 4 provided to face the working electrode 3.
- a charge transfer layer 5 made of an electrolyte such as an electrolyte is formed between the working electrode 3 and the counter electrode 4.
- an oxide semiconductor porous film 2 carrying a sensitizing dye is formed on the surface of the electrode substrate 1, and the electrode substrate 1 and the oxide semiconductor porous film 2
- the working electrode 3 of the photoelectric conversion element 6 is formed.
- the electrode substrate 1 is the electrode substrate 1 having the configuration shown in FIG. It is not limited to this!
- the oxide semiconductor porous film 2 includes titanium oxide (TiO 2), tin oxide (SnO 2),
- the average particle size of the oxide semiconductor fine particles is preferably in the range of 1 to: LOOOnm.
- the thickness of the oxide semiconductor porous film 2 is preferably about 0.5 to 50 ⁇ m.
- the method for forming the oxide semiconductor porous film 2 is not particularly limited.
- a dispersion obtained by dispersing commercially available oxide semiconductor fine particles in a desired dispersion medium, or a zeolite After adding a desired additive to the colloidal solution that can be adjusted by the gel method, the screen printing method, inkjet printing method, roll coating method, doctor blade method, spin coating method, spray coating method, etc.
- the method of applying is mentioned.
- the electrode substrate 1 is immersed in a colloidal solution, and electrophoretic deposition is performed by electrophoretic deposition of oxide semiconductor particles on the electrode substrate 1, and a colloidal solution or dispersion is mixed with a foaming agent and applied.
- a method of sintering and porous formation, after mixing and applying polymer microbeads, the polymer microbeads are removed by heat treatment or chemical treatment to form voids and make porous Methods etc. can be applied.
- the sensitizing dye supported on the oxide semiconductor porous film 2 is not particularly limited.
- a ruthenium complex containing a biviridine structure, a terpyridine structure or the like as a ligand, an iron complex, or a porphyrin Selected from organic and phthalocyanine-based metal-containing complexes, organic dyes such as coumarin, eosin, podamine, merocyanine, etc. that have excitation behavior suitable for the application and oxide semiconductor. be able to.
- the charge transport layer 5 is composed of an electrolyte
- an electrolytic solution containing a redox pair can be used.
- a gel electrolyte obtained by quasi-solidifying the above electrolytic solution with a suitable gelling agent such as a polymer gelling agent, a low molecular weight gelling agent, various nano particles, or carbon nanotubes may be used.
- Solvents for the electrolyte include organic solvents such as acetonitrile, methoxyacetonitrile, propio-tolyl, propylene carbonate, jetyl carbonate, and ⁇ -butyroratone, imidazolium cation, pyrrolidinium cation, and pyridinium. Cation and iodide ion, bistrifluoromethylsulfurimide-one It can be used by selecting a room-temperature molten salt force that has power such as dicyanamido-one and thiocyanate-on.
- the oxidation-reduction pair contained in the electrolyte can be obtained by adding a pair of iodine Z iodide ion, bromine Z bromide ion, etc., without particular limitation.
- iodide ion or bromide ion lithium salt, quaternized imidazolium salt, tetraptylammonium salt and the like can be used alone or in combination. If necessary, additives such as 4 tert butylpyridine (TBP) may be added to the electrolyte!
- the counter electrode 4 for example, on a conductive substrate or a substrate made of a non-conductive material such as glass, various carbon materials, conductive polymers, metal materials such as gold and platinum, ITO, etc.
- a conductive oxide semiconductor power such as FTO can be used.
- the electrode is a platinum film, for example, a method of applying chloroplatinic acid and heat-treating it can be exemplified. Further, the electrode may be formed by vapor deposition or sputtering.
- the electrode substrate 1 since the electrode substrate 1 has the metal wiring layer 12 electrically connected to the transparent conductive layer 11, the resistance of the electrode substrate 1 is reduced.
- the cell characteristics can be greatly improved.
- the electrode substrate 1 of this embodiment if the thermal expansion coefficient of the substrate 10 is defined as oc and the thermal expansion coefficient of the insulating layer 14 is defined as ⁇ , a> ⁇ is satisfied.
- the metal wiring layer 12, which is less prone to cracking due to the volume change, is reliably shielded from the electrolyte in the charge transfer layer 5, etc., and the characteristics are deteriorated due to leakage from the metal wiring to the electrolyte and corrosion of the metal wiring layer. Can be suppressed.
- the electrode substrate shown in FIG. 1 was produced by the following procedure.
- indium (III) chloride tetrahydrate and tin (II) chloride dihydrate were dissolved in ethanol to prepare a raw material solution for a capsule.
- a saturated aqueous solution of ammonium fluoride was added to an ethanol solution of tin (IV) chloride pentahydrate and dissolved to prepare an FTO membrane raw material solution.
- lOOmm consisting of soda lime glass as shown in Table 1 X IOOmm thickness 1.
- a silver paste for printing (with a volume resistivity after sintering of 3 X 10_ ° ⁇ ) was screen-printed on the FTO film, and after leveling for 10 minutes, 135 ° C, 20 It was dried in a hot air circulating furnace for 1 minute and baked at 550 ° C. for 15 minutes to form a metal wiring layer 12 having a silver circuit force.
- the metal wiring layer 12 has a circuit width of 300 m and a film thickness of 5 m, and is formed in a shape extending in a strip shape from the current collecting terminal.
- the insulating layer 14 is formed by overlaying the metal wiring layer 12 and printing and baking low-melting glass shown in 7 in Table 1 by screen printing.
- an electrode substrate of Experimental Example 1 was obtained.
- the formation width of the insulating layer 14 was 500 ⁇ m formed on both sides in the width direction of the metal wiring layer 12 so as to have an excess of 100 m per side.
- Table 1 shows the thermal expansion coefficients of the materials used in Experimental Examples 1 to 8.
- Table 2 shows combinations of the material of the base material 10 and the material of the insulating layer 14 in Experimental Examples 1 to 8.
- Experimental Example 7 and Experimental Example 8 are comparative examples that do not satisfy ⁇ > ⁇ .
- a transparent conductive layer 11 similar to that in Experimental Example 1 was formed on the same base material 10 as in Experimental Example 1, and the electrode substrate of Experimental Example 9 was obtained.
- the electrode substrates obtained in this manner, Experimental Example 2, Experimental Example 3, Experimental Example 7, and Experimental Example 9 were each interposed with a 50 m thick insulating resin sheet as a spacer.
- a 50 m thick insulating resin sheet On the surface The glass substrate on which the electrode composed of the platinum layer and the FTO film was formed, and the metal wiring layer 12 of the electrode substrate and the electrode of the glass substrate were placed facing each other.
- 0.5 (molZD 1,3-dialkylimidazolium fluoride salt and 0.05 (molZD iodine are dissolved in methoxyacetonitrile) between the electrode substrate and the glass substrate.
- iodine electrolyte containing l (molZl) lithium iodide (Lil) and 0.5 (mol / 1) 4-tert-butylpyridine (TBP)
- TBP 4-tert-butylpyridine
- the leakage current density of Experimental Example 7 was 1 ⁇ 10 _4 AZcm 2 , and the leakage current was observed.
- the leakage current density in Experimental Example 2 and Example 3 was 1 ⁇ 10 _8 AZcm 2 , which is the measurement limit level as in Experimental Example 9 without the metal wiring layer 12.
- FIG. 5A is a cross-sectional view in the width direction of the metal wiring layer 12 showing a part of the electrode substrate 1 of Experimental Example 2 and Experimental Example 3 enlarged
- FIG. 5B is a part of the electrode substrate 1 of Experimental Example 7.
- FIG. 3 is a cross-sectional view in the width direction of a metal wiring layer 12 shown in an enlarged manner.
- Experimental Example 7 which is a comparative example, it was found that the color of the iodine electrolyte was faded, and the iodine electrolyte that entered from the crack of the insulating layer 14 reacted with the silver constituting the metal wiring layer 12. .
- Experimental Examples 2 and 3 which are examples of the present invention, the discoloration of the iodine electrolyte was not observed, and it was found that the iodine electrolyte reacted with the metal wiring layer 12.
- leakage current was observed in Experimental Example 7, but the leakage current in Experimental Example 2 and Example 3 was below the measurement limit level as in Experimental Example 9 without the metal wiring layer 12.
- the photoelectric conversion element shown in FIG. 4 was produced according to the following procedure.
- a titanium oxide dispersion with an average particle diameter of 13 to 20 nm was applied, dried, heated and sintered at 450 ° C for 1 hour, An oxide semiconductor porous film 2 was formed.
- the working electrode 3 was prepared by immersing the solution in an ethanol solution of ruthenium biviridine complex (N3 dye) overnight.
- a platinum sputtered FTO glass electrode substrate is used as the counter electrode 4, and the counter electrode 4 and the working electrode 3 are opposed to each other with a 50 m thick thermoplastic resin sheet interposed as a spacer. Both electrodes 3 and 4 were fixed by heat melting. At this time, a part of the counter electrode 4 side was left open to serve as an electrolyte injection port.
- Experiment Example 1 which is an embodiment of the present invention, the conversion efficiency was 3.1%, in Experiment Example 2, the conversion efficiency was 4.8%, in Experiment Example 3, the conversion efficiency was 4.8%, and in Experiment Example 4. The conversion efficiency was 5.0%, the conversion efficiency in Experiment 5 was 4.5%, and the conversion efficiency in Experiment 6 was 4.6%, indicating good output characteristics.
- the electrode substrate shown in FIG. 1 was produced by the following procedure.
- the same ITO film raw material solution as in Experimental Example 1 was prepared.
- a 100 mm X 100 mm base material 10 made of any of the materials 1 3 4 5 in Table 1 is placed on the heater plate and heated, and the ITO film material solution is applied onto the base material 10 using a spray nozzle.
- the transparent conductive layer 11 was formed by spraying to form an ITO film having the thickness shown in Table 3.
- Example 9 to Experiment Example 12 Experiment Example 15 to Experiment Example 25, Experiment Example 28 to Experiment Example 31 were obtained.
- the electrode substrate shown in FIG. 1 was produced by the following procedure.
- the electrode substrate shown in FIG. 1 was produced by the following procedure. First, the same ITO film raw material solution and FTO film raw material solution as in Experimental Example 1 were prepared. Next, a 100mm x 100mm base material 10 made of any of the materials 1, 4 and 5 in Table 1 was placed on the heater plate and heated, and the ITO film raw material liquid was used as the base material using a spray nozzle. After spraying onto 10 and forming an ITO film with a thickness of 0.8 m, the FTO film raw material solution is sprayed onto the substrate 10 with a spray nozzle to form an FTO film with a thickness of 0. A transparent conductive layer 11 having a thickness of 1 ⁇ m made of a composite film of FTO and ITO was formed.
- Table 1 shows the coefficient of thermal expansion of the materials used in Experimental Example 9 to Experimental Example 33.
- Tables 3 to 6 show combinations of the material of the base material 10 and the material of the insulating layer 14 in Experimental Example 9 to Experimental Example 33.
- ⁇ The value is less than 5 when the sheet resistance is 1 when the thickness of the transparent conductive layer is 0.7 m.
- ⁇ When the sheet resistance when the thickness of the transparent conductive layer is 0.7 / zm is 1, the value is in the range of 5 to L000.
- X Value exceeding 1000 when the sheet resistance is 1 when the thickness of the transparent conductive layer is 0.7 / zm.
- ⁇ When the thickness of the transparent conductive layer is 0.7 / zm, the light transmittance is 1, and the value exceeds 0.9.
- the sheet resistance is 1000 or less when the transparent conductive layer thickness is 0.05 m or more and the value when the transparent conductive layer thickness is 0.7 m is 1 or less.
- the thickness of the transparent conductive layer was 0.2 ⁇ m or more, there was a tendency for the value to be 5 or less when the value when the thickness of the transparent conductive layer was 0.7 ⁇ m was 1.
- the thickness of the transparent conductive layer is in the range of 0.05 to 5 / ⁇ ⁇ , the surface will not crack.
- Light transmittance force The value when the thickness of the transparent conductive layer is 0.7 / zm is set to 1. When the value exceeds 0.6, the sheet resistance, and when the transparent conductive layer thickness is 0.7 m, the value is less than 1000, preferably 1. Furthermore, if the thickness of the transparent conductive layer is in the range of 0.2 to 2 / ⁇ ⁇ , the light transmittance is 0 when the value when the thickness of the transparent conductive layer is 0.7 m is 1. A value exceeding 9, a sheet resistance, and a value when the thickness of the transparent conductive layer was 0.7 / zm was 5 or less when the value was 1, confirming that it was more preferable. Industrial applicability
- the present invention it is possible to reduce the resistance of the electrode substrate, and it is also possible to suppress deterioration of characteristics due to leakage from the metal wiring to the electrolyte and corrosion of the metal wiring layer.
- the photoelectric conversion element used suitably for a solar cell can be provided.
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Abstract
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JP2003203681A (ja) | 2001-12-28 | 2003-07-18 | Fujikura Ltd | 光電変換素子用導電性ガラス |
JP2004164970A (ja) * | 2002-11-12 | 2004-06-10 | Fujikura Ltd | 電極基板および光電変換素子 |
JP2005078857A (ja) * | 2003-08-28 | 2005-03-24 | Fujikura Ltd | 電極基板、光電変換素子、並びに色素増感太陽電池 |
EP1548868A1 (en) | 2002-10-03 | 2005-06-29 | Fujikura Ltd. | Electrode substrate, photoelectric conversion elememt, conductive glass substrate and production method therefo, and pigment sensitizing solar cell |
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JP3510761B2 (ja) * | 1997-03-26 | 2004-03-29 | 太陽インキ製造株式会社 | アルカリ現像型光硬化性導電性ペースト組成物及びそれを用いて電極形成したプラズマディスプレイパネル |
US6313052B1 (en) * | 1998-02-27 | 2001-11-06 | Asahi Glass Company Ltd. | Glass for a substrate |
TW565539B (en) * | 1998-08-11 | 2003-12-11 | Asahi Glass Co Ltd | Glass for a substrate |
ATE409947T1 (de) * | 1999-09-24 | 2008-10-15 | Toshiba Kk | Elektrolyt-zusammensetzung, sonnenzelle, die solche elektrolyt-zusammensetzung anwendet, und herstellungsverfahren der sonnenzelle |
KR100679877B1 (ko) * | 1999-11-22 | 2007-02-07 | 소니 가부시끼 가이샤 | 기능성 디바이스 및 그 제조 방법 |
US6987358B2 (en) * | 2002-08-08 | 2006-01-17 | Asahi Glass Company, Limited | Glass for covering electrodes, colored powder for covering electrodes and plasma display device |
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2005
- 2005-08-02 JP JP2005223920A patent/JP5008841B2/ja not_active Expired - Fee Related
-
2006
- 2006-06-22 CN CNA2006800270235A patent/CN101228660A/zh active Pending
- 2006-06-22 EP EP06780634.9A patent/EP1919023B1/en not_active Not-in-force
- 2006-06-22 WO PCT/JP2006/312548 patent/WO2007015342A1/ja active Application Filing
- 2006-06-22 KR KR1020087002997A patent/KR101017920B1/ko active IP Right Grant
- 2006-06-22 AU AU2006276649A patent/AU2006276649C1/en not_active Ceased
-
2008
- 2008-02-01 US US12/024,727 patent/US20080169022A1/en not_active Abandoned
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2012
- 2012-12-31 US US13/732,005 patent/US20130139880A1/en not_active Abandoned
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EP1548868A1 (en) | 2002-10-03 | 2005-06-29 | Fujikura Ltd. | Electrode substrate, photoelectric conversion elememt, conductive glass substrate and production method therefo, and pigment sensitizing solar cell |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2151884A4 (en) * | 2007-05-30 | 2014-04-16 | Nippon Electric Glass Co | LAMINATE AND SUNBATTERY WITH LAMINATE |
RU2494844C2 (ru) * | 2008-05-28 | 2013-10-10 | Фрониус Интернэшнл Гмбх | Способ изготовления структуры на поверхности металлической детали |
Also Published As
Publication number | Publication date |
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JP2007042366A (ja) | 2007-02-15 |
CN101228660A (zh) | 2008-07-23 |
AU2006276649B2 (en) | 2009-10-01 |
US20130139880A1 (en) | 2013-06-06 |
KR101017920B1 (ko) | 2011-03-04 |
AU2006276649A1 (en) | 2007-02-08 |
JP5008841B2 (ja) | 2012-08-22 |
EP1919023B1 (en) | 2014-10-22 |
EP1919023A1 (en) | 2008-05-07 |
AU2006276649C1 (en) | 2010-06-24 |
EP1919023A4 (en) | 2012-04-11 |
KR20080036071A (ko) | 2008-04-24 |
US20080169022A1 (en) | 2008-07-17 |
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