TWI583016B - Organic and inorganic hybrid solar cell manufacturing methods and organic and inorganic hybrid solar cells - Google Patents
Organic and inorganic hybrid solar cell manufacturing methods and organic and inorganic hybrid solar cells Download PDFInfo
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- TWI583016B TWI583016B TW102142804A TW102142804A TWI583016B TW I583016 B TWI583016 B TW I583016B TW 102142804 A TW102142804 A TW 102142804A TW 102142804 A TW102142804 A TW 102142804A TW I583016 B TWI583016 B TW I583016B
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- Prior art keywords
- inorganic oxide
- organic
- solar cell
- oxide layer
- hybrid solar
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/02—1,2-Oxazines; Hydrogenated 1,2-oxazines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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- B32B2264/102—Oxide or hydroxide
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/944—Layers comprising zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- H01L31/0256—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 the material
- H01L2031/0344—Organic materials
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Description
本發明係關於一種即便以低溫燒成(low-temperature firing)亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層的太陽電池之製造方法。又,本發明係關於一種使用該太陽電池之製造方法而製造的太陽電池。
在化石燃料之枯竭問題或全球暖化問題之背景下,作為乾淨能源之太陽電池近年來非常受關注,業界正如火如荼地進行研究開發。先前,已被實際應用的是以單晶矽、多晶矽、非晶矽等為代表之矽系太陽電池,但隨著價格昂貴或原料矽(Si)之不足問題等表面化,對下一代太陽電池之要求不斷高漲。
作為對應於此之太陽電池,色素增感太陽電池、有機薄膜太陽電池、有機無機混合太陽電池等有機系太陽電池近年來備受矚目。於色素增感太陽電池中,先前使用於形成有導電層(電極)之基材上形成有層狀之氧化鈦者作為電極材料。該氧化鈦層具有1)吸附增感色素、2)承收自經激發之增感色素注入之電子、3)向導電層傳輸電子、4)提供電子自碘化物離子向色素之遷移(還原)反應場所、以及5)光散射及光封入等作用,並為決定太陽電池之性能之最重要之因素之一。其中,關於「1)吸附增感色素」,為了提高光電轉換效率而必須吸附更多之增感色素。因此,要
求氧化鈦層為多孔質狀,且要求儘可能增大其表面積,儘可能減少雜質。
又,氧化鈦層於有機薄膜太陽電池或有機無機混合太陽電池中亦用作電極材料。有機薄膜太陽電池或有機無機混合太陽電池中,於氧化鈦層積層有半導體,於該半導體中藉由光激發而產生電子與電洞。與色素增感太陽電池之情形同樣地,為了提高光電轉換效率而必須與更多之半導體接觸,要求氧化鈦層為多孔質狀。
通常,作為形成此種多孔質之氧化鈦層之方法,使用有將含有氧化鈦粒子與有機黏合劑之漿料塗佈於基材上,使溶劑揮發後,進而利用高溫燒成處理使有機黏合劑消失的方法。藉此,可將氧化鈦粒子彼此燒結,並且獲得層中存在大量微細之空隙之多孔質膜。然而,於進行如超過500℃之高溫燒成處理之情形時,近年來為了進一步降低成本而存在無法使用需求持續高漲之樹脂基材之問題。又,於進行低溫燒成處理之情形時,有機黏合劑之殘渣殘留於氧化鈦粒子表面,因此亦存在光電轉換效率明顯降低之問題。
對此,例如專利文獻1中揭示有使用減少了有機黏合劑之含量之漿料進行低溫下之燒成處理。然而,專利文獻1中所記載之漿料存在如下問題:黏度較低,塗佈後之形狀保持較為困難,會產生膜厚之不均勻化或端部形狀之崩解,又,於印刷成微細配線狀時會產生配線彼此之附接。
專利文獻1:日本專利第4801899號公報
本發明之目的在於提供一種即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層的太陽電池之製造方法。又,本發明之目的在於提供一種使用該太陽電池之製造方法而製造的太陽電池。
本發明係一種太陽電池之製造方法,其具有:於表面形成有導電層之基材上之形成有該導電層之面塗佈含有無機氧化物微粒子、黏合劑樹脂、及有機溶劑之無機氧化物漿料而於該基材上形成無機氧化物層的步驟;對上述無機氧化物層進行燒成的步驟;對上述無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟;及於上述多孔質無機氧化物層上積層半導體的步驟。
以下,對本發明進行詳細敍述。
本發明者等人進行努力研究,結果發現,於使用含有無機氧化物微粒子、黏合劑樹脂、及有機溶劑之無機氧化物漿料之太陽電池之製造方法中,藉由在對無機氧化物層進行燒成後實施活性能量線照射或臭氧分解處理,而即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層,因此可實現較高之光電轉換效率。又,亦發現,於此種多孔質無機氧化物層,可以短時間充分地吸附或積層增感色素或半導體。
進而,本發明者等人發現,對於此種多孔質無機氧化物層,於吸附有增感色素之情形時亦可實現較高之光電轉換效率,但於吸附或積層有用於有機薄膜太陽電池或有機無機混合太陽電池之半導體之情形時可實現特別高之光電轉換效率,從而完成了本發明。其理由尚不明確,但推測其原因在於,受多孔質無機氧化物層之表面狀態影響之半導體之吸附程度小於增感色素。
本發明之太陽電池之製造方法具有於表面形成有導電層之基材上之形成有該導電層之面塗佈含有無機氧化物微粒子、黏合劑樹脂、及有機溶劑之無機氧化物漿料而於該基材上形成無機氧化物層的步驟。
上述無機氧化物漿料只要可藉由塗佈於表面形成有導電層之基材上之形成有該導電層之面而形成無機氧化物層即可,亦可於導電層與無機氧化
物層之間視需要存在其他層(例如即便進行燒成亦不會成為多孔質狀之無機氧化物層)。
藉由塗佈上述無機氧化物漿料而形成之無機氧化物層之厚度的較佳之下限為100nm,較佳之上限為5000nm,更佳之下限為150nm,更佳之上限為2000nm。
作為塗佈上述無機氧化物漿料之方法,並無特別限定,較佳為使用旋轉塗佈法。又,亦較佳為使用網版印刷法等印刷法,於基材具有柔軟性之情形時,藉由使用利用卷對卷方式之連續印刷步驟,就量產性及生產成本之觀點而言,具有較大優點。再者,較佳為於塗佈後進行乾燥。
關於利用上述網版印刷法之步驟中之網版之網眼之大小、刮漿板攻角、刮漿板速度、刮漿板擠壓力等,較佳為適當設定。
作為上述基材,只要為表面形成有導電層之基材,則並無特別限定,例如可列舉形成有透明導電層之透明基板。作為上述透明基板,只要為透明之基板,則並無特別限定,可列舉矽酸鹽玻璃等玻璃基板等。又,上述玻璃基板亦可使用經化學強化、熱強化者。進而,只要可確保透光性,則亦可使用各種塑膠基板等。
上述透明基板之厚度較佳為0.1~10mm,更佳為0.3~5mm。
作為上述透明導電層,可列舉由In2O3或SnO2之導電性金屬氧化物構成之層或由金屬等導電性材料構成之層。作為上述導電性金屬氧化物,例如可列舉:In2O3:Sn(ITO)、SnO2:Sb、SnO2:F、ZnO:Al、ZnO:F、CdSnO4等。
上述無機氧化物漿料含有無機氧化物微粒子。作為上述無機氧化物微粒子,例如可列舉:氧化鈦微粒子、氧化鋁微粒子、氧化矽微粒子等。其中,較佳為氧化鈦微粒子。氧化鈦因帶隙較寬且資源亦相對較豐富地存在之理由而可較佳地使用。
作為上述氧化鈦微粒子,例如通常可使用金紅石型之氧化鈦微粒子、銳鈦礦型之氧化鈦微粒子、板鈦礦型之氧化鈦微粒子及將該等晶質氧化鈦改質而成之氧化鈦微粒子等。
上述無機氧化物微粒子之平均粒徑的較佳之下限為5nm,較佳之上限為100nm,更佳之下限為10nm,更佳之上限為50nm,進而較佳之上限為25nm。藉由設為上述範圍內,而使所獲得之多孔質無機氧化物層成為具有充分之比表面積者。又,可防止電子與電洞之再結合。又,亦可混合粒徑分佈不同之2種以上之微粒子。
再者,上述平均粒徑可藉由如下方式而求出:使用穿透式電子顯微鏡(TEM)以於1視野中可觀察到約100個微粒子之倍率對微粒子進行觀察,利用游標卡尺測定任意選擇之50個微粒子之最長徑並求出平均值。
上述無機氧化物微粒子之添加量的較佳之下限為無機氧化物漿料中之1重量%,較佳之上限為75重量%。若上述添加量為1重量%以上,則可獲得充分之厚度之多孔質無機氧化物層。若上述添加量為75重量%以下,則可抑制上述無機氧化物漿料之黏度上升,可更平滑地塗佈。上述添加量的更佳之下限為3重量%,更佳之上限為50重量%,進而較佳之上限為35重量%。
上述無機氧化物漿料含有黏合劑樹脂。作為上述黏合劑樹脂,例如可列舉:乙基纖維素(EC)、(甲基)丙烯酸系樹脂、聚乙烯醇(PVA)、聚乙烯丁醛(PVB)、聚乙二醇、聚苯乙烯、聚乳酸等。其中,較佳為(甲基)丙烯酸系樹脂。此處,所謂(甲基)丙烯酸系樹脂,意指丙烯酸系樹脂或甲基丙烯酸系樹脂。
上述(甲基)丙烯酸系樹脂由於低溫分解性優異,故而即便於進行低溫燒成之情形時亦可製成有機殘渣量較少之無機氧化物漿料。又,上述(甲基)丙烯酸系樹脂由於為低黏度特性,故而即便於作業環境(例如,長期曝於
外部氣體、或於網版印刷時自網版或刮漿板等裝置受到較強之剪切等外力之情況)下引起溶劑揮發亦可大幅度抑制黏度特性之變化,因此可進行穩定之塗佈。
作為上述(甲基)丙烯酸系樹脂,只要為於300℃左右之低溫發生分解者,則並無特別限定,例如可較佳地使用由選自由(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸苄酯及具有聚氧伸烷基結構之(甲基)丙烯酸系單體所組成之群中之至少1種構成的聚合物。此處,例如所謂(甲基)丙烯酸酯,意指丙烯酸酯或甲基丙烯酸酯。其中,就可以較少之樹脂之量獲得較高之黏度而言,較佳為玻璃轉移溫度(Tg)較高且低溫脫脂性優異之作為甲基丙烯酸異丁酯之聚合物的聚甲基丙烯酸異丁酯(甲基丙烯酸異丁酯聚合物)。
上述黏合劑樹脂之利用聚苯乙烯換算之重量平均分子量的較佳之下限為5000,較佳之上限為500000。若上述重量平均分子量為5000以上,則成為表現出充分之黏度而可較佳地進行塗佈之無機氧化物漿料。若上述重量平均分子量為500000以下,則抑制由上述無機氧化物漿料之黏著力變高所致之拉絲之產生而使塗敷性進一步提高。上述重量平均分子量的更佳之上限為100000,進而較佳之上限為50000。再者,利用聚苯乙烯換算之重量平均分子量可藉由使用例如Column LF-804(SHOKO公司製造)作為管柱進行GPC測定而獲得。
作為上述無機氧化物漿料中之黏合劑樹脂之含量,並無特別限定,較佳之下限為1重量%,較佳之上限為50重量%。若上述黏合劑樹脂之含量為1重量%以上,則可使無機氧化物漿料獲得充分之黏度,使塗敷性提高。若上述黏合劑樹脂之含量為50重量%以下,則成為適度之黏度及
黏著力之無機氧化物漿料,使塗敷性提高。
再者,上述黏合劑樹脂較佳為少於上述無機氧化物微粒子之含量。若上述黏合劑樹脂多於上述無機氧化物微粒子,則有燒成後之有機殘渣量變多之情況。
上述無機氧化物漿料含有有機溶劑。作為上述有機溶劑,較佳為黏合劑樹脂之溶解性優異且極性較高者,例如可列舉:α-松油醇、γ-松油醇等萜烯系溶劑,乙醇、異丙醇等醇系溶劑,二醇、三醇等多元醇系溶劑,上述醇系溶劑/烴等之混合溶劑,二甲基甲醯胺、二甲基亞碸、四氫呋喃等雜化合物等。其中,較佳為萜烯系溶劑。
上述有機溶劑之沸點較佳為50~300℃。若上述有機溶劑之沸點為50℃以上,則所獲得之無機氧化物漿料適度地乾燥,因此亦可用於長時間之連續印刷。若上述沸點為300℃以下,則所獲得之無機氧化物漿料於塗佈後之乾燥步驟中之乾燥性提高。再者,上述沸點意指於常壓之沸點。
上述有機溶劑之含量的較佳之下限為55重量%,較佳之上限為95重量%。若上述有機溶劑之含量為上述範圍內,則所獲得之無機氧化物漿料成為適度之黏度,使塗敷性提高。上述有機溶劑之含量之更佳之下限為60重量%。
上述無機氧化物漿料較佳為含有光酸產生劑。藉由含有上述光酸產生劑,而產生利用後述之燒成後之處理的氧化分解、以及利用源自光酸產生劑之酸的有機物分解這兩種作用,因此可更有效地進行殘渣分解。
作為上述光酸產生劑,只要為若照射光則產生酸者,則並無特別限定。作為上述光酸產生劑,例如可列舉酸化合物與光吸收化合物以酯鍵鍵結而成之化合物等。作為上述光酸產生劑之具體例,可列舉:Midori Kagaku公司製造之商品名「TPS-105」(CAS No.66003-78-9)、「TPS-109」(CAS No.144317-44-2)、「MDS-105」(CAS No.116808-67-4)、「MDS-205」(CAS
No.81416-37-7)、「DTS-105」(CAS No.111281-12-0)、「NDS-105」(CAS No.195057-83-1)、「NDS-165」(CAS No.316821-98-4)等鋶鹽化合物;「DPI-105」(CAS No.66003-76-7)、「DPI-106」(CAS No.214534-44-8)、「DPI-109」(CAS No.194999-82-1)、「DPI-201」(CAS No.6293-66-9)、「BI-105(CAS No.154557-16-1)、「MPI-105」(CAS No.115298-63-0)、「MPI-106」(CAS No.260061-46-9)、「MPI-109」(CAS.No.260061-47-0)、「BBI-105」(CAS No.84563-54-2)、「BBI-106」(CAS No.185195-30-6)、「BBI-109」(CAS No.194999-85-4)、「BBI-110」(CAS No.213740-80-8)、「BBI-201」(CAS No.142342-33-4)等錪鹽化合物;Midori Kagaku公司製造之商品名「NAI-106」(萘二甲醯亞胺樟腦磺酸鹽,CAS No.83697-56-7)、「NAI-100」(CAS No.83697-53-4)、「NAI-1002」(CAS No.76656-48-9)、「NAI-1004」(CAS No.83697-60-3)、「NAI-101」(CAS No.5551-72-4)、「NAI-105」(CAS No.85342-62-7)、「NAI-109」(CAS No.171417-91-7)、「NI-101」(CAS No.131526-99-3)、「NI-105」(CAS No.85342-63-8)、「NDI-101」(CAS No.141714-82-1)、「NDI-105」(CAS No.133710-62-0)、「NDI-106」(CAS No.210218-57-8)、「NDI-109」(CAS No.307531-76-6)、「PAI-01」(CAS No.17512-88-8)、「PAI-101」(CAS No.82424-53-1)、「PAI-106」(CAS No.202419-88-3)、「PAI-1001」(CAS No.193222-02-5)、「SI-101」(CAS No.55048-39-0)、「SI-105」(CAS No.34684-40-7)、「SI-106」(CAS No.179419-32-0)、「SI-109」(CAS No.252937-66-9)、「PI-105」(CAS No.41580-58-9)、「PI-106」(CAS No.83697-51-2);Ciba Specialty Chemicals公司製造之商品名「PAG-121」、「CGI1397」、「CGI1325」、「CGI1380」、「CGI1311」、「CGI263」、「GGI268」等磺酸酯系化合物;Midori Kagaku公司製造之商品名「DTS200」(CAS No.203573-06-2);Rhodia Japan公司製造之商品名「RHODORSIL PHOTOINITIATOR-2074」(CAS No.178233-72-2)等以
BF4 -為相對離子之化合物等。光酸產生劑可單獨使用,亦可併用2種以上。其中,較佳為使用具有下述式(1)所示之結構之光酸產生劑。
作為上述光酸產生劑之含量,並無特別限定,較佳之下限為0.0025重量%,較佳之上限為2.5重量%。若上述光酸產生劑之含量為0.0025重量%以上,則藉由添加光酸產生劑可獲得充分之有機物分解效果。若上述光酸產生劑之含量為2.5重量%以下,則例如可減少由上述光吸收化合物之比率亦增加引起之不良影響。上述光酸產生劑之含量的更佳之下限為0.025重量%,更佳之上限為1.25重量%。
上述無機氧化物漿料較佳為於大氣氛圍下自25℃以10℃/min之升溫速度加熱至300℃後之黏合劑樹脂及有機溶劑之含量為1重量%以下。
該情形時,上述無機氧化物漿料由於加熱後之表面雜質較少,故而容易引起無機氧化物微粒子間之結合(頸縮(necking)),其結果可減少粒子間阻力,因此可實現較高之光電轉換效率。
若上述含量超過1重量%,則有因雜質殘留於無機氧化物微粒子表面而無法良好地積層半導體之情況。再者,上述含量為相對於無機氧化物微粒子之含量。
上述無機氧化物漿料不僅塗敷性優異,而且即便以低溫燒成亦可較佳地製造孔隙率較高且雜質較少之多孔質無機氧化物層。
又,上述無機氧化物漿料由於與網版之洗淨中通常所使用之有機溶劑
之相溶性優異,於使用後可充分地洗淨去除,故而可減少網版之孔堵塞,可穩定地長期進行網版印刷。
作為製造上述無機氧化物漿料之方法,可使用具有將無機氧化物微粒子、黏合劑樹脂、及有機溶劑混合之混合步驟的方法。作為上述混合之手段,例如可列舉:使用兩輥研磨機、三輥研磨機、珠磨機、球磨機、分散機、行星式混合機、自轉公轉式攪拌裝置、捏合機、擠出機、旋轉混合器、攪拌器等進行混合之方法等。
本發明之太陽電池之製造方法具有對上述無機氧化物層進行燒成的步驟。
上述無機氧化物層之燒成可根據所塗敷之基材之種類等而適當調整溫度、時間、氛圍等。例如較佳為於大氣下或不活性氣體氛圍下,於50~800℃左右之範圍內,進行10秒~12小時左右之燒成。藉由本發明之太陽電池之製造方法,即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層,因此亦可採用300℃以下之相對較低之溫度作為燒成溫度。
又,乾燥及燒成可於單一之溫度進行1次或改變溫度而進行2次以上。
本發明之太陽電池之製造方法具有對上述無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟。
藉由進行上述步驟,可藉由無機氧化物之觸媒活性效果而將無機氧化物層中之微量之有機殘渣氧化分解。其結果,可有助於太陽電池之性能之進一步提高。又,上述步驟之效果於使用(甲基)丙烯酸系樹脂作為黏合劑樹脂之情形時表現得尤其明顯。此外,於使用平均粒徑較小之無機氧化物微粒子之情形時,可使無機氧化物與黏合劑樹脂之接觸面積增加。其結果,可進一步提高無機氧化物之觸媒活性效果。
對上述無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟可與對上述無機氧化物層進行燒成之步
驟同時進行,亦可於對上述無機氧化物層進行燒成之步驟後進行。
作為上述活性能量線,例如可列舉:紫外線、電漿、電子束等。
於上述活性能量線為紫外線之情形時,較佳為以紫外線之累計光量成為100J/cm2以上之方式對上述無機氧化物層照射紫外線。若上述累計光量為100J/cm2以上,則可充分地進行有機殘渣之去除。上述累計光量的更佳之下限為150J/cm2,較佳之上限為10000J/cm2。再者,累計光量可利用照射強度(mW/cm2)×照射時間(秒)而簡便地算出。
又,紫外線之照射強度較佳為0.5~1000mW/cm2。
進而,紫外線之照射時間較佳為1秒~300分鐘,更佳為1秒~60分鐘。若照射強度過小、或照射時間過短,則僅部分性地進行有機殘渣之去除,因此無法獲得充分之效果,若照射強度過大、或照射時間過長,則有引起透明基板之紫外線劣化或熱劣化之情況。
於上述活性能量線為電漿之情形時,電漿處理強度較佳為50~1000W。
進而,電漿處理時間較佳為1秒~30分鐘,更佳為10秒~10分鐘。若處理強度過小、或處理時間過短,則僅部分性地進行有機殘渣之去除,因此無法獲得充分之效果,若處理強度過大、或處理時間過長,則有產生由電漿引起之基板之劣化或熱劣化之情況。
又,作為電漿處理時之氛圍,例如可列舉:氮、氧、氬等氛圍。藉由進行氮電漿處理,可部分性地進行氮化處理、或修補因氧電漿處理進行了處理之無機氧化物之氧空位。
作為照射上述活性能量線之方法,並無特別限定,例如可列舉:使用低壓水銀燈、高壓水銀燈、水銀-氙氣燈等照射紫外線的方法、使用電漿產生裝置等照射電漿的方法等。
於照射上述活性能量線之情形時,較佳為自上述無機氧化物層之表側(與基材相反之側)及背側(基材側)這兩側照射活性能量線。藉此,可使活性能量線充分地照射至無機氧化物層之內部。其結果,即便以較少之累計光量等亦可充分地獲得活性能量線照射之效果,從而可縮短製造步驟整體之時間。再者,自表側之照射、及自背側之照射可同時進行,亦可分為複數次依序進行。
於本發明之太陽電池之製造方法中,較佳為於進行對上述無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟之後,進而進行照射脈衝寬度較小之脈衝白色光之步驟。藉由照射上述脈衝白色光,而引起多孔質無機氧化物層中之無機氧化物微粒子間之表面之利用熔融之緻密化,其結果可使表面電阻降低。
上述脈衝光之脈衝寬度較佳為0.1~10ms。藉此可瞬間照射強力之光能。
作為上述脈衝光之累計光量,並無特別限定,較佳為4J/cm2以上。藉此,可對無機氧化物微粒子間之融合施加充分之能量。較佳為15~40J/cm2。進而,照射次數較理想為1~5次。
作為用以照射上述脈衝光之手段,可列舉:鹵素閃光燈、氙氣閃光燈、LED閃光燈等,尤佳為使用氙氣閃光燈。
本發明之太陽電池之製造方法具有於上述多孔質無機氧化物層上積層半導體的步驟。
於上述多孔質無機氧化物層可以短時間充分地積層半導體。對以此種方式獲得之於表面形成有導電層之基材上之形成有該導電層之面至少具有多孔質無機氧化物層與半導體的積層體進而視需要積層其他層之後設置對向電極(導電層),藉此可製造太陽電池。以此種方式獲得之太陽電池可達成較高之光電轉換效率。再者,對於上述多孔質無機氧化物層,於吸附有
增感色素之情形時亦可實現較高之光電轉換效率,但於吸附或積層有用於有機薄膜太陽電池或有機無機混合太陽電池之半導體之情形時可實現特別高之光電轉換效率。
上述半導體只要含有通常用於有機薄膜太陽電池或有機無機混合太陽電池的作為N型半導體而發揮功能者與作為P型半導體而發揮功能者,則並無特別限定。於此種半導體中,藉由光激發而產生電子與電洞,且電子於N型半導體內遷移,電洞於P型半導體內遷移,藉此產生電場。
作為上述半導體,具體而言,較佳為週期表15族元素之硫化物、有機無機混合半導體。
作為上述週期表15族元素之硫化物,較佳為硫化銻、硫化鉍,就光電轉換效率提高而言,更佳為硫化銻。上述週期表15族元素之硫化物可單獨使用,亦可併用2種以上。又,上述週期表15族元素之硫化物亦可為同一分子中含有週期表15族元素之2種以上之元素之複合硫化物。
上述有機無機混合半導體只要為結構中具有有機成分與無機成分這兩者之半導體,則並無特別限定,但較佳為含有鹵素。藉由在結構中含有鹵素,而變得可溶於有機溶劑,從而可應用於廉價之印刷法等。
又,上述有機無機混合半導體較佳為以通式R-M-X3(R為有機分子,M為金屬原子,X為鹵素原子)表示,此時,進而較佳為具有體心配置有金屬原子M、各頂點配置有有機分子R、面心配置有鹵素原子X之立方晶系之結構。
上述R為有機分子,較佳為以ClNmHn(l、m、n均為正整數)表示之分子,具體而言,例如可列舉:甲基胺、乙基胺、丙基胺、丁基胺、戊基胺、己基胺、二甲基胺、二乙基胺、二丙基胺、二丁基胺、二戊基胺、二己基胺、三甲基胺、三乙基胺、三丙基胺、三丁基胺、三戊基胺、三己
基胺、乙基甲基胺、甲基丙基胺、丁基甲基胺、甲基戊基胺、己基甲基胺、乙基丙基胺、乙基丁基胺、咪唑、唑(azole)、吡咯、氮丙啶、氮雜環丙烯(azirine)、吖丁啶(azetidine)、氮雜環丁二烯(azete)、咪唑啉、咔唑及該等之離子、或苯乙基銨等。其中,較佳為甲基胺、乙基胺、丙基胺、丁基胺、戊基胺、己基胺及該等之離子、或苯乙基銨,更佳為甲基胺、乙基胺、丙基胺及該等之離子。
上述M為金屬原子,例如可列舉:鉛、錫、鋅、鈦、銻、鉍、鎳、鐵、鈷、銀、銅、鎵、鍺、鎂、鈣、銦、鋁、錳、鉻、鉬、銪等。上述M可單獨使用,亦可併用2種以上。
上述X為鹵素原子,例如可列舉:氯、溴、碘等。上述X可單獨使用,亦可併用2種以上。其中,就能帶隙變窄而言,較佳為包含碘。
作為積層上述半導體之方法,例如可列舉藉由旋轉塗佈法塗佈溶解有上述半導體或其前驅物之半導體製膜用溶液並進行乾燥之方法等。
藉由本發明之太陽電池之製造方法,即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層,可實現較高之光電轉換效率。又,使用本發明之太陽電池之製造方法而製造之太陽電池亦為本發明之一。
藉由本發明,可提供一種即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層的太陽電池之製造方法。又,藉由本發明,可提供一種使用該太陽電池之製造方法而製造的太陽電池。
以下,舉出實施例進一步詳細地說明本發明,但本發明並不僅限定於該等實施例。
(實施例1)
(氧化鈦漿料之製作)
使用氧化鈦微粒子(平均粒徑為10nm及30nm之混合物)、作為黏合劑樹脂之聚甲基丙烯酸異丁酯(重量平均分子量50000)、作為有機溶劑之α-松油醇(沸點219℃)及乙醇(沸點78℃)之混合溶劑,以成為表1之組成之方式使用珠磨機均勻地混合,藉此製作氧化鈦漿料。
(多孔質氧化鈦層之形成)
於玻璃基板上形成厚度1000nm之FTO透明電極作為陰極,依順序使用純水、丙酮、甲醇進行各10分鐘之超音波洗淨後,使之乾燥。
藉由旋轉塗佈法將製備成2重量%之異丙醇鈦之乙醇溶液塗佈於FTO透明電極之表面上並於150℃燒成10分鐘而製成電子傳輸性之緩衝層(氧化鈦層(1))。藉由旋轉塗佈法將上述所獲得之氧化鈦漿料塗佈於玻璃基板上之形成有FTO透明電極與氧化鈦層(1)之面,並於150℃燒成10分鐘(氧化鈦層(2))。氧化鈦層(1)及(2)具有合計約500nm之厚度。其後,進而使用高壓水銀燈(SEN LIGHTS公司製造,HLR100T-2),自與玻璃基板相反之側(表側)以照射強度500mW/cm2照射紫外線60分鐘,藉此獲得多孔質氧化鈦層。
(太陽電池之製作)
於N,N-二甲基甲醯胺(DMF)中溶解氯化銻與硫脲(莫耳比1:2),將氯化銻與硫脲之合計濃度調整為20重量%,獲得半導體製膜用溶液(1)。
藉由旋轉塗佈法將該半導體製膜用溶液(1)塗佈於上述獲得之多孔質氧化鈦層上並進行乾燥。進而,於氯苯25μL中溶解Spiro-OMeTAD 68mM、第三丁基吡啶55mM、雙(三氟甲基磺醯基)醯亞胺鋰鹽9mM,獲得半導體製膜用溶液(2)。藉由旋轉塗佈法將該半導體製膜用溶液(2)塗佈於所獲得之半導體層上並進行乾燥。
藉由真空蒸鍍於所獲得之半導體層上形成厚度100nm之金膜作為陽極,而獲得太陽電池。
(實施例2~14、比較例1)
如表1所示般變更黏合劑樹脂、無機氧化物微粒子、燒成之條件、燒成後之處理(紫外線照射或電漿照射)之條件、半導體,除此以外,以與實施例1相同之方式獲得多孔質氧化鈦層、太陽電池。
再者,於實施例12中,由CH3NH3PbI2Cl構成之半導體層係由N,N-二甲基甲醯胺(DMF)中溶解有CH3NH3I與PbCl2(莫耳比3:1)之半導體製膜用溶液(1)所獲得。於實施例13、14中,於表1所示之條件下進行電漿處理代替紫外線照射。
<評價1>
對實施例1~14及比較例1中所獲得之太陽電池進行以下評價。將結果示於表1。
(太陽電池之性能評價)
將電源(236型號,KEITHLEY公司製造)連接於所獲得之太陽電池之電極間,使用100mW/cm2之強度之太陽模擬器(山下電裝公司製造)測定太陽電池之光電轉換效率。
又,將使除了於550℃下燒成60分鐘以外於相同條件下製作的太陽電池之光電轉換效率標準化為1時之相對轉換效率示於表1。
(比較例2)
(氧化鈦漿料之製作)
使用平均粒徑為20nm之氧化鈦微粒子、作為黏合劑樹脂之聚甲基丙烯酸異丁酯(重量平均分子量50000)、作為有機溶劑之α-松油醇(沸點219℃),以成為表1之組成之方式使用珠磨機均勻地混合,藉此製作氧化鈦漿料。
(多孔質氧化鈦層之形成)
將所獲得之氧化鈦漿料於25mm見方之已形成有FTO透明電極之玻璃基板上印刷成5mm見方之正方形狀,於150℃燒成60分鐘。再者,以使所獲得之多孔質氧化鈦層之厚度成為10μm之方式進行印刷條件之微調整。
(色素增感太陽電池之製作)
將所獲得之附有多孔質氧化鈦層之基板於Ru錯合物色素(N719)之乙腈:第三丁醇=1:1之溶液(濃度0.3mM)中浸漬1天,藉此使增感色素吸附於多孔質氧化鈦層表面。
其次,於該基板上以除一方向外包圍多孔質氧化鈦層之方式載置厚度30μm之Himilan公司製造之膜,進而自其上方載置蒸鍍有鉑電極之玻璃基板,並向其間隙中注入碘化鋰及碘之乙腈溶液進行密封,藉此獲得色素增感太陽電池。
(比較例3、4)
如表1所示般進行燒成後之處理(紫外線照射),除此以外,以與比較例2相同之方式獲得多孔質氧化鈦層、色素增感太陽電池。
<評價2>
對比較例2~4中所獲得之色素增感太陽電池進行以下評價。將結果示於表1。
(色素增感太陽電池之性能評價)
將電源(236型號,KEITHLEY公司製造)連接於所獲得之色素增感太
陽電池之電極間,使用100mW/cm2之強度之太陽模擬器(山下電裝公司製造)測定色素增感太陽電池之光電轉換效率。
又,將使除了於550℃燒成60分鐘以外於相同之條件下製作的色素增感太陽電池之光電轉換效率標準化為1時之相對轉換效率示於表1。
若將實施例1~14中所獲得之太陽電池之光電轉換效率與比較例1中所獲得之太陽電池之光電轉換效率加以比較,則判明藉由進行燒成後之處理(紫外線照射或電漿照射),可實現較高之光電轉換效率。
又,若將實施例1~14中所獲得之太陽電池之光電轉換效率與比較例3、4中所獲得之色素增感太陽電池之光電轉換效率加以比較,則判明與使增感色素吸附於多孔質氧化鈦層而製作色素增感太陽電池之情形(比較例3、4)相比,於使有機薄膜太陽電池或有機無機混合太陽電池中所使用之半導體吸附或積層於多孔質氧化鈦層之情形(實施例1~14)時可實現特別高之光電轉換效率。
[產業上之可利用性]
藉由本發明,可提供一種即便以低溫燒成亦可製造孔隙率較高且雜質較少之多孔質無機氧化物層的太陽電池之製造方法。又,藉由本發明,可提供一種使用該太陽電池之製造方法而製造的太陽電池。
Claims (7)
- 一種有機無機混合太陽電池之製造方法,其具有:於表面形成有導電層之基材上之形成有該導電層之面塗佈含有無機氧化物微粒子、黏合劑樹脂、及有機溶劑之無機氧化物漿料而於該基材上形成無機氧化物層的步驟;對上述無機氧化物層以50~300℃進行燒成的步驟;對上述無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟;及於上述多孔質無機氧化物層上積層由週期表15族元素之硫化物構成之半導體、或以通式R-M-X3(R為有機分子,M為金屬原子,X為鹵素原子)表示之有機無機混合半導體的步驟。
- 如申請專利範圍第1項之有機無機混合太陽電池之製造方法,其中黏合劑樹脂為(甲基)丙烯酸系樹脂。
- 如申請專利範圍第2項之有機無機混合太陽電池之製造方法,其中(甲基)丙烯酸系樹脂為聚甲基丙烯酸異丁酯。
- 如申請專利範圍第1、2或3項之有機無機混合太陽電池之製造方法,其中有機溶劑之沸點為50~300℃。
- 如申請專利範圍第1、2或3項之有機無機混合太陽電池之製造方法,其中無機氧化物微粒子為氧化鈦微粒子。
- 如申請專利範圍第1、2或3項之有機無機混合太陽電池之製造方法,其中於對無機氧化物層實施活性能量線照射或臭氧分解處理而獲得多孔質無機氧化物層的步驟中,活性能量線為紫外線,並以上述紫外線之累計光量成為100J/cm2以上之方式對無機氧化物層照射上述紫外線而獲得多孔質無機氧化物層。
- 如申請專利範圍第1、2或3項之有機無機混合太陽電池之製造方 法,其中無機氧化物微粒子之平均粒徑為5~100nm。
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