JP5127329B2 - 光電変換素子およびその製造方法 - Google Patents
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- 238000006243 chemical reaction Methods 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000758 substrate Substances 0.000 claims description 58
- 239000002245 particle Substances 0.000 claims description 49
- 239000011941 photocatalyst Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000002041 carbon nanotube Substances 0.000 claims description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 35
- 230000002165 photosensitisation Effects 0.000 claims description 16
- 239000003504 photosensitizing agent Substances 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
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- 239000010408 film Substances 0.000 description 69
- 239000000975 dye Substances 0.000 description 19
- 239000008151 electrolyte solution Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000002238 carbon nanotube film Substances 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000001962 electrophoresis Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
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- 229910052707 ruthenium Inorganic materials 0.000 description 4
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- 150000004706 metal oxides Chemical class 0.000 description 3
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- 238000000016 photochemical curing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical group CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000007865 diluting 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
- 238000005530 etching Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 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
- 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
- 239000003960 organic solvent Substances 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
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2072—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells comprising two or more photoelectrodes sensible to different parts of the solar spectrum, e.g. tandem cells
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- 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
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- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description
透明基板の片面上に透明導電膜を介して、光増感色素で染色された光触媒膜を形成することで電極を構成し、
得られた2枚の電極を対向状に配置し、
これらの電極間に、複数の開口部を有する対極用基板の非開口部全体を覆う導電性接着剤層を介して、同基板表面に対して実質上垂直に配向したブラシ状カーボンナノチューブを設けることで構成した対極を配置する
ことを特徴とする方法である。
図1において、ガラスまたはプラスチック製の電極用の透明基板(1) の片面に透明導電膜(2) を形成し、同導電膜(2) 上に酸化チタン粒子(3)からなる光触媒膜(8)を厚さ10〜15μmで形成した。光触媒膜(8) は、平均粒径20〜30nmの酸化チタン粒子を含むペーストを透明基板(1) に塗布し、焼結して形成したものである。
発生電圧は0.44V程度であるが、光電流密度は通常セルの約1.4倍となる16mA/cm2を得ることができ、結果として電力変換効率が向上した。
図2において、表面をITO等の透明導電膜(18)で覆われているガラスまたはプラスチック製の透明基板(1)に対し、この透明導電膜上にPEDOTまたはPEDOT/PSS等の導電性高分子の透明導電膜(2)を形成した。別途、熱化学蒸着、プラズマ化学蒸着などの方法で基材に実質上垂直に形成したカーボンナノチューブを同透明導電膜(2)に実質上垂直に配向するように転写した。カーボンナノチューブ膜(15)は約8μm厚であった。
図3において、ガラスまたはプラスチック製の電極用の透明基板(1) の片面に透明導電膜(2) を形成した。
図7において、表面をITOなどの透明導電膜(2)で覆われたガラス基板またはプラスチック製の電極用の透明基板(1)を、高電圧電源(14)が接続された金属板製の電極(12)上に配置し、この基板(1)に対向するように金属板製の対向電極(13)を配置した。これらの電極(12)(13)間に負高電圧を印加し、静電場を形成した。なお、電極(12)側が負高圧、対向電極(13)側が接地となるように両者が接続されている。
(2)(18) 透明導電膜
(3) 酸化チタン粒子
(4) 対極用基板
(5)(15) カーボンナノチューブ膜
(6) 封止片
(7) 導電性接着剤層
(8) 光触媒膜
(9) 開口部
(10) 光触媒電極(負極)
(11) 対極(正極)
(12)(13) 電極
(14) 高電圧電源
(16) ドクターブレード
(17) 分散液
(25) カーボンナノチューブ粒子
Claims (8)
- 透明基板の片面上に透明導電膜を介して、光増感色素で染色された光触媒膜を形成することで構成した2枚の電極を対向状に配置し、これらの電極間に対極を配置し、前記対極は、複数の開口部を有する対極用基板の非開口部全体を覆う導電性接着剤層を介して、別途形成のブラシ状カーボンナノチューブを同基板表面に対して実質上垂直に配向するように転写することで構成したものであることを特徴とする、光電変換素子。
- 前記電極は、透明基板上の透明導電膜に基板面に対して実質上垂直に設けられたブラシ状カーボンナノチューブに光触媒粒子を担持させ、同粒子を光増感色素で染色することで構成したものであることを特徴とする、請求項1記載の光電変換素子。
- 前記電極は、透明基板上の透明導電膜にカーボンナノチューブ粒子と光触媒粒子の混合物からなる光触媒膜を形成し、同触媒膜を光増感色素で染色することで構成したものであることを特徴とする、請求項1記載の光電変換素子。
- 前記電極は、前記対極のブラシ状カーボンナノチューブと接触していることを特徴とする、請求項3記載の光電変換素子。
- 透明基板の片面上に透明導電膜を形成し、同導電膜に別途形成のブラシ状カーボンナノチューブを基板面に対して実質上垂直に配向するように転写し、同カーボンナノチューブに光触媒粒子を担持させ、同粒子を光増感色素で染色することで電極を構成し、
得られた2枚の電極を対向状に配置し、
これらの電極間に、複数の開口部を有する対極用基板の非開口部全体を覆う導電性接着剤層を介して、同基板表面に対して実質上垂直に配向したブラシ状カーボンナノチューブを設けることで構成した対極を配置する
ことを特徴とする、光電変換素子の製造方法。 - 透明基板上に透明導電膜を形成し、同導電膜にカーボンナノチューブ粒子と光触媒粒子の混合物からなる光触媒膜を形成し、同触媒膜を光増感色素で染色することで、前記電極を構成することを特徴とする、請求項5記載の光電変換素子の製造方法。
- 前記透明導電膜にカーボンナノチューブ粒子と光触媒粒子の混合物からなる光触媒膜を形成するに当たり、前記混合物を含むペーストを透明導電膜上に塗布し、乾燥させることを特徴とする、請求項6記載の光電変換素子の製造方法。
- 前記ペーストを透明導電膜上に塗布するに当たり、透明導電膜とこれに対向する電極との間に静電場を形成した状態で塗布を行うことを特徴とする、請求項7記載の光電変換素子の製造方法。
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JP2007183327A JP5127329B2 (ja) | 2007-07-12 | 2007-07-12 | 光電変換素子およびその製造方法 |
TW097126061A TW200910611A (en) | 2007-07-12 | 2008-07-10 | Photoelectric conversion element and method of manufacturing the same |
US12/452,568 US20100132777A1 (en) | 2007-07-12 | 2008-07-11 | Photoelectic conversion element and method of producing the same |
KR1020107000665A KR20100036314A (ko) | 2007-07-12 | 2008-07-11 | 광전 변환 소자 및 그 제조 방법 |
PCT/JP2008/062546 WO2009008495A1 (ja) | 2007-07-12 | 2008-07-11 | 光電変換素子およびその製造方法 |
CN200880024444A CN101743662A (zh) | 2007-07-12 | 2008-07-11 | 光电转换元件及其制造方法 |
EP08791076A EP2173004A4 (en) | 2007-07-12 | 2008-07-11 | PHOTOELECTRIC CONVERSION ELEMENT AND METHOD FOR MANUFACTURING THE SAME |
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JP2011142027A (ja) * | 2010-01-08 | 2011-07-21 | Hitachi Zosen Corp | 色素増感太陽電池の製造方法 |
US10128393B2 (en) | 2010-07-21 | 2018-11-13 | First Solar, Inc. | Connection assembly protection |
JP6021104B2 (ja) * | 2012-08-30 | 2016-11-02 | 日立造船株式会社 | 太陽電池の発電層およびその製造方法並びに太陽電池 |
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EP2173004A4 (en) | 2010-09-22 |
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