JPH01119072A - Manufacture of flexible photoelectric conversion element - Google Patents
Manufacture of flexible photoelectric conversion elementInfo
- Publication number
- JPH01119072A JPH01119072A JP62277125A JP27712587A JPH01119072A JP H01119072 A JPH01119072 A JP H01119072A JP 62277125 A JP62277125 A JP 62277125A JP 27712587 A JP27712587 A JP 27712587A JP H01119072 A JPH01119072 A JP H01119072A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- conversion element
- substrate
- electrode layer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 239000004065 semiconductor Substances 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920003023 plastic Polymers 0.000 claims abstract description 13
- 238000010292 electrical insulation Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 27
- 239000011888 foil Substances 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 abstract description 25
- 239000010408 film Substances 0.000 abstract description 22
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 20
- 238000005530 etching Methods 0.000 abstract description 14
- 239000010409 thin film Substances 0.000 abstract description 11
- 239000004642 Polyimide Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 2
- 238000009751 slip forming Methods 0.000 abstract description 2
- 150000003949 imides Chemical class 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000000489 vacuum metal deposition Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 131
- 229910021419 crystalline silicon Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000008602 contraction Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- -1 pentene terephthalate Chemical compound 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000357293 Leptobrama muelleri Species 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03921—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic Table
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【発明の詳細な説明】
(、)産業上の利用分野
本発明は、可撓性充電変換素子の製造方法に関し、特に
透明プラスチックを基板とする可撓性光電変換素子のP
JI遣方法に関する。DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention relates to a method for manufacturing a flexible charge conversion element, and in particular to a method for manufacturing a flexible photoelectric conversion element using transparent plastic as a substrate.
Regarding JI dispatch method.
(b)従来の技術
光を入力して電気を出力する光電変換素子としては、光
導電素子、ホトダイオード、太陽電池、ホ))ランジス
タ、ホトサイリスタ等が知られている。(b) Prior Art Photoconductive elements, photodiodes, solar cells, e) transistors, photothyristors, and the like are known as photoelectric conversion elements that input light and output electricity.
これらの光電変換素子には光導電性を有する半導体が使
用されているが、中でも、非晶質シリコンを使用するも
のは安価であり、太陽電池或いは光センサとして広く普
及している。Semiconductors having photoconductivity are used in these photoelectric conversion elements, and among them, those using amorphous silicon are inexpensive and widely used as solar cells or optical sensors.
例えば太陽電池では、電極に兼用される金属板からなる
基板の上にp形、 i形、p形の非晶質シリコンを順次
薄膜状に堆積させ、更にその上に透明電極層をNfr4
したもの、或いは、ガラス板から成る基板の上に透明電
極層、p形弁晶質シリコン、i形弁晶質シリコン、n形
弁晶質シリコンを順次堆積し、更にアルミニウム等から
なる金属電極層をMt層したもの等が実用化されている
。For example, in a solar cell, p-type, i-type, and p-type amorphous silicon are sequentially deposited in thin films on a substrate made of a metal plate that also serves as an electrode, and then a transparent electrode layer is formed on top of the Nfr4 amorphous silicon.
Alternatively, a transparent electrode layer, p-type crystalline silicon, i-type crystalline silicon, and n-type crystalline silicon are sequentially deposited on a substrate made of a glass plate, and further a metal electrode layer made of aluminum or the like. Those with an Mt layer have been put into practical use.
金属電極層に兼用される基板は、例えば、ステンレス鋼
、アルミニウム、銅などの箔や薄板で形成され、透明電
極層は、例えば、酸化錫、酸化インジウム等で構成され
る。The substrate that also serves as the metal electrode layer is made of, for example, a foil or thin plate of stainless steel, aluminum, copper, etc., and the transparent electrode layer is made of, for example, tin oxide, indium oxide, or the like.
金属基板を使用する前者では、基板の電気抵抗が充分に
低いので、一定面積の基板から大出力を得ることができ
る。In the former case, which uses a metal substrate, the electric resistance of the substrate is sufficiently low, so a large output can be obtained from a substrate of a fixed area.
また、ガラス板を基板として使用する後者では、基板が
絶縁性を備えるので、複数の半導体を互いに隣接させて
配置し、これらを導電体で直列接続することにより2倍
以上の電圧を得ることが極めて容易である。In addition, in the latter case where a glass plate is used as a substrate, since the substrate has insulating properties, it is possible to obtain more than twice the voltage by arranging multiple semiconductors adjacent to each other and connecting them in series with a conductor. It's extremely easy.
ところで、このような非晶質シリコンを使用する太陽電
池(非晶質シリコン太陽電池と呼ばれている)について
は、現在、材料コストの低減、軽量化、薄型化等を図る
とともに、生産工程或いは輸送中の取扱いの容易性を図
り、生産コストや輸送コスト等の低減を図るために、可
撓性を有する基板を使用することが提案されている。By the way, solar cells using such amorphous silicon (referred to as amorphous silicon solar cells) are currently undergoing efforts to reduce material costs, be lighter, thinner, etc., as well as improve production processes and The use of flexible substrates has been proposed in order to facilitate handling during transportation and reduce production costs, transportation costs, and the like.
例えば、ポリイミドフィルム等の耐熱性プラスチックフ
ィルムを基板とし、この基板上にステンレスW4製の笛
や膜等の金属電極層と、非晶質シリコン層と、透明電極
層とを積層したものが提案されている(例えば、特開昭
54−149489号公報、特開昭55−4994号公
報、特開昭55−29154号公報、特開昭57−10
3839号公報等)。For example, it has been proposed that a heat-resistant plastic film such as a polyimide film is used as a substrate, and a metal electrode layer such as a whistle or membrane made of stainless steel W4, an amorphous silicon layer, and a transparent electrode layer are laminated on this substrate. (For example, JP-A-54-149489, JP-A-55-4994, JP-A-55-29154, JP-A-57-10)
3839, etc.).
この種の非晶質シリコン太陽電池は、軽量、薄型で、且
つ材料コストが低く、また、可撓性に富んでいるのでロ
ール状に巻回して連続処理することにより、生産コスト
或いは輸送コストを軽減する上で非常に有利である。This type of amorphous silicon solar cell is lightweight, thin, and has low material cost, and is highly flexible, so it can be rolled into a roll and processed continuously to reduce production and transportation costs. It is very advantageous in reducing
更に、任意の形状に形成できることも相俟って広範囲に
わたる応用、用途が期待されている。Furthermore, since it can be formed into any shape, it is expected to have a wide range of applications and uses.
(c)発明が解決しようとする問題点
しかしながら、現在までのところ、ポリイミドフィルム
等の耐熱性プラスチックフィルムを基板とする非晶質シ
リコン太陽電池は、このような期待を抱かれているにも
かかわらず、次のような問題があるために実用化される
に至っていないのである。(c) Problems to be Solved by the Invention However, to date, amorphous silicon solar cells using heat-resistant plastic films such as polyimide films as substrates have not met with high expectations. However, it has not been put into practical use due to the following problems.
即ち、製造中、基板フィルムを加熱昇温させるときに基
板フィルムにカールが発生すること、基板フィルムと非
晶質シリコン層の熱膨張係数の差異によって製品にカー
ルが発生すること等が問題となっている。That is, during manufacturing, curling occurs on the substrate film when the substrate film is heated to an elevated temperature, and curling occurs on the product due to the difference in thermal expansion coefficient between the substrate film and the amorphous silicon layer. ing.
また、このようなカールの発生は、単に取扱い性の点で
問題になるだけでなく、カールの発生が一因となって光
電変換効率を低下させるという問題もある。In addition, the occurrence of such curls not only poses a problem in terms of handling, but also causes a problem in that the photoelectric conversion efficiency is reduced due to the occurrence of curls.
更に、このようなカールが極端になると、非晶質シリコ
ン層に亀裂が発生して断線状態になり、信頼性が低下す
る。Furthermore, if such curling becomes extreme, cracks will occur in the amorphous silicon layer, resulting in disconnection, reducing reliability.
ところで、ポリイミドフィルムよりも高温時(250〜
350°C)での初期ヤング率が高い芳香族ポリイミド
フィルムを基板に使用する場合には、高温時の初期ヤン
グ率は改良されるのであるが、温度300℃における熱
収縮率は、従来品のそれが0.5%であるのに対して芳
香族ポリイミドフィルムのそれは0.7%以下であり、
半導体層のそれに対して1桁程度大きいので、製品のカ
ール発生を防止することはできない。By the way, at higher temperatures than polyimide film (250 ~
If an aromatic polyimide film with a high initial Young's modulus at 350°C is used for the substrate, the initial Young's modulus at high temperatures will be improved, but the thermal shrinkage at 300°C will be lower than that of conventional products. While it is 0.5%, that of aromatic polyimide film is less than 0.7%.
Since it is about one order of magnitude larger than that of the semiconductor layer, curling of the product cannot be prevented.
本発明に係る可撓性光電変換素子の製造方法は、耐熱性
及び電気絶縁性を有する透明プラスチックを基板とする
可撓性光電変換素子の製造方法に伴う上記の事情を考慮
してなされたものであって、製品にカールが発生するこ
とを防止できるようにした可撓性光電変換素子の製造方
法を提供することを目的とするものである。The method for manufacturing a flexible photoelectric conversion element according to the present invention was made in consideration of the above-mentioned circumstances associated with the method for manufacturing a flexible photoelectric conversion element using a transparent plastic having heat resistance and electrical insulation properties as a substrate. The object of the present invention is to provide a method for manufacturing a flexible photoelectric conversion element that can prevent curling of the product.
本発明に係る可撓性光電変換素子の製造方法は、支持体
の表面上に耐熱性、可視性及び電気絶縁性を有する透明
プラスチック製の基板を形成する工程(A)と、
上記工程(A)において形成された基板の表面上に透明
電極層を積層する工程(B)と、上記工程(B)におい
て形成された透明電極層の表面上に光起電性を有する半
導体層を形成する工程(C)と、
上記工程(C)において形成された半導体層の表面上に
背面電極層を形成する工程<D>と、上記工程(D)に
おいて形成された背面電極層の表面上に上記基板と同等
の熱収縮特性を有し、且つ耐熱性及び可撓性を有する電
気絶縁層を形成する工程(E)と、
上記支持体を、エツチング処理により、上記の工程(A
)〜工程(E)を順に経て得られた可視性光電変換素子
から除去する工程(F)、
から構成されてなるものである。The method for manufacturing a flexible photoelectric conversion element according to the present invention includes a step (A) of forming a transparent plastic substrate having heat resistance, visibility, and electrical insulation on the surface of a support; and the step (A). ) A step (B) of laminating a transparent electrode layer on the surface of the substrate formed in step (B), and a step of forming a photovoltaic semiconductor layer on the surface of the transparent electrode layer formed in step (B) above. (C), a step <D> of forming a back electrode layer on the surface of the semiconductor layer formed in the above step (C), and a step <D> of forming a back electrode layer on the surface of the back electrode layer formed in the above step (D); Step (E) of forming an electrically insulating layer having heat shrinkage characteristics equivalent to that of , and having heat resistance and flexibility;
) to step (F) of removing it from the visible photoelectric conversion element obtained through steps (E) in this order.
つまり、本発明は可撓性光電変換素子の91遣方法につ
いてのものであるが、本発明において可撓性光電変換素
子とは、光を入力して電気を出力する光電変換素子であ
って可視性を有するものの総て含んでおり、具体的には
、光導電素子、ホトダイオード、太陽電池、ホトトラン
ジスタ、ホトサイリスク等を挙げることができる。また
、ここでいう光には、可視光線のみならず、赤外線及び
紫外線も含まれる。In other words, the present invention relates to a method for using a flexible photoelectric conversion element, and in the present invention, a flexible photoelectric conversion element is a photoelectric conversion element that inputs light and outputs electricity, and is visible. It includes everything that has properties, and specific examples include photoconductive elements, photodiodes, solar cells, phototransistors, and photocyclists. Furthermore, the light referred to here includes not only visible light but also infrared and ultraviolet rays.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においては、先ず、支持体の表面上に耐熱性、可
撓性及び電気絶縁性を有する透明プラスチック製の基板
を形成・する工程(A)を実施する。In the present invention, first, the step (A) of forming a transparent plastic substrate having heat resistance, flexibility, and electrical insulation properties on the surface of a support is carried out.
基板を構成する透明なプラスチックは、耐熱性、可撓性
及び電気絶縁性を有するものであれば特に限定されるも
のではなく、具体的な代表例としては、ポリニーチルサ
ル7オン
リエーテルイミド、4−メチルペンテンテレフタレート
等のフィルムを列挙することができる。The transparent plastic constituting the substrate is not particularly limited as long as it has heat resistance, flexibility, and electrical insulation properties, and typical examples include polynythiol 7-one etherimide, 4-methyl Films such as pentene terephthalate may be mentioned.
これらのうち、特に、次の一般式(1)又は(II)、
或いは(I)及び(II)によって表される繰り返し単
位を有するポリイミドを主成分とするポリイミドフィル
ムが耐熱性及び光透過性の面で良好であり特に推奨され
る。Among these, in particular, the following general formula (1) or (II),
Alternatively, a polyimide film mainly composed of polyimide having repeating units represented by (I) and (II) is particularly recommended since it has good heat resistance and light transmittance.
即ち、このポリイミドフィルムは、膜厚50±5μmの
ポリイミドフィルムに対する可視光線(500nLL1
)透過率が70%以上であって、黄色度(イエローイン
デックス)が40以下のものを+11う。That is, this polyimide film has a visible light (500nLL1
) If the transmittance is 70% or more and the yellow index is 40 or less, increase by +11.
尚、ここで主成分とするとは、全体が上記の一般式(1
)及び/又は(II)のみからなる場合も含める趣旨で
ある。It should be noted that the term "main component" as used herein means that the entire component corresponds to the above general formula (1
) and/or (II) only.
及び/又は
このような透明なポリイミドフィルム製の基板は、例え
ば、次のような工程により、支持体の表面上に優れた耐
熱性、可視性及び電気絶縁性を有する無色透明なポリイ
ミドフィルム製基板として形成される。And/or such a transparent polyimide film substrate can be prepared by, for example, producing a colorless transparent polyimide film substrate having excellent heat resistance, visibility, and electrical insulation on the surface of the support by the following process. is formed as.
即ち、このようなポリイミドフィルム製基板は、一般式
(I[)
で示されるビフェニルテトラカルボン酸二無水物と一般
式(IV)及び(V)
で表される芳香族ジアミノ化合物との反応によって得ら
れる。That is, such a polyimide film substrate is obtained by reacting biphenyltetracarboxylic dianhydride represented by the general formula (I[) with aromatic diamino compounds represented by the general formulas (IV) and (V). It will be done.
本工程(A)に用いられる支持体としては、亜鉛、錫、
銅及びアルミニウム等の金属やこれらを主成分とする合
金製の薄板或いは箔が使用される。The support used in this step (A) includes zinc, tin,
Thin plates or foils made of metals such as copper and aluminum or alloys containing these as main components are used.
この支持体の厚さとしては、強度やエツチングによる除
去の難易度等を考慮すると、5〜500μm、好ましく
は10〜300μmの範囲とするのが都合が良い。The thickness of this support is conveniently in the range of 5 to 500 .mu.m, preferably 10 to 300 .mu.m, considering the strength and the difficulty of removal by etching.
これらのうち、連続的に各工程の処理を行うには、アル
ミニウム又は銅製の金属箔が最も適している。Among these, aluminum or copper metal foil is most suitable for performing each process continuously.
この場合、アルミニウム箔の厚さとしては5〜500μ
m、特に10〜300μmの範囲とするのが好ましく、
又、銅箔の厚さとしては5〜500μ糟、特に10〜3
00μm の範囲とするのが望ましい。In this case, the thickness of the aluminum foil is 5 to 500 μm.
m, particularly preferably in the range of 10 to 300 μm,
In addition, the thickness of the copper foil is 5 to 500 μm, especially 10 to 3 μm.
It is desirable to set it in the range of 00 μm.
このように、支持体として銅箔及びアルミニツム箔を用
いたとき、その厚みが、厚過ぎると各工程を連続的に処
理したり或いは最終工程での支持体のエツチングが困難
になる。As described above, when copper foil or aluminum foil is used as a support, if the thickness is too thick, it becomes difficult to carry out each step continuously or to etch the support in the final step.
一方、あまり薄過ぎると、支持体としての剛性が欠け、
基板の形成後及び半導体層形成の際に、カールが発生す
る。On the other hand, if it is too thin, it will lack the rigidity as a support.
Curling occurs after forming the substrate and during forming the semiconductor layer.
尤も、室温で基板が内側にカールしていても、半導体層
形成温度(例えばグロー放電法では非晶質シリコンの堆
積に都合のよい250°C程度)で、基板層が熱膨張し
て、カールが矯正されるように調整するのが望ましく、
支持体上に塗工された基板形成用の樹脂溶液(例えば、
ポリイミド前駆体溶液)を用いて形成するための温度と
、半導体層堆積(形成)温度を近付けておくことは非常
に有利である。However, even if the substrate curls inward at room temperature, the substrate layer will thermally expand and curl at the semiconductor layer formation temperature (for example, around 250°C, which is convenient for depositing amorphous silicon in the glow discharge method). It is desirable to make adjustments so that the
A resin solution for forming a substrate coated on a support (for example,
It is very advantageous to keep the temperature for formation using a polyimide precursor solution and the semiconductor layer deposition (formation) temperature close to each other.
常温においては、ロール状に巻いておいたり、テンショ
ンをかけることで強制的にカールを防止することができ
る。At room temperature, curling can be forcibly prevented by winding it into a roll or applying tension.
尚、本工程(A)の後、後述する工程(B)に先立って
ホーニング処理、化学処理等により、透明プラスチック
製の基板の表面を凹凸形状に処理しておくと、この面で
の入射光の乱反射を誘起し反射の軽減と、半導体層での
光路の拡大に有利であり、このため、光電変換効率が向
上するので有利である。Note that after this step (A) and prior to step (B) described later, if the surface of the transparent plastic substrate is processed to have an uneven shape by honing, chemical treatment, etc., the incident light on this surface will be This is advantageous in inducing diffuse reflection of light, reducing the reflection, and expanding the optical path in the semiconductor layer, which is advantageous in improving photoelectric conversion efficiency.
又、上記透明ポリイミド前駆体やその溶液中に予めシリ
カ粉、炭酸カルシウム粉、ケイ酸カルシウム粉を添加し
ておくと、製膜後にこれらの粒子によって表面に凹凸が
形成され、これによって、入射光の乱反射を誘起させる
ことができる。Furthermore, if silica powder, calcium carbonate powder, or calcium silicate powder is added to the transparent polyimide precursor or its solution in advance, these particles will form irregularities on the surface after film formation, which will prevent incident light from entering. can induce diffuse reflection.
上記工程(A)において形成された基板の表面上に透明
電極層を積層する工程(B)を実施する。A step (B) of laminating a transparent electrode layer on the surface of the substrate formed in the above step (A) is performed.
この工程(B)においては、上記基板の上に透明電極層
がスパッタリング、蒸着、印刷等の方法によって形成さ
れる。In this step (B), a transparent electrode layer is formed on the substrate by a method such as sputtering, vapor deposition, or printing.
透明電極層の厚さは、特に限定されるものではないが、
例えば、500〜5000人程度にすれば入熱。透明電
極層の厚さが薄くなりすぎると所望の導電性(表面抵抗
が1000Ω/口以下)が得られなくなるので好ましく
なく、一方、厚くなり過ぎると透明電極層の透明性が低
下する恐れが生ずるので好ましくない。The thickness of the transparent electrode layer is not particularly limited, but
For example, if there are 500 to 5,000 people, there will be a lot of heat. If the thickness of the transparent electrode layer becomes too thin, the desired conductivity (surface resistance of 1000 Ω/mouth or less) cannot be obtained, which is undesirable.On the other hand, if it becomes too thick, the transparency of the transparent electrode layer may decrease. So I don't like it.
尚、複数のセルを1枚の基板上に形成する場合等には、
例えば、7オトエツチング等の手法により透明電極の不
要部分が除去される。In addition, when forming multiple cells on one substrate,
For example, unnecessary portions of the transparent electrode are removed by a technique such as 7-etching.
透明電極層は、公知の材質のものを使用すればよく、例
えば、酸化錫、酸化インジウム、或いは両者の固溶体(
ITO)等で構成される。The transparent electrode layer may be made of a known material, such as tin oxide, indium oxide, or a solid solution of both (
ITO), etc.
本発明においては、上記工程(B)において形成された
基板上における透明電極層の表面上に光起電性を有する
半導体層を形成する工程(C)を実施する。In the present invention, a step (C) of forming a photovoltaic semiconductor layer on the surface of the transparent electrode layer on the substrate formed in the step (B) is performed.
この工程(C)においては、上記工程(B)で得られた
積層シートを移送しつつ連続的に半導体層を形成しても
よいが、積層シートを裁断してその−枚づつに半導体層
を形成してもよいのである。In this step (C), the semiconductor layer may be continuously formed while transporting the laminated sheet obtained in the above step (B), but the laminated sheet may be cut and the semiconductor layer formed one by one. It may be formed.
上記半導体層を構成する半導体は、光起電性を有するも
のであれば特に限定されず、例えば、赤外線用のデルマ
ニウム(G e)、セレン(Se)、インジウムアンチ
モン(InSb)、X線、γ線及び可視光線用の硫化カ
ドミウム(CdS)、セレン化カドミウム(CclSe
)、可視光線用のシリコン(S i)等が例として挙げ
られる。The semiconductor constituting the semiconductor layer is not particularly limited as long as it has photovoltaic properties, and examples include infrared ray derma (Ge), selenium (Se), indium antimony (InSb), Cadmium sulfide (CdS), cadmium selenide (CclSe) for radiation and visible light.
), silicon for visible light (S i ), etc. are listed as examples.
又、これら半導体には、活性不純物として、塩化カドミ
ウム(CdCN2)、塩化銅(CuC12)や銀の塩類
を使用することは自由である。Furthermore, cadmium chloride (CdCN2), copper chloride (CuC12), and silver salts may be freely used as active impurities in these semiconductors.
例えば、p形弁晶質シリコン、 i形弁晶質シリコン及
びn形弁晶質シリコンを順次堆積することが半導体層の
薄膜化を図る上で有利である。For example, it is advantageous to deposit p-type valvate silicon, i-type valvate silicon, and n-type valvate silicon in sequence in order to reduce the thickness of the semiconductor layer.
又、p形弁晶質シリコン層、 l形弁晶質シリコン層及
びn形弁晶質シリコン層を順次堆積する方法として、グ
ロー放電法、光CVD法等の各種の方法を採用しうる。Furthermore, various methods such as a glow discharge method and a photo-CVD method can be employed to sequentially deposit the p-type valvus silicon layer, the l-type valvate silicon layer, and the n-type valvate silicon layer.
例えば、グロー放電法を採用する場合を例に採って具体
的に説明すれば、温度250℃前後(200〜350℃
)に加熱されたホルダーに透明電極層を形成した基板を
保持し、真空度0.2Torr程度において、水素で1
0モル%程度に希釈したシランと水素で5+000pρ
m程度に希釈したジボランの混合気[B2H6/ (S
iH4+ B2H6)= 0.1〜0.6モル%、好
ましくは06363モル%程を全流量11003CC流
入させ、その雰囲気の下で、上記ホルダーを一方の電極
とし、これに対する対極との間に13.56MHz、I
OW程度の高周波電力を印加して上記透明電極層上にほ
う素をドープしたp形弁晶質シリコン層を厚さ200人
にわたって堆積させる。For example, if we take the case of adopting the glow discharge method as an example and explain it specifically, the temperature will be around 250℃ (200~350℃).
) The substrate on which the transparent electrode layer was formed was held in a holder heated to
5+000 ppr with silane and hydrogen diluted to about 0 mol%
A mixture of diborane diluted to about m [B2H6/ (S
iH4+ B2H6) = 0.1 to 0.6 mol%, preferably about 06363 mol%, is injected at a total flow rate of 11003 CC, and in that atmosphere, the holder is used as one electrode, and 13. 56MHz, I
A p-type crystalline silicon layer doped with boron is deposited to a thickness of 200 mm on the transparent electrode layer by applying high frequency power of approximately OW.
引き続いて、水素希釈シランのみを全流量11008C
Cで導入した雰囲気の下で、上記と同様にして/ンドー
プの i形弁晶質シッフン層を17さ4500人にわた
って堆積させ、更に、水素希釈シランと水素で5,00
0ppmに希釈した7オスフイン(PH3)の混合気[
P H3/ (S iH−+ P Hz)= 01〜0
.6モル%、好ましくは0.3モル%]を全流量110
08CCで導入した雰囲気の下で同様にしてリンでドー
プしたn形弁晶質シリコン層を厚さ500人にわたって
堆積させる。Subsequently, only hydrogen diluted silane was added at a total flow rate of 11008C.
An undoped i-type crystalline Schiffen layer was deposited in the same manner as described above under the atmosphere introduced at C, and further deposited with hydrogen-diluted silane and hydrogen for 5,000 nm.
A mixture of 7 osphin (PH3) diluted to 0 ppm [
P H3/ (S iH-+ P Hz) = 01~0
.. 6 mol%, preferably 0.3 mol%] at a total flow rate of 110
A phosphorus-doped n-type crystalline silicon layer is similarly deposited to a thickness of 500 nm under the atmosphere introduced in 08CC.
ところで、便宜上、光起電性を有する半導体層としてp
−1−n型の非晶質シリコンの例で説明してきたが、
p層には非晶質シリ°コン以外にp型非晶質炭化ケイ素
(膜組成を5ixC,−xで示すと、X=0.6〜0.
95、望ましくはx=0.8程度で、ノボランB2H,
等でドープした膜)も使用できる。 この場合、炭化源
としては、メタンやエタン等の飽和炭化水素やエチレン
、プロピレン等の不飽和炭化水素が用いられる。By the way, for convenience, p is used as a photovoltaic semiconductor layer.
-1-Although we have explained using the example of n-type amorphous silicon,
In addition to amorphous silicon, the p layer contains p-type amorphous silicon carbide (the film composition is 5ixC, -x, where X=0.6 to 0.
95, preferably with x=0.8 or so, noborane B2H,
membranes doped with etc.) can also be used. In this case, the carbonization source used is a saturated hydrocarbon such as methane or ethane, or an unsaturated hydrocarbon such as ethylene or propylene.
原料ガスとして用いられるシラン(S iH4)やジシ
ラン(Si28s)と上記の炭化水素類のモル比は、下
記の如く決定される。The molar ratio of silane (S iH4) or disilane (Si28s) used as the raw material gas and the above-mentioned hydrocarbons is determined as follows.
即ち、例えば膜組成S io、sCo、2の膜を製する
には、S i H+とCH,のモル比0.8N0.2(
又、5i2HaとCH,では0.4対0.2)、SiH
,とC2H6では0.8対0.1、Si2HgとC2H
,では0.4対o、iの如く、原料ガスのSi原子数と
C原子数よりモル比が決定される。That is, for example, to produce a film with a film composition of S io, sCo, 2, the molar ratio of S i H+ and CH, 0.8N0.2 (
Also, 5i2Ha and CH, 0.4 vs. 0.2), SiH
, and 0.8 vs. 0.1 for C2H6, Si2Hg and C2H
, the molar ratio is determined from the number of Si atoms and the number of C atoms in the source gas, such as 0.4 to o, i.
本発明では、かくして得られた半導体層上に更に背面電
極層が積層される工程(D)を実施する。In the present invention, a step (D) is performed in which a back electrode layer is further laminated on the semiconductor layer thus obtained.
上記背面電極層は、基板と半導体層との間に積層されて
いる透明電極層と同様に酸化錫、酸化インジウム、或い
は両者の固溶体(ITO)等で61成してもよく、また
、アルミニウム、ニッケル、チタン、クロム、鉄、ステ
ンレス鋼、ニッケルクロム等の金属で構成してもよい。The back electrode layer may be made of tin oxide, indium oxide, or a solid solution of both (ITO), etc., like the transparent electrode layer laminated between the substrate and the semiconductor layer, and may also be made of aluminum, It may be made of metal such as nickel, titanium, chromium, iron, stainless steel, nickel-chromium, or the like.
背面電極層は印刷法、スパッタリング法、蒸着法等の方
法で形1′#、される。例えば蒸着法による場合であれ
ば、10−4〜ITorrの真空中で、蒸着源の温度は
使用される材料の融点付近という条件の下で行なわれる
。The back electrode layer is formed into a shape 1'# by a method such as a printing method, a sputtering method, or a vapor deposition method. For example, in the case of a vapor deposition method, it is carried out in a vacuum of 10<-4> to I Torr under the condition that the temperature of the vapor deposition source is near the melting point of the material used.
背面電極層の膜厚は特に限定されないが、可撓性光電変
換素子全体の可撓性を者しく低下させない範囲で且つ所
要の導電性を有するに足る膜厚以上であることが必要で
あり、例えば、アルミニウム背面電極層の場合であれば
0.1μm程度が適当とされる。The thickness of the back electrode layer is not particularly limited, but it needs to be within a range that does not significantly reduce the flexibility of the entire flexible photoelectric conversion element and is at least thick enough to have the required conductivity. For example, in the case of an aluminum back electrode layer, approximately 0.1 μm is considered appropriate.
このようにして、支持体に耐熱性、可撓性及び電気J8
縁性を有する透明プラスチック製の基板上に透明電極層
、p形−1形−n形弁晶質シリコンからなる半導体層及
び背面電極層を積層した充電変換素子(太陽電池)が形
成される。In this way, the support has heat resistant, flexible and electric J8
A charge conversion element (solar cell) is formed by laminating a transparent electrode layer, a semiconductor layer made of p-type-1-n-type valve crystalline silicon, and a back electrode layer on a substrate made of transparent plastic.
この場合、支持体を透明な素材で形成している場合には
、この段階で支持板側から光を入射させて充電変換素子
の特性を評価することができる。In this case, if the support is made of a transparent material, the characteristics of the charge conversion element can be evaluated by allowing light to enter from the support plate side at this stage.
本発明においては、次に、上記工程(D)においで形成
された背面電極層の表面上に上記基板と同等の熱収縮性
を有し、゛且つ耐熱性及び可撓性を有する電気絶縁層を
形成する工程(E)を実施する。In the present invention, next, on the surface of the back electrode layer formed in the above step (D), an electrical insulating layer having heat shrinkability equivalent to that of the above substrate, and having heat resistance and flexibility is provided. Step (E) of forming is carried out.
本発明の可撓性光電変換素子の製造方法において、重要
な特徴の一つは、上記工程(A)から工程(Il!l)
を経て積層された背面電極層上に電極端子取付は用スペ
ースを除き更に電気絶縁層が積層される点にある。In the method for manufacturing a flexible photoelectric conversion element of the present invention, one of the important features is that from the above step (A) to the step (Il!l)
An electrical insulating layer is further laminated on the back electrode layer laminated through the steps except for the space for electrode terminal attachment.
この電気絶縁層は、電気絶縁性、耐熱性及び可視性を有
するものであり、しかも、基板と同等の熱収縮特性を有
することが必要である。This electrical insulating layer must have electrical insulation, heat resistance, and visibility, and must also have heat shrinkage characteristics equivalent to those of the substrate.
この電気絶縁層は、a述するように、これと半導体Mと
の熱収縮率の差異によって、基板と半導体層との熱収縮
率の差異によるカールを打ち消す方向にカールさせる応
力を発生させるためのものである。As described in a, this electrical insulating layer generates stress that curls in a direction that cancels the curl caused by the difference in thermal contraction rate between the substrate and the semiconductor layer due to the difference in thermal contraction rate between this and the semiconductor M. It is something.
即ち、例えば、半導体層がp形−1形−n形弁晶質シリ
コン層で構成されている場合を例にとれば、熱収縮率の
差異から生じる可撓性光電変換素子或いは半導体層のカ
ールの曲率半径が40av+よりも小さくなれば半導体
層内に亀裂が発生するので、基板の熱膨張係数をαい電
気絶縁層の熱膨張係数をα2、基板の厚さと電気絶縁層
の厚さの和をh(IIlm)、非晶質シリコン堆積温度
と室温との温度差を八Tい電気絶縁層形成温度と室温と
の温度差をΔT2とすると、
を満足することが必要とされる。That is, for example, in the case where the semiconductor layer is composed of a p-type-1-n-type crystalline silicon layer, curling of the flexible photoelectric conversion element or the semiconductor layer due to the difference in thermal shrinkage rate may occur. If the radius of curvature of becomes smaller than 40av+, cracks will occur in the semiconductor layer, so the coefficient of thermal expansion of the substrate is α, the coefficient of thermal expansion of the electrically insulating layer is α2, the sum of the thickness of the substrate and the thickness of the electrically insulating layer. If h(IIlm) is h(IIlm), the temperature difference between the amorphous silicon deposition temperature and room temperature is 8T, and the temperature difference between the electrical insulating layer formation temperature and room temperature is ΔT2, then it is necessary to satisfy the following.
最も好ましくは、基板と電気絶縁層とを全く同じ材質で
同じ形状及び寸法(同じ厚さ)に形成することである。Most preferably, the substrate and the electrical insulating layer are made of exactly the same material and have the same shape and size (same thickness).
例えば、基板を形成するときと同様のポリイミド前駆体
の溶液を背面電極層上に同様の厚さに流延して皮膜を形
成し、熱風乾燥してイミド化反応を完全に行うことによ
り、電気絶縁性、耐熱性及び可撓性を有し、しかも、基
板と同等の熱収縮特性を有する電気絶1&層を形成する
ことができる。For example, by casting the same polyimide precursor solution as when forming the substrate onto the back electrode layer to form a film and drying it with hot air to completely carry out the imidization reaction, it is possible to It is possible to form an electrically insulating layer 1&layer that has insulation, heat resistance, and flexibility, and also has heat shrinkage characteristics equivalent to that of the substrate.
本発明においては、最後に、支持体を、エツチング処理
により、上記の工程(A)〜(E)を経て得られた可視
性光電変換素子から除去する工程(F)を実施する。In the present invention, finally, a step (F) is performed in which the support is removed from the visible photoelectric conversion element obtained through the above steps (A) to (E) by etching treatment.
この工程(F)は上記各工程を経て形成された可撓性光
電変換素子から支持体を、エツチング処理により除去す
ることにより、透明電極層、半導体層及び背面電極層が
透明電極層側の透明プラスチック製の基板と背面電極側
の電気絶縁層とで挟まれた積層構造の可撓性光導電性素
子が得られる。In this step (F), the support is removed from the flexible photoelectric conversion element formed through the above steps by etching treatment, so that the transparent electrode layer, the semiconductor layer, and the back electrode layer are transparent on the transparent electrode layer side. A flexible photoconductive element having a laminated structure sandwiched between a plastic substrate and an electrically insulating layer on the back electrode side is obtained.
かくして得られた可撓性光電変換素子は電気絶縁層の形
成によって、そのカールが防止されるのである。The thus obtained flexible photoelectric conversion element is prevented from curling by forming the electrically insulating layer.
本発明の製造方法では、エツチング処理、つまり化学的
に支持体を除去する点に最も大きな特徴を有するが、こ
のエツチング処理の条件としては通常、fA箔やアルミ
ニウム箔をエツチングするための条件が選択、使用され
る。例えば、塩化第二鉄や塩化銅、過疎゛酸アンモニウ
ム等の酸性のエツチング液やアンモニウム塩更にアンモ
ニア系錯体等のアルカリ性のエツチング液をスプレィ式
エツチャーを用いて吹′き付けたり、このエツチング液
に浸漬したりして支持体を除去することができるのであ
る。The manufacturing method of the present invention has the greatest feature in etching treatment, that is, chemically removing the support, and the conditions for this etching treatment are usually those for etching fA foil or aluminum foil. ,used. For example, an acidic etching solution such as ferric chloride, copper chloride, or ammonium superphosphate, or an alkaline etching solution such as an ammonium salt or an ammonia complex may be sprayed onto the etching solution using a spray etcher. The support can be removed by immersion.
(e)作用
以上のように、本発明は、透明電極層、半導体層及び背
面電極層が透明電極層側の透明プラスチック製の基板と
背面電極層側の電気絶縁層とで挟まれた積層構造の可撓
性光電変換素子のv1造方法であり、かくして得られた
可撓性光電変換素子は高温で形成された後、常温に冷却
したときに、その充電変換素子を熱膨張係数が大きい基
板側にカールさせようとする熱収縮力が内部に発生する
のに対して、該基板と熱膨張係数がほぼ同じ電気絶縁層
を背面電極層を介して半導体層と高温で接合させること
により、常温に冷却したときに、その光電変換素子を熱
膨張係数が大きい電気絶縁層側にカールさせようとする
熱収縮力が内部に発生する。(e) Function As described above, the present invention has a laminated structure in which a transparent electrode layer, a semiconductor layer, and a back electrode layer are sandwiched between a transparent plastic substrate on the transparent electrode layer side and an electrical insulating layer on the back electrode layer side. V1 manufacturing method for a flexible photoelectric conversion element, in which the thus obtained flexible photoelectric conversion element is formed at a high temperature, and then when cooled to room temperature, the charge conversion element is attached to a substrate with a large coefficient of thermal expansion. In contrast to the internal thermal contraction force that tends to curl the substrate, by bonding the electrical insulating layer, which has almost the same coefficient of thermal expansion as the substrate, to the semiconductor layer via the back electrode layer at a high temperature, When the photoelectric conversion element is cooled down, a thermal contraction force is generated inside the photoelectric conversion element that tends to curl it toward the electrical insulating layer having a large coefficient of thermal expansion.
そしてこれらの相反する方向に可視性光電変換素子をカ
ールさせようとする熱収縮力が互いに打ち消し合う結果
、可撓性光電変換素子をカールさせようとする見掛は上
の熱収縮力が減少ないし渭滅し、可撓性光電変換素子の
カールの発生が防止される作用を有するのである。As a result of these thermal contraction forces trying to curl the visible photoelectric conversion element in opposite directions canceling each other out, the apparent thermal contraction force trying to curl the flexible photoelectric conversion element does not decrease. This has the effect of preventing curling of the flexible photoelectric conversion element.
又、本発明の光電変換素子の製造方法によると、上記の
カール発生を防止した光電変換素子を製造するにあたり
適度にバランスある剛性の支持体を選択して用い、これ
をロール状に巻回し、これを連続的に繰り出しつつ可視
性光電変換素子の製造が可能であり、又、この製造工程
中にカールの発生が防止され、優れた充電変換効率を有
し、しがも信頼性が高い可視性光電変換素子が得られる
作用を有するのである。Further, according to the method for producing a photoelectric conversion element of the present invention, in order to produce the photoelectric conversion element that prevents the occurrence of curling, a support having a suitably balanced rigidity is selected and used, and this is wound into a roll. It is possible to manufacture a visible photoelectric conversion element by continuously rolling out this element, and it also prevents the occurrence of curling during this manufacturing process, has excellent charge conversion efficiency, and is capable of producing highly reliable visible photoelectric conversion elements. This has the effect of providing a photoelectric conversion element with a high level of photovoltaic properties.
また、本発明の製造工程は、特に、機械的に支持体を剥
離するのではなく、化学的に除去するものであるから、
支持体の除去の際に歪みが生じたり、機械的応力によっ
て光電変換素子本体に損傷を与えることなく、支持体を
除去しうる作用を有するのである。In addition, the manufacturing process of the present invention does not involve mechanically peeling off the support, but chemically removing it.
This has the effect of allowing the support to be removed without causing distortion or damaging the photoelectric conversion element body due to mechanical stress during removal of the support.
(f)実施例
以下、本発明を実施例に基づき詳細に説明するが、本発
明はこれに限定されるものではない。(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
実施例1
溶媒としてN、N−ツメチルアセトアミドを用い、39
3’−97ミノジフエニルスル7オン!に対し、3.3
’4.4’−ビフェニルテトラカルボン酸二無水物を1
mo1反応させポリイミド前駆体の溶液を得た。この
溶液を厚み90μmのロール状銅箔からなる支持体上に
キャスティングして皮膜を連続的に形成し、この皮膜を
熱風乾燥し、更に温度300°Cで1時間加熱してイミ
ド化反応を完全に行い、上記支持体上に厚み50μmの
ポリイミドフィルムよりなる透明なプラスチック製の基
板を形成した。Example 1 Using N,N-trimethylacetamide as a solvent, 39
3'-97minodiphenylsul7one! For 3.3
'4.4'-biphenyltetracarboxylic dianhydride 1
A mo1 reaction was carried out to obtain a solution of a polyimide precursor. This solution was cast onto a support made of rolled copper foil with a thickness of 90 μm to form a film continuously, and this film was dried with hot air and further heated at 300°C for 1 hour to complete the imidization reaction. A transparent plastic substrate made of a polyimide film having a thickness of 50 μm was formed on the support.
このフィルムの光線透過率(波長5 0 0 nm)は
85%であって、黄色度(イエローインデックス)が2
5であった。The light transmittance (wavelength: 500 nm) of this film is 85%, and the degree of yellowness (yellow index) is 2.
It was 5.
次に、上記支持体の付いたままの透明ポリイミドフィル
ム基板の表面に、スパッタリング法によって厚み600
人のITOからなる透明電極層を連続的に設け、この透
明電極層付きの基板を、内部電極型の高周波(1 3.
5 6MHz)グロー放電装置内のヒーター付きホルダ
ーに保持し、温度250℃前後に保持した後、水素で1
0モル%に希釈したシランと、水素で5,000ppm
に希釈したノボランを混合[B 2H a/ (S i
H 4+ B 2H g)= 0 。Next, a film with a thickness of 600 mm was coated on the surface of the transparent polyimide film substrate with the support still attached by sputtering.
A transparent electrode layer made of ITO was continuously provided, and the substrate with the transparent electrode layer was subjected to an internal electrode type high frequency wave (13.
5 6MHz) It is held in a holder with a heater in a glow discharge device, and after keeping the temperature around 250℃, it is heated with hydrogen.
Silane diluted to 0 mol% and 5,000 ppm hydrogen
Mix noborane diluted to [B 2H a/ (S i
H 4+ B 2H g) = 0.
3モル%]し、これを全流量として100SCCMグロ
ー放電装置内に導入し、真空度0,2Torrの雰囲気
下でIOWの高周波電力を印加して該基盤上にほう素を
ドープした200人のp形弁晶質シリコン層を設けた。3 mol%] was introduced into a 100SCCM glow discharge device as a total flow rate, and high frequency power of IOW was applied in an atmosphere with a degree of vacuum of 0.2 Torr to form a sample of 200 people doped with boron on the substrate. A crystalline silicon layer was provided.
引き続いて、上記の水素希釈シランのみを導入し、同様
に反応を行い、上記p形弁晶質シリコン層の上にノンド
ープで厚み4500人の i形弁晶質シリコン薄膜を堆
積し、更に水素希釈シランと、水素で5,000ppm
に希釈した7オスフイン(PH3)を混合EP Hs/
(S rH − 十P H z)= 0 、 5モ
ル%1し、グロー放電装置内に全流量1008CCM導
入してi形弁晶質シリコン薄膜にリンをドープした50
0人のn形弁晶質シリコン薄膜を形成した。。Subsequently, only the above hydrogen-diluted silane was introduced and a similar reaction was carried out to deposit a non-doped I-type valvous silicon thin film with a thickness of 4500 nm on the above-mentioned p-type valvate silicon layer, and further hydrogen dilution was performed. 5,000ppm of silane and hydrogen
EP Hs/
(S rH − 10 P Hz) = 0, 5 mol% 1, and a total flow rate of 1008 CCM was introduced into the glow discharge device to dope the i-type crystalline silicon thin film with phosphorus.
An n-type crystalline silicon thin film was formed. .
即ち、無色透明のポリイミドフィルム製基板上に、IT
Oの導電性薄膜を介して、n形−n形−n形の非晶質シ
リコン薄膜から成る光導電性を有する半導体層を形成し
た。That is, IT is placed on a colorless and transparent polyimide film substrate.
A photoconductive semiconductor layer consisting of an n-type-n-n-type amorphous silicon thin film was formed via an O conductive thin film.
次に、これを真空蒸着装置内に保持し、通常の蒸着法に
よって、n形弁晶質シリコン薄膜上に厚み0.1μmの
アルミニウム製背面電極層を積層した。Next, this was held in a vacuum evaporation apparatus, and an aluminum back electrode layer having a thickness of 0.1 μm was laminated on the n-type crystalline silicon thin film by a normal evaporation method.
次に、支持体を付けたまま背面電極層上に電極端子部分
を除き基板用のポリイミド前駆体溶液と同様のポリイミ
ド前駆体の溶液を、基板と同様の厚みになるように流延
して皮膜形成し、熱風乾燥し、更に温度200℃で5時
間加熱して完全にイミド化を行うことにより、電気絶縁
層を形成した。Next, with the support still attached, a polyimide precursor solution similar to the polyimide precursor solution for the substrate is cast on the back electrode layer, except for the electrode terminal portion, to a thickness similar to that of the substrate. An electrical insulating layer was formed by forming, drying with hot air, and further heating at a temperature of 200° C. for 5 hours to completely imidize.
更に、これを40℃の塩化第二鉄系エツチング液でスプ
レィしてエツチングすることにより支持体を除去し、基
板、透明電極層、半導体層、背面電極層及び電気絶縁層
からなる可撓性の光電変換素子を得た。Further, the support was removed by spraying and etching with a ferric chloride-based etching solution at 40°C, and a flexible structure consisting of the substrate, transparent electrode layer, semiconductor layer, back electrode layer, and electrical insulating layer was formed. A photoelectric conversion element was obtained.
このようにして得られた可撓性光電変換素子は外観上全
くフラットでカールは生じなかった。The flexible photoelectric conversion element thus obtained had a completely flat appearance and no curling occurred.
この光電変換効率は4.1%であった。This photoelectric conversion efficiency was 4.1%.
又、この受光素子は可視性があり、曲率半径4cmに湾
曲させても光電変換効率の低下は認められなかった。Further, this light receiving element was visible, and no decrease in photoelectric conversion efficiency was observed even when it was curved to a radius of curvature of 4 cm.
実施例2
実施例1のn形弁晶質シリコン層膜上にアルミニウム製
の背面電極層を形成した可撓性光電変換素子半製品につ
いて、この背面電極層側に、下記の配合比のエポキシ樹
脂をアプリケータにより厚み50μmになるように塗工
した。Example 2 Regarding the flexible photoelectric conversion element semi-finished product in which an aluminum back electrode layer was formed on the n-type crystalline silicon layer of Example 1, an epoxy resin having the following compounding ratio was applied to the back electrode layer side. was applied to a thickness of 50 μm using an applicator.
配合比
ビスフェノールA型エポキシ樹脂 60部(油化
シェルエポキシ(株)エビコー)828)1.6−ヘキ
サノオールジグリシジルエーテル12部
(板本薬品(株)SR−16H)
可撓性エポキシ樹m s部(板
本薬品(株)SR−PTMG)
芳香族アミン 20部(板本
薬品(株)SDA−07)
次に、これを、温度90℃で2時間予備的に熱風乾燥し
た後、更に、温度150℃に設定した熱風乾燥器中に保
ち、3時間加熱しエポキシ層を硬化させて電気絶縁層を
形成したのち、同様に支持体をエツチング除去して得ら
れた可撓性充電変換素子は外観上全くフラットでカール
は生じなかった。Compounding ratio Bisphenol A type epoxy resin 60 parts (Yuka Shell Epoxy Co., Ltd., Ebiko Co., Ltd.) 828) 1.6-hexanool diglycidyl ether 12 parts (Itamoto Yakuhin Co., Ltd. SR-16H) Flexible epoxy resin m s part (Itamoto Pharmaceutical Co., Ltd. SR-PTMG) Aromatic amine 20 parts (Itamoto Pharmaceutical Co., Ltd. SDA-07) Next, this was preliminarily dried with hot air at a temperature of 90°C for 2 hours, and then further A flexible charge conversion element obtained by keeping the epoxy layer in a hot air dryer set at a temperature of 150°C for 3 hours to harden the epoxy layer to form an electrical insulating layer, and then removing the support by etching in the same manner. The appearance was completely flat and no curls were observed.
また、この可撓性光電変換素子は4.0%であった。Moreover, the content of this flexible photoelectric conversion element was 4.0%.
更に、この可撓性光電変換素子を曲率半径4cmに湾曲
させても充電変換効率の低下は認められなかった。Further, even when this flexible photoelectric conversion element was curved to a radius of curvature of 4 cm, no decrease in charge conversion efficiency was observed.
比較例1
基板として、厚み50μmの従来から市販されているポ
リイミドフィルム(デュポン社製、商品名:カプトンH
)を使用し、これを温度110℃、30分間乾燥後、ス
パッタリング装置内に保ち、片面上に厚み1000人の
ステンレス鋼製背面電極層を形成した。Comparative Example 1 A conventional commercially available polyimide film (manufactured by DuPont, trade name: Kapton H) with a thickness of 50 μm was used as a substrate.
) was dried at a temperature of 110° C. for 30 minutes and then kept in a sputtering device to form a stainless steel back electrode layer with a thickness of 1000 μm on one side.
次に、実施例1で使用したのと同じグロー放電装置内に
これを保持し、温度250°Cに加熱すると、カールが
発生したので、フィルムを緊張下にて保持し、リンをド
ープしたE′Lさ500人のn形弁晶質シリコン層、ノ
ンドープで厚さ4,500人の i形弁晶質シリコン層
及びほう素をドープしr:、厚さ200人のp形弁晶質
シリコン層の各層の成長条件を実施例1と同様に行い、
且つ実施例1と同様の順序で形成した。Next, the film was held in the same glow discharge device as used in Example 1 and heated to a temperature of 250°C. Since curling occurred, the film was held under tension and the phosphorus-doped E A layer of n-type crystalline silicon with a thickness of 500 mm, an undoped I-type crystalline silicon layer with a thickness of 4,500 mm, and a p-type crystalline silicon layer doped with boron and a thickness of 200 mm. The growth conditions for each layer were the same as in Example 1,
In addition, they were formed in the same order as in Example 1.
しかし、このようにして背面電極層及び半導体層を結合
したフィルムを室温下で取り出すとポリイミドフィルム
を内側にして著しいカールが発生した。However, when the film in which the back electrode layer and the semiconductor layer were combined in this manner was taken out at room temperature, significant curling occurred with the polyimide film inside.
次に、実施例1で使用したのと同じスパッタリング装置
内にフィルムを緊張下に保ち、厚み600人のITOか
らなる透明電極層を p形弁晶質シリコン層上に形成し
た。Next, the film was kept under tension in the same sputtering apparatus used in Example 1, and a transparent electrode layer of 600 nm thick ITO was formed on the p-type crystalline silicon layer.
かくして得られた充電変換素子は、基板を内側にして者
しくカールしていた。The charge conversion element thus obtained was neatly curled with the substrate facing inside.
この光電変換素子を強制的に伸展させて光電変換効率の
測定を行ったところ、非晶質シリコン層で亀裂が発生し
、又、内部で断線しており、大部分のセルは光起電能力
を確認できなかった。When this photoelectric conversion element was forcibly stretched and the photoelectric conversion efficiency was measured, cracks occurred in the amorphous silicon layer and internal wires were broken, indicating that most of the cells had no photovoltaic ability. could not be confirmed.
断線を免れた一部の試料については変換効率は1.3〜
2.1%であった。For some samples that escaped disconnection, the conversion efficiency was 1.3~
It was 2.1%.
比較例2
実施例1のn形弁晶質シリコン薄膜上にアルミニウム製
背面電極層を形成した光電変換素子半製品(ガラス製支
持体付き半製品)について、この背面電極層側に、Fi
、さ75μ情のアクリル系粘着剤層を介して厚さ75μ
mのポリエチレンテレフタレートフィルムを張り合わせ
たのち、室温の水中に1時間浸漬し、支持体より剥離さ
せて光電変換素子を製作した。Comparative Example 2 Regarding the photoelectric conversion element semi-finished product (semi-finished product with glass support) in which an aluminum back electrode layer was formed on the n-type crystalline silicon thin film of Example 1, Fi
, 75μ thick through 75μ thick acrylic adhesive layer
After laminating a polyethylene terephthalate film of 300 m in size, the film was immersed in water at room temperature for 1 hour and peeled off from the support to produce a photoelectric conversion element.
このようにして得た光電変換素子は、曲率半径が3cm
′1′者しくカールしており、強制的にフィルムを伸ば
し充電変換効率の測定を行ったが、大部分のセルがa線
していた。The photoelectric conversion element thus obtained had a radius of curvature of 3 cm.
The film was curled in a strange way, and when the film was forcibly stretched and the charge conversion efficiency was measured, most of the cells were A-line.
実施例3
支持体として、厚み150μmのアルミニウム箔な用い
、実施例1と同じ条件で処理を行った。Example 3 The treatment was carried out under the same conditions as in Example 1, using an aluminum foil with a thickness of 150 μm as the support.
但し、ポリイミドフィルムの基板の形成と、IToから
なる透明電極層の形成は、ロール状で連続的に行ったが
、非晶質シリコン層の形成は、単板状で処理した。However, although the formation of the polyimide film substrate and the formation of the transparent electrode layer made of ITo were carried out continuously in the form of a roll, the formation of the amorphous silicon layer was carried out in the form of a single plate.
中間材料の積層物はグロー放電装置で処理するに先立っ
て、単板状に裁断したところ、強制力を解除すると、曲
率半径100cm程度にカールしたが、非晶質堆積温度
250°Cに加熱すると平坦状態になった。When the intermediate material laminate was cut into a single plate before being treated with a glow discharge device, it curled to a radius of curvature of about 100 cm when the force was released, but when heated to an amorphous deposition temperature of 250°C. It became flat.
以後、実施例1と同様の処理を行い、光電変換効率4%
でカールのない可撓性光電変換素子を得た。Thereafter, the same treatment as in Example 1 was performed, and the photoelectric conversion efficiency was 4%.
A curl-free flexible photoelectric conversion element was obtained.
(g)発明の効果
本発明は、透明電極層、半導体層及び背面電極層が透明
電極層側の透明プラスチック製の基板と背面電極層側の
電気絶縁層とで挟まれた積層構造の可撓性光電変換素子
の製造方法であり、可撓性光電変換素子を高温で形成し
た後、常温に冷却したとき、この光電変換素子を熱膨張
係数が大きい基板側にカールさせようとする熱収縮力が
内部に発生するのに対して、該基板と熱膨張係数がほぼ
等しい電気絶縁層がその熱収縮力を打ち消す方向に働く
結果、可撓性光電変換素子をカールさせようとする見掛
は上の熱収縮力が減少ないし消滅し、可撓性光電変換素
子のカールの発生が防止されるのであり、このため優れ
た光電変換効率を有し、しかも信頼性が高い可撓性光電
変換素子が得られる効果を有するのである。(g) Effects of the invention The present invention provides a flexible laminated structure in which a transparent electrode layer, a semiconductor layer, and a back electrode layer are sandwiched between a transparent plastic substrate on the transparent electrode layer side and an electrical insulating layer on the back electrode layer side. This is a method for manufacturing a flexible photoelectric conversion element, in which a flexible photoelectric conversion element is formed at high temperature and then cooled to room temperature, the thermal contraction force that tends to curl the photoelectric conversion element toward a substrate having a large coefficient of thermal expansion. occurs internally, whereas the electrical insulating layer, which has a coefficient of thermal expansion almost equal to that of the substrate, acts in a direction to cancel out the thermal contraction force, so that the appearance of curling the flexible photoelectric conversion element becomes worse. Thermal shrinkage force is reduced or eliminated, and curling of the flexible photoelectric conversion element is prevented. Therefore, a flexible photoelectric conversion element with excellent photoelectric conversion efficiency and high reliability can be produced. It has the effect that can be obtained.
又、本発明の可撓性光電変換素子の製造方法によると、
支持体をロール状に巻回し、これを連続的に繰り出しつ
つ可撓性光電変換素子の製造が可能であり、しかもこの
製造工程中に可撓性光電変換素子のカールの発生が防止
されるうえ、生産性を著しく向上させる効果、を有する
のである。Further, according to the method for manufacturing a flexible photoelectric conversion element of the present invention,
It is possible to manufacture a flexible photoelectric conversion element by winding the support into a roll and continuously unrolling the support, and moreover, it is possible to prevent curling of the flexible photoelectric conversion element during this manufacturing process. This has the effect of significantly improving productivity.
また、本発明の製造工程では、特に、支持体を機械的且
つ強制的に剥離、除去するのではなく、支持体を化学的
に除去するものであるから、支持体の除去の際に光電変
換素子本体に歪みが生じたり、機械的応力によって光電
変換素子本体に損傷が生じることがなく、この点からも
信頼性が高い可撓性光電変換素子が得られる効果を有す
るのである。In addition, in the manufacturing process of the present invention, the support is not mechanically and forcibly peeled off or removed, but is chemically removed, so photoelectric conversion is performed when the support is removed. There is no distortion in the element body or damage to the photoelectric conversion element body due to mechanical stress, and from this point of view as well, a highly reliable flexible photoelectric conversion element can be obtained.
Claims (5)
を有する透明プラスチック製の基板を形成する工程(A
)、 上記工程(A)において形成された基板の表面上に透明
電極層を積層する工程(B)、 上記工程(B)において形成された透明電極層の表面上
に光起電性を有する半導体層を形成する工程(C)、 上記工程(C)において形成された半導体層の表面に背
面電極層を形成する工程(D)、 上記工程(D)において形成された背面電極層の表面上
に上記基板と同等の熱収縮性を有し、且つ耐熱性及び可
撓性を有する電気絶縁層を形成する工程(E)、 上記支持体を、エッチング処理により、上記の工程(A
)〜工程(E)を経て得られた可撓性光電変換素子から
除去する工程(F)、 よりなる可撓性光電変換素子の製造方法。(1) Step of forming a transparent plastic substrate having heat resistance, flexibility and electrical insulation on the surface of the support (A
), a step (B) of laminating a transparent electrode layer on the surface of the substrate formed in the above step (A), a semiconductor having photovoltaic properties on the surface of the transparent electrode layer formed in the above step (B) a step (C) of forming a layer, a step (D) of forming a back electrode layer on the surface of the semiconductor layer formed in the above step (C), a step (D) of forming a back electrode layer on the surface of the back electrode layer formed in the above step (D); Step (E) of forming an electrically insulating layer having heat shrinkability equivalent to that of the substrate and having heat resistance and flexibility;
) to step (F) of removing from the flexible photoelectric conversion element obtained through step (E).
1項に記載の可撓性光電変換素子の製造方法。(2) The method for manufacturing a flexible photoelectric conversion element according to claim 1, wherein the support is an aluminum foil.
の可撓性光電変換素子の製造方法。(3) The method for manufacturing a flexible photoelectric conversion element according to claim 1, wherein the support is a copper foil.
許請求の範囲第2項に記載の可撓性光電変換素子の製造
方法。(4) The method for manufacturing a flexible photoelectric conversion element according to claim 2, wherein the aluminum foil has a thickness of 5 to 500 μm.
囲第3項に記載の可撓性光電変換素子の製造方法。(5) The method for manufacturing a flexible photoelectric conversion element according to claim 3, wherein the copper foil has a thickness of 5 to 500 μm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62277125A JPH01119072A (en) | 1987-10-31 | 1987-10-31 | Manufacture of flexible photoelectric conversion element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62277125A JPH01119072A (en) | 1987-10-31 | 1987-10-31 | Manufacture of flexible photoelectric conversion element |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01119072A true JPH01119072A (en) | 1989-05-11 |
Family
ID=17579140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62277125A Pending JPH01119072A (en) | 1987-10-31 | 1987-10-31 | Manufacture of flexible photoelectric conversion element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01119072A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5069727A (en) * | 1989-09-06 | 1991-12-03 | Sanyo Electric Co., Ltd. | Flexible photovoltaic device and manufacturing method thereof |
US5344501A (en) * | 1992-03-23 | 1994-09-06 | Canon Kabushiki Kaisha | Solar cell |
WO1999049483A1 (en) * | 1998-03-26 | 1999-09-30 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
-
1987
- 1987-10-31 JP JP62277125A patent/JPH01119072A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5069727A (en) * | 1989-09-06 | 1991-12-03 | Sanyo Electric Co., Ltd. | Flexible photovoltaic device and manufacturing method thereof |
US5344501A (en) * | 1992-03-23 | 1994-09-06 | Canon Kabushiki Kaisha | Solar cell |
WO1999049483A1 (en) * | 1998-03-26 | 1999-09-30 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
EP0948004A1 (en) * | 1998-03-26 | 1999-10-06 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
AU741400B2 (en) * | 1998-03-26 | 2001-11-29 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
JP2002508573A (en) * | 1998-03-26 | 2002-03-19 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing dye-containing photovoltaic cell |
US6613598B1 (en) | 1998-03-26 | 2003-09-02 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
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