JPH0249475A - Manufacture of amorphous silicon solar cell - Google Patents
Manufacture of amorphous silicon solar cellInfo
- Publication number
- JPH0249475A JPH0249475A JP1091576A JP9157689A JPH0249475A JP H0249475 A JPH0249475 A JP H0249475A JP 1091576 A JP1091576 A JP 1091576A JP 9157689 A JP9157689 A JP 9157689A JP H0249475 A JPH0249475 A JP H0249475A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous silicon
- substrate
- solar cell
- polyimide film
- support
- 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
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000000758 substrate Substances 0.000 claims abstract description 103
- 229920001721 polyimide Polymers 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000004642 Polyimide Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 206010040844 Skin exfoliation Diseases 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- -1 perfluoro group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000077 silane Inorganic materials 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 230000000306 recurrent effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 89
- 239000000243 solution Substances 0.000 description 19
- 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 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000007654 immersion 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
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- DCSSXQMBIGEQGN-UHFFFAOYSA-N 4,6-dimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C=C1N DCSSXQMBIGEQGN-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 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
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- Y02E10/548—Amorphous silicon PV cells
Landscapes
- Photovoltaic Devices (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（ａ）産業上の利用分野
本発明は基板として無色透明なポリイミドフィルムを用
い、該基板側から光を照射することにより、光劣化を抑
制して充電変換効率を向上させると共に、信頼性を向上
させた非晶質シリコン太陽電池の製造方法に関するもの
である。Detailed Description of the Invention (a) Industrial Application Field The present invention uses a colorless and transparent polyimide film as a substrate, and irradiates light from the substrate side to suppress photodeterioration and improve charge conversion efficiency. The present invention relates to a method of manufacturing an amorphous silicon solar cell that improves reliability.
（ｂ）従来の技術
非晶質シリコン太陽電池は、電卓・腕時計などの電子製
品の内蔵電源、テレビ・ラノオなどの外部電源および蓄
電池の放電を防ぐバッテリーチャーツヤなどの補助電源
として広く使用されているが、近年、極薄型電卓やレジ
ャーなどに用いる持ち運び容易な外部電源が要求される
ようになり、非晶質シリコン太陽電池の薄型化・軽量化
が必要となってきた。(b) Conventional technology Amorphous silicon solar cells are widely used as built-in power supplies for electronic products such as calculators and wristwatches, external power supplies for TVs and laptops, and auxiliary power supplies for battery chargers that prevent storage batteries from discharging. However, in recent years, there has been a demand for easily portable external power sources for use in ultra-thin calculators and leisure equipment, and there has been a need to make amorphous silicon solar cells thinner and lighter.
このような背景をもとに、非晶質シリコン太陽電池の基
板として従来の〃ラスに代えてアルミ、ステンレスなど
が検討されているか、より薄型化、軽量化及び７レキシ
プル化を付与することができることから高分子フィルム
製の基板が有望視されている。Based on this background, aluminum, stainless steel, etc. are being considered as a substrate for amorphous silicon solar cells instead of conventional lath, or it is possible to make them thinner, lighter, and more flexible. Substrates made of polymer film are seen as promising because of their ability to do so.
この高分子フィルム製基板としては、耐熱性が要求され
るため、一般にはカプトンに代表されるポリイミドフィ
ルムが使用されている。Since heat resistance is required for this polymer film substrate, a polyimide film typified by Kapton is generally used.
上記のようなポリイミドフィルムは光透過性が欠けるた
め、この種ポリイミドフィルムを非晶質シリコン太陽電
池の基板として用いる場合には第１図に示す構成をとる
必要がある。Since the above polyimide film lacks light transmittance, when this type of polyimide film is used as a substrate for an amorphous silicon solar cell, it is necessary to adopt the configuration shown in FIG. 1.
即ち、ポリイミドフィルム製基板（１）上に金属製の背
面電極層（２）を形成し、該背面電極層（２）上にｐ型
非晶質シリコン層（９層）（３）、真性非晶質シリコン
層（ｉ層）（４）、ｎ型非晶質シリコン層（１層）（５
）を順次積層し、該ｎ型非晶質シリコン層（１層）（５
）上に透明電極Ｍ（６）を形成し、更に、該透明電極層
（６）上に、表面保護用の透明樹脂層（７）が形成され
てなる。That is, a metal back electrode layer (2) is formed on a polyimide film substrate (1), and a p-type amorphous silicon layer (9 layers) (3) and an intrinsic non-crystalline silicon layer (3) are formed on the back electrode layer (2). Crystalline silicon layer (i layer) (4), n-type amorphous silicon layer (1 layer) (5
) are sequentially stacked to form the n-type amorphous silicon layer (1 layer) (5 layers).
), and a transparent resin layer (7) for surface protection is further formed on the transparent electrode layer (6).
この構成において、光は透明樹脂層（７）側から入り、
透明電極層（６）、ｎ層→ｉ層→ｐ層の非晶質シリコン
の順で光が透過する。この光の透過順序は、従来のガラ
ス製基板の場合と反対になり（ガラス製基板では光の透
過がｐｉ−４ｉ層→ｎ／ｌの順となる。）、これでは光
電変換効率の点で好ましくなく、また光劣化が大きく信
頼性に欠けることが知られている。一方、上記構造の太
陽電池において、非晶質シリコン層の形成順序を逆にし
て、光の入る順序をｐｍ−ｉ層→ｎｉとする試みもなさ
れているが、この場合には、非晶質シリコンの膜質を低
下させることが知られており、満足する特性が得られな
いのである。In this configuration, light enters from the transparent resin layer (7) side,
Light passes through the transparent electrode layer (6) and the amorphous silicon of the n-layer→i-layer→p-layer in this order. This order of light transmission is opposite to that of conventional glass substrates (in glass substrates, light transmission is in the order of the pi-4i layer → n/l layer), and this reduces the photoelectric conversion efficiency. This is not desirable and is known to suffer from significant photodeterioration and lack reliability. On the other hand, in solar cells with the above structure, attempts have been made to reverse the formation order of the amorphous silicon layers and change the order of light entry from the pm-i layer to the ni layer. It is known that it deteriorates the film quality of silicon, making it impossible to obtain satisfactory characteristics.
以上より、通常のポリイミドフィルム製基板を用いる場
合には、該基板に光透過性がないか、或いは光透過性が
乏しいために、基板側から光を入射することができず、
その反対側の透明樹脂層（７）から光を入射している。From the above, when using a normal polyimide film substrate, the substrate does not have light transmittance or has poor light transmittance, so light cannot enter from the substrate side.
Light is incident from the transparent resin layer (7) on the opposite side.
このような光の入れ方をするために、上述したように充
電変換効率及び光劣化に関して満足する特性が得られな
いのが実状である。Due to this method of inputting light, the actual situation is that satisfactory characteristics regarding charge conversion efficiency and photodeterioration cannot be obtained as described above.
このため、非晶質シリコン太陽電池の基板として無色透
明なポリイミドフィルムを用いることが提案されている
（特開昭６２−３６８８２号公報）。For this reason, it has been proposed to use a colorless and transparent polyimide film as a substrate for an amorphous silicon solar cell (Japanese Unexamined Patent Publication No. 62-36882).
この場合には、上記非晶質シリコン太陽電池と異なった
構成をとる。In this case, a configuration different from that of the amorphous silicon solar cell described above is adopted.
即ち、第２図に示すように、無色透明なポリイミドフィ
ルム製基板（８）上に透明電極Ｍ（６）を形成し、該透
明電極層（６）上に、ｐ型非晶質シリコンＮ（３）、ｎ
型非晶質シリコン層（４）、ｎ型非晶質シリコン層（５
）を順次積層し、該ｎ型非晶質シリコン層（５）上に金
属製の背面電極層（２）を形成し、更に、該背面電極層
（２）上に、表面保護用の樹脂Ｍ（９）が形成されてな
る。That is, as shown in FIG. 2, a transparent electrode M (6) is formed on a colorless and transparent polyimide film substrate (8), and p-type amorphous silicon N ( 3), n
type amorphous silicon layer (4), n-type amorphous silicon layer (5)
) are sequentially laminated, a metal back electrode layer (2) is formed on the n-type amorphous silicon layer (5), and a surface protection resin M is further formed on the back electrode layer (2). (9) is formed.
そして、この場合には、光が、透明ポリイミドフィルム
製基板側から入り、ｐｍ−４ｉ層→ｎ層の順で透過する
。この光の透過順序によると、第１図に示す、非晶質シ
リコン太陽電池において同居であった光電変換効率の低
下や光劣化がなくなり、高性能の７レキシプルな非晶質
シリコン太陽電池を得ることができるのである。In this case, light enters from the transparent polyimide film substrate side and passes through the pm-4i layer→n layer in this order. According to this light transmission order, the decrease in photoelectric conversion efficiency and photodeterioration that were present in amorphous silicon solar cells, as shown in Figure 1, are eliminated, and a high-performance 7-lexiple amorphous silicon solar cell can be obtained. It is possible.
（ｃ）発明が解決しようとする課題
このように、特開昭６２−３６８８２号公報に開示され
ている非晶質シリコン太陽電池は、充電変換効率が極め
て高く、また光劣化も小さく、これらの点に関しては非
常に大きな効果が得られるが、非晶質シリコン太陽電池
の製作工程時の熱により、つまり透明電極層及び非晶質
シリコン層の形成時に透明ポリイミドフィルム製基板が
、温度２００〜３００℃の雰囲気に１に露されるため、
その熱収縮が起こり、このため非晶質シリコン層を破壊
することがあり、非晶質シリコン太陽電池の信頼性を低
下させてしまう場合がある。(c) Problems to be Solved by the Invention As described above, the amorphous silicon solar cell disclosed in JP-A No. 62-36882 has extremely high charge conversion efficiency and little photodegradation. However, due to the heat during the manufacturing process of amorphous silicon solar cells, in other words, the transparent polyimide film substrate is heated to a temperature of 200 to 300% during the formation of the transparent electrode layer and the amorphous silicon layer. Because it is exposed to an atmosphere of 1°C,
Thermal shrinkage occurs, which may destroy the amorphous silicon layer and reduce the reliability of the amorphous silicon solar cell.
この場合、非晶質シリコン太陽電池の信頼性を向上させ
るため、予め、ポリイミドフィルム製基板を熱処理し、
熱収縮率を小さくすることも考えられるが、このような
方法を用いても熱収縮率の問題を解決できず、信頼性の
点で間層が残るのである。In this case, in order to improve the reliability of the amorphous silicon solar cell, the polyimide film substrate is heat-treated in advance.
Although it is possible to reduce the heat shrinkage rate, even if such a method is used, the problem of heat shrinkage rate cannot be solved, and an interlayer remains from the viewpoint of reliability.
（ｃｌ） ｉ！ｉｌを解決するための手段そこで、本発
明者らは、無色透明なポリイミドフィルム製基板を用い
、更に、非晶質シリコン太陽電池の製作工程における当
該ポリイミドフィルム製基板の熱収縮率を確実に抑える
方法について鋭意検討した結果、この種無色透明なポリ
イミドフィルム製基板を支持体で保持すると、ポリイミ
ドフィルム製基板の熱収縮を確実に抑えることができ、
しかも信頼性の優れた非晶質シリコン太陽電池が得られ
ることを見い出し、本発明を完成するに至ったものであ
る。(cl) i! Therefore, the present inventors used a colorless and transparent polyimide film substrate, and also reliably suppressed the heat shrinkage rate of the polyimide film substrate in the manufacturing process of an amorphous silicon solar cell. As a result of intensive research on methods, we found that by holding this kind of colorless and transparent polyimide film substrate with a support, thermal shrinkage of the polyimide film substrate can be reliably suppressed.
In addition, they discovered that an amorphous silicon solar cell with excellent reliability can be obtained, leading to the completion of the present invention.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の非晶質シリコン太陽電池は、耐熱性の支持体上
に無色透明なポリイミドフィルム製の基板を作製し、該
基板上に光エネルギーを電気エネルギーに変換する光電
変換素子を設けた後、上記支持体を上記基板から分離す
ることを特徴とするものである。In the amorphous silicon solar cell of the present invention, a colorless and transparent polyimide film substrate is prepared on a heat-resistant support, and a photoelectric conversion element that converts light energy into electrical energy is provided on the substrate. The method is characterized in that the support body is separated from the substrate.
本発明において、耐熱性の支持体としては、非晶質シリ
コン太陽電池の作製工程時における温度２００〜３００
℃の雰囲気温度で寸法変化や反り、更にたわみなどを起
こさず、しかも非晶質シリコン太陽電池の作製後に、ポ
リイミドフィルム製基板から分離できる板状のものであ
れば特に限定されるものではない。In the present invention, the heat-resistant support has a temperature of 200 to 300 during the manufacturing process of an amorphous silicon solar cell.
It is not particularly limited as long as it does not undergo dimensional changes, warping, or deflection at an ambient temperature of °C, and can be separated from the polyimide film substrate after producing an amorphous silicon solar cell.
このような支持体としては、通常がラス板、金属板、セ
ラミックス板などが挙げられる。Such supports usually include lath plates, metal plates, ceramic plates, and the like.
次に、本発明の非晶質シリコン太陽電池の製造方法につ
いて説明する。Next, a method for manufacturing an amorphous silicon solar cell according to the present invention will be explained.
本発明の方法においては、まず、上記の支持体上に無色
透明なポリイミドフィルム製基板を形成するが、それに
は以下のような方法を用いる。In the method of the present invention, first, a colorless and transparent polyimide film substrate is formed on the above-mentioned support, using the following method.
ポリイミド前駆体溶液を用いる場合は、少なくとも片面
が鏡面に仕上げられたガラス板、ステンレス板などを支
持体とし、この支持体の鏡面上にポリイミド前駆体溶液
を一定の厚みになるように流延し、５０〜３５０℃の温
度で徐々に加熱して脱溶媒と脱水閉環を促進してポリイ
ミド前駆体をイミド化することにより行なわれる。When using a polyimide precursor solution, use a glass plate, stainless steel plate, etc. with a mirror finish on at least one side as a support, and cast the polyimide precursor solution onto the mirror surface of this support to a certain thickness. The polyimide precursor is imidized by gradually heating at a temperature of 50 to 350° C. to promote desolvation and dehydration and ring closure.
この場合、ポリイミド前駆体溶液からポリイミドフィル
ム製基板形成における有機溶媒の除去及びイミド化のた
めの加熱工程は真空下（減圧下）又は不活性〃ス雰囲気
下で行ってもよい。更に、短時間であれば温度４００℃
前後まで最終的に加熱することにより、得られるポリイ
ミドフィルム製基板の特性を向上させることができる。In this case, the heating step for removing the organic solvent and imidizing the polyimide precursor solution in forming the polyimide film substrate may be performed under vacuum (under reduced pressure) or under an inert gas atmosphere. Furthermore, the temperature can be increased to 400℃ for a short period of time.
By finally heating the substrate from front to back, it is possible to improve the properties of the resulting polyimide film substrate.
このようにしてポリイミド前駆体をイミド化してポリイ
ミドとする場合において、生成ポリイミドは特性の点か
ら対数粘度（９７％硫酸中０．５ｇ／ｄｌの濃度で３０
℃で測定）を０．５〜５．０の範囲内に設定するのが好
ましい。最も好ましいのは０．７〜３．０である。When a polyimide precursor is imidized to form polyimide in this way, the resulting polyimide has a logarithmic viscosity (30 at a concentration of 0.5 g/dl in 97% sulfuric acid)
C) is preferably set within the range of 0.5 to 5.0. The most preferred range is 0.7 to 3.0.
また、支持体上に無色透明なポリイミドフィルム製の基
板を形成する他の方法としては、ポリイミド溶液を用い
る方法があり、この場合もポリイミド前駆体溶液を用い
る場合と同様に、支持体上にポリイミド溶液を一定の厚
みになるように流延し、５０〜２００℃の温度で加熱し
て溶媒を除去することにより得ることができる。このよ
うな脱溶媒のための加熱工程は真空下（減圧下）又は不
活性ガス雰囲気下で行ってもよい。Another method for forming a colorless and transparent polyimide film substrate on a support is to use a polyimide solution. It can be obtained by casting a solution to a certain thickness and heating it at a temperature of 50 to 200°C to remove the solvent. Such a heating step for removing the solvent may be performed under vacuum (under reduced pressure) or under an inert gas atmosphere.
上記のようにして、支持体上に形成する無色透明なポリ
イミドフィルム製基板の厚みは１０〜１００μ−程度に
設定することが望ましい、この厚さが１００μ−を超え
ると光の透過率が低下して、非晶質シリコン太陽電池の
光電変換効率を悪化させると共に７レキシビリテイーを
低くするという問題が生じ、逆に１０μ−未満になると
充分な機械的強度が得られなくなると共にピンホールな
どに起因して、その信頼性を低下させる恐れがある。The thickness of the colorless and transparent polyimide film substrate formed on the support as described above is preferably set to about 10 to 100 μ-. If this thickness exceeds 100 μ-, the light transmittance decreases. As a result, the photoelectric conversion efficiency of the amorphous silicon solar cell deteriorates, and the flexibility also decreases.On the other hand, if the flexibility is less than 10μ, sufficient mechanical strength cannot be obtained and the flexibility is caused by pinholes, etc. This may reduce its reliability.
そして、本発明においては、無色透明な光透過性のある
ポリイミドフィルム製基板が用いられるが、この無色透
明とは、ｉ厚５０±５μ−のポリイミドフィルム製基板
に対する可視光線（５００ｎ−）透過率が８０％以上で
あって、且つ黄色度［イエローネスインデックス（Ｙ
Ｉ ）］が２５以下のことをいう。In the present invention, a colorless and transparent light-transmitting polyimide film substrate is used, and this colorless and transparent means visible light (500n-) transmittance for a polyimide film-made substrate with an i thickness of 50±5μ-. is 80% or more, and the yellowness [yellowness index (Y
I)] is 25 or less.
以上のようにして得られた、支持体付きの無色透明なポ
リイミドフィルム製基板（以下、頃に基板という）を用
い、本発明の非晶質シリコン太陽電池を製造するには以
下の手順で行えばより・。The amorphous silicon solar cell of the present invention can be manufactured using the colorless and transparent polyimide film substrate with a support (hereinafter referred to as substrate) obtained as described above, using the following steps. For example...
即ち、第１の工程として、上記支持体付き基板の当該基
板上に透明電極層を形成する。これには、酸化インジウ
ム−酸化スズ膜（通称１７０層と−１う）が好適に用い
られるが、これは蒸着法またはスパッタリング法等によ
り形成することができる。That is, as a first step, a transparent electrode layer is formed on the substrate of the support-equipped substrate. An indium oxide-tin oxide film (commonly referred to as 170 layer) is suitably used for this, but this can be formed by a vapor deposition method, a sputtering method, or the like.
この透明電極層の厚みとしては０．０１〜１゜０μ論と
するのが好ましく、０．０１μｍ未満では所望の導電性
が得られず、逆に１．０μ−を超えると透明電極の透明
性が損なわれるため好ましくない。The thickness of this transparent electrode layer is preferably 0.01 to 1.0 μm; if it is less than 0.01 μm, the desired conductivity cannot be obtained, and if it exceeds 1.0 μm, the transparency of the transparent electrode will be reduced. This is undesirable because it damages the
次に、第２の工程として、上記透明電極層上に充電変換
素子となる非晶質シリコン層を形成する。Next, as a second step, an amorphous silicon layer serving as a charge conversion element is formed on the transparent electrode layer.
非晶質シリコン層としては、公知の方法により、ｐ形→
ｉ形→ｎ形の順序で堆積してなるものの他に、ｐ形非晶
質シリコンカーバイド層→ｉ形非晶質シリコン層→ｎ形
非晶質シリコン層の順序で堆積してなるものなど各種の
ものを用いることができる。As the amorphous silicon layer, p-type →
In addition to those deposited in the order of i-type → n-type, there are various types such as those deposited in the order of p-type amorphous silicon carbide layer → i-type amorphous silicon layer → n-type amorphous silicon layer. can be used.
これらの非晶質シリコンの堆積方法としては、スパッタ
リング法、グロー放電法、光ＣＶ Ｄ法、イオンブレー
ティング法などの各種の方法がある。As methods for depositing these amorphous silicones, there are various methods such as sputtering method, glow discharge method, photo CVD method, and ion blating method.
例えば、グロー放電の場合は温度２００〜３００℃に加
熱されたホルダーに、透明電極層を形成した基板（支持
体付き）を保持させ、該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の高周波電力
を供給する。そして、例えばｐ形弁晶質シリコン層を形
成するにはシランにノボラン（Ｂ ２Ｈ、）を導入し、
又ｎ形非晶質シリコン層を形成するにはシランにホスフ
ィン（Ｐ Ｈ３）を導入すればよいのである。For example, in the case of glow discharge, a substrate (with a support) on which a transparent electrode layer is formed is held in a holder heated to a temperature of 200 to 300°C, and the holder is used as one electrode, and a counter electrode is placed between the holder and the opposite electrode. Supplies high frequency power of 13°56MHz. For example, to form a p-type crystalline silicon layer, noborane (B2H, ) is introduced into silane,
Furthermore, in order to form an n-type amorphous silicon layer, phosphine (PH3) may be introduced into silane.
また、上記非晶質シリコン層とは、水素化非晶質シリコ
ン層とフッ素化非晶質シリコン層をいう。Further, the amorphous silicon layer refers to a hydrogenated amorphous silicon layer and a fluorinated amorphous silicon layer.
第３の工程として、上記のようにして得られたｎ型非晶
質シリコン層上に金属製の背面電極層を公知の方法で形
成する。As a third step, a metal back electrode layer is formed by a known method on the n-type amorphous silicon layer obtained as described above.
この背面電極層に用いられる金属としては、アルミニウ
ム、ニッケル、チタン、クロム、銅、鉄、ステンレス、
ニッケルクロム合金などが挙げられるのであり、これら
の金属を用い蒸着法或いはスパッタリング法などの適宜
の方法で背面電極層を形成することができる。Metals used for this back electrode layer include aluminum, nickel, titanium, chromium, copper, iron, stainless steel,
Examples include nickel-chromium alloys, and the back electrode layer can be formed using these metals by an appropriate method such as vapor deposition or sputtering.
第４の工程として、上記の非晶質シリコン層及び背面電
極層の保護を目的として樹脂による裏打ちを行う。As a fourth step, lining with resin is performed for the purpose of protecting the amorphous silicon layer and the back electrode layer.
この目的に用いる樹脂としては、耐湿性、７レキシビリ
テイーを有していれば特に制限はなく、エポキシ樹脂、
ウレタン樹脂、アクリル樹脂、ポリイミド樹脂などを好
適に用いることができる。There are no particular restrictions on the resin used for this purpose as long as it has moisture resistance and 7 flexibility, such as epoxy resin,
Urethane resin, acrylic resin, polyimide resin, etc. can be suitably used.
最後の工程として、上記支持体を上記基板から分離する
。As a final step, the support is separated from the substrate.
この方法としては、上記の各工程を経て得られた充電変
換素子を水中或いは有機溶媒中に浸漬する方法、ヒート
ショック、超音波を用いる方法などがあり、支持体との
Ｖ着性との兼合いで適宜単独又は併せて用いることがで
きる。Examples of this method include a method of immersing the charge conversion element obtained through each of the above steps in water or an organic solvent, a method of using heat shock, and a method of using ultrasonic waves. They can be used alone or in combination as appropriate.
本発明の非晶質シリコン太陽電池の製造方法において、
その無色透明なポリイミドフィルム製の基板として以下
に述べる、一般式に示すのものを用いると、透明度が一
層良好で光電変換効率が極めて高いのであり、又、耐熱
性も良好なので好ましい。In the method for manufacturing an amorphous silicon solar cell of the present invention,
It is preferable to use the colorless and transparent polyimide film substrate represented by the general formula described below because it has better transparency, extremely high photoelectric conversion efficiency, and good heat resistance.
即ち、基板が、一般式
で示される繰り返し単位を有するポリイミドを主成分と
する無色透明なポリイミドフィルムで形成されたもので
ある。That is, the substrate is formed of a colorless and transparent polyimide film whose main component is polyimide having a repeating unit represented by the general formula.
本発明に用いられる無色透明なポリイミドフィルムは、
一般式
で示されるテトラカルボン酸二無水物と一般式Ｈ２Ｎ
Ｒ２Ｎ Ｈ２
で示される芳香族ジアミノとの反応によって得られる。The colorless and transparent polyimide film used in the present invention is
Tetracarboxylic dianhydride represented by the general formula and H2N
It is obtained by reaction with an aromatic diamino represented by R2N H2.
上記テトラカルボン酸二無水物としては、３゜３°、４
．４ ’−ビフェニルテトラカルボン酸二無水物、２．
３．３ ’、４ ’−ビ７ヱニルテトラカルポン酸二無
水物、３，３°、４，４°−ノフェニルスルホンテトラ
カルボン酸二無水物、２，２−ビス（３゜４−ノカルポ
キシフェニル）へキサフルオロプロパンニ無水物が挙げ
られ、これら単独で又は適宜組み合わせて用いることが
できる。The above tetracarboxylic dianhydride includes 3°3°, 4
．． 4'-biphenyltetracarboxylic dianhydride, 2.
3.3',4'-Bi7enyltetracarboxylic dianhydride, 3,3°,4,4°-nophenylsulfonetetracarboxylic dianhydride, 2,2-bis(3°4- (carpoxyphenyl) hexafluoropropane dianhydride, which can be used alone or in appropriate combinations.
また、上記芳香族ジアミンとしては、以下の化合物が挙
げられる。Furthermore, examples of the aromatic diamine include the following compounds.
芳香族１核体ジアミンとしては論−フェニレンジアミン
、輸−トリレンジアミン、４，６−ジメチル−ｍ−フェ
ニレンジアミン、２，４−ノアミノノシチレン、４−ク
ロロ−一−フェニレンジアミン、３．５−ノアミノ安息
香酸、５−ニトロ一一−フェニレンジアミンなどが挙げ
られる。Examples of the aromatic mononuclear diamine include phenylenediamine, trans-tolylenediamine, 4,6-dimethyl-m-phenylenediamine, 2,4-noaminositylene, 4-chloro-1-phenylenediamine, 3. Examples include 5-noaminobenzoic acid and 5-nitro-1-phenylenediamine.
芳香族２核体ジアミンとしては、３，３゛−ジアミ７ジ
フェニルエーテル、３，３′−ジ７ミノノフェニルスル
ホン、３．３’−ジアミノジフェニルスルホキシド、３
．３’−ノアミノジフェニルスルフィド、３．３′−ノ
アミノジフェニルメタン、３，３゜−ノアミノベンゾフ
ェノン、３．３’−ノアミノビフェニル、２，２−ビス
（３−７ミノフエノキシ）へキサフルオロプロパン、２
，２−ビス（４−７ミノフエノキシ）へキサフルオロプ
ロパンなどが挙げられる。Examples of aromatic dinuclear diamines include 3,3'-diami7 diphenyl ether, 3,3'-di7minophenyl sulfone, 3,3'-diaminodiphenylsulfoxide, 3
．． 3'-noaminodiphenyl sulfide, 3.3'-noaminodiphenylmethane, 3,3°-noaminobenzophenone, 3.3'-noaminobiphenyl, 2,2-bis(3-7minophenoxy)hexafluoropropane ,2
, 2-bis(4-7minophenoxy)hexafluoropropane, and the like.
芳香族３核体としては、１，４−ビス（３−７ミ／フエ
ノキシ）ベンゼン、１，３−ビス（３−７ミノフエノキ
シ）ベンゼン、１，４−ビス（３−７ミ／フェニル）ベ
ンゼン、１，３−ビス（３−７ミノフエニル）ベンゼン
などが挙げられる。As aromatic trinuclear bodies, 1,4-bis(3-7mi/phenoxy)benzene, 1,3-bis(3-7minophenoxy)benzene, 1,4-bis(3-7mi/phenyl)benzene , 1,3-bis(3-7minophenyl)benzene, and the like.
芳香族４４ｆ体としては、ビス［４−（３−７ミノフエ
ノキン）フェニル１スルホン、ビス（４−（３−７ミ／
フエノキシ）フェニル１エーテル、４，４゜ビス（３−
７ミ／フエノキシ）ビフェニル、２，２−ビス［４−（
３−７ミノフエノキシ）フェニル１プロパン、２，２−
ビス（４−（３−７ミノフエノキシ）フェニルＪヘキサ
フルオロプロパン、２．２−ビス［４−（４−７ミノ７
エ／キシ）フェニル］へキサフルオロプロパンなどが挙
げられる。The aromatic 44f isomers include bis[4-(3-7minofenoquine)phenyl 1-sulfone, bis(4-(3-7mi/
phenoxy) phenyl 1 ether, 4,4゜bis(3-
7mi/phenoxy) biphenyl, 2,2-bis[4-(
3-7minophenoxy)phenyl 1propane, 2,2-
Bis(4-(3-7 minophenoxy)phenyl J hexafluoropropane, 2,2-bis[4-(4-7 minophenoxy)
Examples include e/xy)phenyl]hexafluoropropane.
そして、これらは単独で又は適宜組み合わせて用いるこ
とができる。These can be used alone or in appropriate combination.
上記のような芳香族テトラカルボン酸二無水物とメタ位
置にアミノ基を有する上記の芳香族ジアミンとを組み合
わせることにより、初めて上記−般式（１）で示される
繰返し単位を主成分とする無色透明なポリイミドが得ら
れるのである。By combining the above-mentioned aromatic tetracarboxylic dianhydride and the above-mentioned aromatic diamine having an amino group at the meta position, a colorless product containing the repeating unit represented by the general formula (1) as a main component can be produced for the first time. A transparent polyimide can be obtained.
ここで、主成分とするとは全体が主成分のみからなる場
合を含める趣旨である。この場合において、無色透明な
ポリイミドの主成分となる上記−般式（１）で示される
繰返し単位の含有量が多い程、得られるポリイミドの無
色透明性が高まる。しかしながら、上記一般式（１）で
示される繰返し単位が８０モル％以上含有されていれば
、少な（ともこの発明で求める全光線透過率及びイエロ
ーネスインデックスが確保されるので、その範囲内にお
いて、上記芳香族テトラカルボン酸二無水物以外のその
他の芳香族テトラカルボン酸二無水物及び上記の芳香族
ジアミン以外のその他の芳香族）７ミンを用いることが
できる。しかし、上記一般式（１）で示される繰返し単
位の含有量の好ましい範囲は８０モル％以上であり、最
も好ましい範囲は９５モル％以上である。Here, the term "principal component" is meant to include the case where the entire component consists only of the main component. In this case, the greater the content of the repeating unit represented by formula (1) above, which is the main component of the colorless and transparent polyimide, the more colorless and transparent the obtained polyimide becomes. However, if the repeating unit represented by the above general formula (1) is contained in an amount of 80 mol% or more, the total light transmittance and yellowness index required by the present invention are secured; Other aromatic tetracarboxylic dianhydrides other than the above-mentioned aromatic tetracarboxylic dianhydrides and other aromatic 7mines other than the above-mentioned aromatic diamines can be used. However, the preferable range of the content of the repeating unit represented by the above general formula (1) is 80 mol% or more, and the most preferable range is 95 mol% or more.
上記その他の芳香族テトラカルボン酸二無水物としては
、ピロメリット酸二無水物、３，３゛−ベンゾ７エ／ン
テトラカルボン酸二無水物、４，４゜−オキシクツタル
酸二無水物、４，４゛−ビス（３゜４−ノカルボキンフ
ェニル）ノフェニルスルホン二無水物、２．３ 、Ｇ
、７−す７タレンテトラカルボン酸二無水物、１．２．
５．６−す７タレンテトラカルボン酸二無水物、１．４
，５．８−す７タレンテトラカルボン酸二無水物などが
挙げられるのであり、これらは単独で、また鴎組み合わ
せて用いることができる。Examples of the above-mentioned other aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3゛-benzo7e/ntetracarboxylic dianhydride, 4,4゜-oxycututaric dianhydride, , 4゛-bis(3゜4-nocarboxymphenyl)nophenylsulfone dianhydride, 2.3, G
, 7-su7talentetracarboxylic dianhydride, 1.2.
5.6-S7talentetracarboxylic dianhydride, 1.4
, 5.8-su7talentetracarboxylic dianhydride, etc., and these can be used alone or in combination.
また、その池の芳香族ジアミンとしては、ｐ−フェニレ
ンノアミン、２．５−）リレンジアミン、ベンジジン、
３．３’−ツメチルベンジノン、４゜４゛−ジアミ７ジ
フェニルエーテル、３，４゛−ノアミ７ノ７ヱニルエー
テル、４，４°−シアミックフェニルスルホン、４．４
’−ノ７ミノノ７ヱニルスルホキシド、４．４’−ノア
ミックフエニルスルフイド％４．４’−ジアミノノフェ
ニルメタン、４゜４゛−７７ミノベンゾフエノン、２，
２−ビス（４−アミノフェニル）プロパン、３，３°−
ツノ）キシ−４，４゛−ジ７ミノノフェニルメタン、３
，３゜−ツメチル−４，４′−ジ７ミ７ノフェニルメタ
ン、１．４−ビス（４，４°−アミノ７エ／キシ）ベン
ゼン、４，４“−ノアミノターフェニル、ビス（４−（
４−アミノ７ヱノキシ）フェニル１スルホン、ビス［４
−（４−７ミ７７エ／キシ）フェニル１エーテル、４．
４゛−ビス（４−アミノフェノキシ）ビフェニル、２．
２−ビス［４−（４−７ミ７フエノキシ）７エ二ル１プ
ロパンなどが挙げられ、これらは単独で又は併せて用い
ることがでさる。In addition, the aromatic diamines in the pond include p-phenylenenoamine, 2.5-)lylenediamine, benzidine,
3.3'-trimethylbenzinone, 4゜4゛-diami7diphenyl ether, 3,4゛-noami7no7denyl ether, 4,4゛-cyamic phenyl sulfone, 4.4
'-7minono7enyl sulfoxide, 4.4'-noamic phenyl sulfide%4.4'-diaminonophenylmethane, 4゜4゛-77minobenzophenone, 2,
2-bis(4-aminophenyl)propane, 3,3°-
Horn) xy-4,4゛-di7minonophenylmethane, 3
, 3゜-tmethyl-4,4'-di7mi7nophenylmethane, 1,4-bis(4,4°-amino7eth/xy)benzene, 4,4''-noaminoterphenyl, bis( 4-(
4-amino-7enoxy)phenyl-1-sulfone, bis[4
-(4-7mi77e/xy)phenyl 1 ether, 4.
4′-bis(4-aminophenoxy)biphenyl, 2.
Examples include 2-bis[4-(4-7my7phenoxy)7enyl1propane, which can be used alone or in combination.
又、本発明の非晶質シリコン太陽電池の製造方法におい
て、耐熱性の支持体が表面剥離処理を施したものを用い
ることにより、耐熱性の支持体と基板との分離性が極め
て良好となり、この結果、この分離の際に非晶質シリコ
ン層の破壊が生じることがなく、このため、信頼性が一
層高くなる上、太陽電池の生産性が着しく向上するので
望ましい。Furthermore, in the method for manufacturing an amorphous silicon solar cell of the present invention, by using a heat-resistant support that has been subjected to surface peeling treatment, the separability between the heat-resistant support and the substrate is extremely good, As a result, the amorphous silicon layer is not destroyed during this separation, which is desirable because the reliability is further increased and the productivity of the solar cell is significantly improved.
即ち、上述の方法で支持体と基板を分離する際、該支持
体に剥離層を形成したものを用いると、この剥離が一層
容易になるのである。That is, when the support and the substrate are separated by the above-described method, the separation becomes easier if the support is provided with a release layer.
上記剥離層としては、支持体上に上記の各層を堆積した
後、つまり太陽電池を設けた後、支持体と基板を剥離す
る際、その剥離が困難であるときに、その剥離を一層容
易にするものであれば特に限定されるものではない。The above-mentioned peeling layer is used to make the peeling easier when peeling off the support and the substrate is difficult after depositing each of the above layers on the support, that is, after providing the solar cell. There is no particular limitation as long as it is.
この剥離層を形成するためのＮ離削としては、例えばシ
リコーン系剥離剤、フッ素系剥離剤等が挙げられる。Examples of the N release agent for forming this release layer include silicone release agents, fluorine release agents, and the like.
上記剥離剤としでは、常用されているポリジメチルシロ
キサンジオールとポリジメチルハイドロジエンシロキサ
ンの混合溶液であるシリコーン系剥離剤［例えば、ＫＳ
−７００（信越化学工業（株））、ＳＨ−７０２０（）
−レ・シリコーン０株））、７５Ｍ８２０（東芝シリコ
ーン（株））］を１００℃〜４００℃で耐熱性支持体表
面へ焼付けることにより上記効果が達成できる。The above-mentioned release agent is a commonly used silicone release agent that is a mixed solution of polydimethylsiloxane diol and polydimethylhydrodiene siloxane [for example, KS
-700 (Shin-Etsu Chemical Co., Ltd.), SH-7020 ()
The above effect can be achieved by baking 75M820 (Toshiba Silicone Co., Ltd.) onto the surface of a heat-resistant support at 100°C to 400°C.
この場合、その処理条件としては、表面剥離処理前号で
あるシリコーン系剥離剤含有分ｏ、ｏｏｓ〜５重１％に
なるように有機溶媒で適宜調整し、薄く耐熱性支持体上
に塗布した後、１００ ’Ｃ〜４００℃で焼付けするこ
とが好ましい。In this case, the treatment conditions were as follows: The silicone release agent content was adjusted appropriately with an organic solvent to 1% by weight of 0, oos to 5% as described in the previous issue of the surface peeling treatment, and the mixture was thinly coated on a heat-resistant support. After that, it is preferable to bake at 100'C to 400C.
表面剥離処理剤溶液のシリコーン系剥離剤含有分が５重
１％を超え、或いは処理温度が４００℃を超える場合は
、透明ポリイミドフィルム製基板製作工程、或いは非晶
質シリコン製作工程において透明ポリイミドフィルム製
基板と該耐熱性支持体どの密着性が保持できないのであ
り、一方、表面剥離処理剤溶液のシリコーン系剥離剤が
０．００５重量％未満の場合は、非晶質シリコン太陽電
池！！！遣工程後、透明ポリイミドフィルム製基板は、
耐熱性支持体よりの離型が困難であり、非晶質シリコン
太陽電池にスジが入ったり損傷する場合が有るので、い
ずれの場合も望ましくない、この際に予め、耐熱性の支
持体表面に施した表面剥離処理の効果により、水中或い
は有機溶媒中に浸漬することにより上記支持体と上記基
板を−層容易に分離することができる。If the silicone release agent content in the surface release agent solution exceeds 5% by weight or the treatment temperature exceeds 400°C, transparent polyimide film may not be used in the transparent polyimide film substrate manufacturing process or amorphous silicon manufacturing process. On the other hand, if the silicone release agent in the surface release agent solution is less than 0.005% by weight, the adhesion between the substrate and the heat-resistant support cannot be maintained. ! ! After the coating process, the transparent polyimide film substrate is
It is difficult to release the mold from the heat-resistant support, and it may cause streaks or damage to the amorphous silicon solar cell, which is undesirable in either case. Due to the effect of the applied surface peeling treatment, the support and the substrate can be easily separated into layers by immersion in water or an organic solvent.
本発明の非晶質シリコン太陽電池の製造方法においで、
表面１１１１１処理斉呼としてシリコーンＸ％剥離剤を
用い、該シリコーン系ＭＩａＭを１００〜３５０℃の加
熱界Ｂ気下で耐熱性の支持体に焼付けられているものが
、支持体と基板の剥離性が良好であり、しかも品質の安
定した剥ｌ！１層が得られるから好ましい。In the method for manufacturing an amorphous silicon solar cell of the present invention,
Surface 11111 treatment Using a silicone Good peeling and stable quality! This is preferred because one layer can be obtained.
このような温度条件により、透明ポリイミドフィルム製
基板製作工程、或いは非晶質シリコン製作工程において
透明ポリイミドフィルム製基板と該耐熱性支持体との密
着性が保持されるのである。Such temperature conditions maintain the adhesion between the transparent polyimide film substrate and the heat-resistant support during the transparent polyimide film substrate manufacturing process or the amorphous silicon manufacturing process.
本発明の非晶質シリコン太陽電池の製造方法においで、
上記支持体（表面剥離処理を施したものと施していない
ものの両方を含む、以下同じ、）上に、上記の無色透明
なポリイミドフィルム製の基板を形成するには、以下の
手法が採用される。In the method for manufacturing an amorphous silicon solar cell of the present invention,
The following method is adopted to form the above colorless and transparent polyimide film substrate on the above support (including both those subjected to surface release treatment and those not subjected to surface release treatment, the same shall apply hereinafter). .
上記の芳香族テトラカルボン酸二無水物及び芳香族ジア
ミンを有機溶媒中において、８０℃以下の温度で反応さ
せることによってポリアミド酸を合成し、このポリアミ
ド酸溶液を用いて、上記耐熱性の支持体上に流延、ロー
ルコーティング等の方法で所望の形状の賦型体を形成し
、これを空気中、不活性ガス中又は真空中で、５０〜３
５０℃の温度条件下で有機溶媒を除去すると同時にポリ
アミド酸を脱水閉環してポリイミドにすることにより得
られる。＊た、上記ポリアミド酸を無水酢酸／ピリジン
混合溶液中に浸漬して脱溶媒とイミド化を同時に行う化
学イミド化法によっても得られる。A polyamic acid is synthesized by reacting the above-mentioned aromatic tetracarboxylic dianhydride and aromatic diamine in an organic solvent at a temperature of 80°C or lower, and using this polyamic acid solution, the above-mentioned heat-resistant support is prepared. A molded body having a desired shape is formed on the top by a method such as casting or roll coating, and this is heated in air, in an inert gas, or in a vacuum to 50 to 30%
It is obtained by simultaneously removing the organic solvent and dehydrating and ring-closing polyamic acid to form polyimide under a temperature condition of 50°C. *It can also be obtained by a chemical imidization method in which the above polyamic acid is immersed in an acetic anhydride/pyridine mixed solution to simultaneously remove the solvent and imidize it.
或いは、ポリアミド酸を貧溶媒中に再沈して単離し、そ
の後加熱或いは化学的なイミド化により脱水閉環してポ
リイミドとすることも可能である。Alternatively, it is also possible to isolate the polyamic acid by reprecipitation in a poor solvent, and then dehydrate and ring-close it by heating or chemical imidization to obtain a polyimide.
さらに、ポリアミド酸溶液をそのまま１００℃以上に加
熱してイミド化することも可能である。Furthermore, it is also possible to heat the polyamic acid solution as it is to 100° C. or higher to imidize it.
この場合において、得られるポリイミドが重合溶媒に対
して溶解性がない場合には沈澱物として単離してくるが
、溶解性がある場合にはそのまま溶液状であるため、ポ
リアミド酸の場合のように貧溶媒中に再沈して単離する
か、又はポリイミド溶液を、支持体上に流延、ロールコ
ーティング等の方法で所望の形状の賦型体を形成し、こ
れを空気中、不活性〃ス中又は真空中で、５０〜２００
℃の温度条件下で有機溶媒の除去を行うことによって得
ることもできる。再沈して単離する場合には濾過洗浄工
程が必要となるが、実質的に同一の無色透明なポリイミ
ドができる。上記の有機溶媒としてはＮ、Ｎ−ジメチル
ホルムアミド、Ｎ、Ｎ−ツメチルアセトアミド、ジグラ
イム、トリグライム、クレゾール、ハロゲン化フェノー
ル、メチルセｄソルプアセテート、ジオキサン、テトラ
ヒドロ７ランなどが好適であるが、特にＮ、Ｎ−ジメチ
ルアセトアミドが好ましい、これらの有機溶媒は単独で
用いてもよいし、或いは２種以上併眉してもよい。In this case, if the polyimide obtained is not soluble in the polymerization solvent, it will be isolated as a precipitate, but if it is soluble, it will remain in the form of a solution, so it will be isolated as a precipitate, as in the case of polyamic acid. Either the polyimide solution is isolated by reprecipitation in a poor solvent, or the polyimide solution is cast onto a support, a molded body having a desired shape is formed by a method such as roll coating, and the molded body is inertly heated in air. 50 to 200 in a bath or vacuum
It can also be obtained by removing the organic solvent under temperature conditions of .degree. In the case of isolation by reprecipitation, a filtration and washing step is required, but substantially the same colorless and transparent polyimide can be obtained. Suitable examples of the above organic solvent include N,N-dimethylformamide, N,N-trimethylacetamide, diglyme, triglyme, cresol, halogenated phenol, methylsedolpacetate, dioxane, and tetrahydro-7rane. N,N-dimethylacetamide is preferred, and these organic solvents may be used alone or in combination of two or more.
これらの有機溶媒は比較的沸点が低いため、加熱による
イミド化の際に分解してその分解物がポリイミド中に残
留して着色の原因になるといった問題が起こらないので
ある。ポリ７ミ）′酸の重合溶媒としてよく用いられて
いる溶媒にＮ−メチル−２−ピロリドンがあるが、この
溶媒は高温に加熱されると分解し、その分解物がポリイ
ミド中に残留し、着色の原因となることが知られている
ため、使用することはできない。Since these organic solvents have relatively low boiling points, there is no problem that they decompose during imidization by heating and the decomposed products remain in the polyimide and cause coloring. N-methyl-2-pyrrolidone is a solvent often used as a polymerization solvent for poly(7m)' acid, but this solvent decomposes when heated to high temperatures, and the decomposed products remain in the polyimide. It cannot be used because it is known to cause discoloration.
なお、上記に例示した好適な有機溶媒を使用する際に、
エタノール、トルエン、ベンゼン、キシレン、ニトロベ
ンゼンなどの溶媒を、ポリイミドフィルムの無色透明性
を損なわない程度に一種又は二種以上適宜混合して用い
てもよい。Note that when using the suitable organic solvents exemplified above,
Solvents such as ethanol, toluene, benzene, xylene, and nitrobenzene may be used alone or in combination as appropriate to the extent that the colorless transparency of the polyimide film is not impaired.
上記のように、無色透明なポリイミドフィルムを製造す
る際にポリイミド前駆体の対数粘度（Ｎ。As mentioned above, when producing a colorless and transparent polyimide film, the logarithmic viscosity (N) of the polyimide precursor is determined.
Ｎ−ツメチルアセトアミド中０．５ｇ／ｄｌの濃度にお
いて３０℃で測定）が、０．５〜５．０の範囲になるよ
うに調整するのが好ましい。待に好適なのは０．７〜２
．０である。この対数粘度が低すぎると得られるポリイ
ミドフィルムの８１械的強度が低下するため好ましくな
い。また逆にＮｔ＆粘度が高すぎるとポリイミド前駆体
溶液を適当な形状に賦形する際に流延させにくくなるた
め好ましくない、ポリイミド前駆体溶液の濃度も、作業
性の観点から５〜４０重１％、好ましくは１５〜３０重
量％に設定することが望ましい。(measured at 30° C. at a concentration of 0.5 g/dl in N-trimethylacetamide) is preferably adjusted to be in the range of 0.5 to 5.0. The suitable value for waiting is 0.7 to 2.
．． It is 0. If the logarithmic viscosity is too low, the mechanical strength of the polyimide film obtained will decrease, which is not preferable. On the other hand, if the Nt and viscosity are too high, it becomes difficult to cast the polyimide precursor solution when shaping it into an appropriate shape, which is undesirable. %, preferably 15 to 30% by weight.
なお、上記対数粘度は次式で計算されるものであり、式
中の時間は毛細管粘度計により測定されるものである。The above logarithmic viscosity is calculated using the following formula, and the time in the formula is measured using a capillary viscometer.
ｔｏ＝ 溶媒の落下時間（秒）
ｔｌ： 溶液の落下時間（秒）
Ｃ： 濃度（ｇ／ｃｌｌ）
（ｅ）作用
本発明は、上記構成を有し、支持体上にポリイミドフィ
ルム製基板が密着しているから、この基板上に透明導電
層等の各層を、加熱下″Ｃ堆積するとき、この基板の熱
収縮は支持体によって阻止されるのであり、このため、
非晶質シリコン層が破壊されるのが防止される作用を有
するのである。to= Falling time of solvent (seconds) tl: Falling time of solution (seconds) C: Concentration (g/cll) (e) Effect The present invention has the above structure, and a polyimide film substrate is tightly attached to a support. Therefore, when each layer such as a transparent conductive layer is deposited on this substrate under heating, thermal shrinkage of this substrate is prevented by the support.
This has the effect of preventing the amorphous silicon layer from being destroyed.
ごの支持体付き太陽電池を水中或いは有機溶媒中に浸漬
したり、ヒートシミツク、超音波を用い、支持体との密
着性との兼合いで適宜単独又は併せて用いることにより
、支持体と太陽電池を容易に分離できる作用を有するの
である。By immersing the solar cell with a support in water or an organic solvent, using heat stains or ultrasonic waves, and using it alone or in combination as appropriate depending on the adhesion with the support, the support and the solar cell can be bonded. It has the ability to easily separate the two.
また、耐熱性の支持体に表面剥離処理を施すことにより
、上記太陽電池の形成後は、この耐熱性支持体は、上記
基板より、上述の方法によって極めて容易に分離できる
作用を有するのである。Further, by subjecting the heat-resistant support to a surface peeling treatment, the heat-resistant support has the ability to be separated from the substrate extremely easily by the method described above after the solar cell is formed.
（「）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。(') EXAMPLES The present invention will be explained in detail based on Examples below, 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、ビス
［４−（３−７ミノフエノキシ）フェニル１スルホン０
，２モルに対して３，３°、４，４°−ビフェニルテト
ラカルボン酸二無水物０．２モルを室温で３０時間反応
させ、ポリアミド酸溶液を得た。このポリアミド酸の対
数粘度を測定したところ１．８１であった。この溶液を
はうけい酸ガラス板上に流延して８１膜を形成し、熱風
循環乾燥機中で１００℃で乾燥し、残存溶媒量が３０重
量％を切ったところで昇温を閏始し、最終的に温度３０
０℃まで加熱してイミド化反応を完全に行い、ガラス製
支持体上に、膜厚３０μ−の無色透明のポリイミドフィ
ルム製基板を得た。このポリイミドフィルム製基板に対
する波長５００ｎ−での光線透過率は８５．２％であり
、イエローネスインデックスは１２．３であった。Example 1 Using N,N-trimethylacetamide as a solvent, bis[4-(3-7minophenoxy)phenyl 1 sulfone 0
, 0.2 mole of 3,3°,4,4°-biphenyltetracarboxylic dianhydride was reacted at room temperature for 30 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid was measured and found to be 1.81. This solution was cast onto a silicate glass plate to form an 81 film, which was dried at 100°C in a hot air circulation dryer, and when the remaining solvent amount was less than 30% by weight, heating was started. , finally the temperature is 30
The imidization reaction was completed by heating to 0° C., and a colorless and transparent polyimide film substrate having a thickness of 30 μm was obtained on a glass support. The light transmittance of this polyimide film substrate at a wavelength of 500 n- was 85.2%, and the yellowness index was 12.3.
この基板上に蒸着法により厚み５００人のＩＴＯ製の透
明電極層を堆積した後、内部電極型の高周波（１３，５
６ＭＨｚ）グロー放１！装置内のヒーター付きホルダー
に保持し、温度２５０℃前後に保ちながら水素で１０モ
ル％に希釈したシランと水素で５０００ ｐｐｍに希釈
したジボラン（Ｂ ２Ｈｓ）を混合し、グロー放電装置
内に導入し、真空度０゜Ｊ Ｔ ｏｒｒの雰囲気下でＩ
ＯＷの高周波電力を印加して該基板上のほう素をドープ
した厚み１５０人のｐ形弁晶質シリコン層を設けた。After depositing a transparent electrode layer made of ITO with a thickness of 500 by vapor deposition on this substrate, an internal electrode type high frequency (13,5
6MHz) Glow release 1! Silane diluted to 10 mol% with hydrogen and diborane (B2Hs) diluted to 5000 ppm with hydrogen were mixed together while maintaining the temperature at around 250°C in a holder with a heater inside the device, and introduced into the glow discharge device. , in an atmosphere with a degree of vacuum of 0°J Torr.
A boron-doped p-type crystalline silicon layer having a thickness of 150 nm was formed on the substrate by applying OW high frequency power.
続いて上記の水素希釈シランのみを導入して同様の反応
を行い／ンドープの厚み５０００人のｉ形弁晶質シリコ
ン層を堆積し、更に水素希釈シランと水素で５０００
ｐｐｍに希釈したホスフィン（ＰＨ，）を混合し、グロ
ー放電装置内に導入してリンをドープした５００人のｎ
形弁晶質シリコン層を設けた。Subsequently, the same reaction was carried out by introducing only the above hydrogen-diluted silane, and an undoped i-type crystalline silicon layer with a thickness of 5,000 yen was deposited, and then with the hydrogen-diluted silane and hydrogen, a 5,000 yen thick layer was deposited.
Phosphine (PH, ) diluted to ppm was mixed and introduced into a glow discharge device to dope 500 people with phosphorus.
A crystalline silicon layer was provided.
即ち、耐熱性の支持体付き基板上に、ＩＴＯ膜を介して
ｐ形、ｉ形、ｎ形の非晶質シリコン層からなる太陽電池
を形成した。That is, a solar cell consisting of p-type, i-type, and n-type amorphous silicon layers was formed on a heat-resistant substrate with a support via an ITO film.
続いて、これを真空蒸着装置内に保持し、常法の蒸着法
により厚み０．１μｌのアルミニウム製の背面電極層を
堆積した。Subsequently, this was held in a vacuum evaporation apparatus, and a 0.1 μl thick aluminum back electrode layer was deposited by a conventional evaporation method.
次に装置から取り出した後、裏打ち材としてエポキシ樹
脂を用い、これを上記背面電極層上に厚み５０μ論でコ
ーティングして保護した。After taking it out from the device, the back electrode layer was coated with epoxy resin to a thickness of 50 μm to protect it as a backing material.
最後に５０°Ｃの温水中に浸漬してガラス製支持体と基
板を分離し、非晶質シリコン太陽電池を得た。Finally, the glass support and substrate were separated by immersion in 50°C hot water to obtain an amorphous silicon solar cell.
このようにして得られた非晶質シリコン太陽電池の光電
変換効率をＡ Ｍ １ 、１００ ｍＷ／ｃＩＩ＋２の
ソーラーシュミレータ−で無色透明なポリイミド基板側
から光を照射して測定した、結果を第１表に示す。The photoelectric conversion efficiency of the amorphous silicon solar cell thus obtained was measured using a solar simulator with AM 1 and 100 mW/cII+2 by irradiating light from the colorless and transparent polyimide substrate side. Shown in the table.
実施例２〜４
溶媒としでＮ、Ｎ−ツメチル７セト７ミドを用い、３．
３’−ジアミノノフェニルスルホン０．２モルに対して
３．３ ’、４．４°−ビフェニルテトラカルボン酸二
無水物０．２モルを溶液のモノマー濃度を３０重量％に
して室温で３０時間反応させ、ポリアミド酸溶液を得た
。このポリアミド酸の対数粘度を測定したところ１．５
４であった。このポリアミド酸溶液を、第１表の実施例
２〜４に示す表面剥離処理を施した耐熱性支持体上に各
々流延してｎ膜を形成し、熱風循環乾ｆｆ！機中で１０
０℃で乾燥し、残存溶媒量が３０重量％を切ったところ
で昇温を開始し、最終的に温度３００℃まで加熱してイ
ミド化反応を完全に行い、耐熱性支持体上に、膜厚３０
μ−の無色透明のポリイミドフィルム製基板を得た。Examples 2 to 4 Using N,N-methyl 7cetomide as a solvent, 3.
0.2 mol of 3.3',4.4°-biphenyltetracarboxylic dianhydride was added to 0.2 mol of 3'-diaminonophenyl sulfone to make the monomer concentration of the solution 30% by weight for 30 hours at room temperature. The reaction was carried out to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid was measured and was 1.5.
It was 4. This polyamic acid solution was cast on each of the heat-resistant supports subjected to the surface peeling treatment shown in Examples 2 to 4 in Table 1 to form an n film, and dried with hot air circulationff! 10 on the plane
Dry at 0°C, start heating when the amount of residual solvent is less than 30% by weight, and finally heat to 300°C to complete the imidization reaction. 30
A transparent, colorless μ-based polyimide film substrate was obtained.
このポリイミドフィルム製基板に対する波長５００ｎ−
での光線透過率は８６．６％であり、イエローネスイン
デックスは９．８であった。Wavelength 500n- for this polyimide film substrate
The light transmittance was 86.6%, and the yellowness index was 9.8.
以下、実施例１と同様にして、耐熱性支持体付き基板上
に、ＩＴＯ９ｉを介してｐ形、ｉ形、ｎ形の非晶質シリ
コン層からなる太陽電池を形成した。Thereafter, in the same manner as in Example 1, a solar cell consisting of p-type, i-type, and n-type amorphous silicon layers was formed on a substrate with a heat-resistant support via ITO9i.
続いて、これを真空蒸着装置内に保持し、常法の蒸着法
により厚み０．１μ−のアルミニ９ム製の背面電極層を
堆積した。Subsequently, this was held in a vacuum evaporation apparatus, and a back electrode layer made of aluminum 9m having a thickness of 0.1 .mu.m was deposited by a conventional evaporation method.
次に装置から取り出した後、裏打ち材としてエポキシ樹
脂を用い、これを上記背面電極層上に厚み５０μ−でコ
ーティングして保護した。After taking it out from the device, the back electrode layer was coated with epoxy resin to a thickness of 50 μm as a backing material to protect it.
最後に４０℃の温水中に浸漬して耐熱性支持体と基板を
各々分離し、非晶質シリコン太陽電池を得た。これらの
表面処理の条件による工程の密着性及び工程終了後の離
型性について評価した結果を第１表に示した。Finally, the heat-resistant support and the substrate were separated by immersion in 40° C. hot water to obtain an amorphous silicon solar cell. Table 1 shows the results of evaluating the adhesion during the process and the releasability after the process was completed under these surface treatment conditions.
（以下余白）
このようにして得られた非晶質シリコン太陽電池の充電
変換効率をＡＭ １．１００ｍＷ／ｃ＋ｅ”のソーラー
シェミレーターで無色透明なポリイミド基板側から光を
照射しで測定した、結果を第２表に示す。(Left below) The charge conversion efficiency of the amorphous silicon solar cell obtained in this way was measured using an AM 1.100 mW/c+e'' solar chemistor by irradiating light from the colorless and transparent polyimide substrate side. are shown in Table 2.
実施例５
ビス［４−（３−７ミノフエノキシ）フェニル１スルホ
ンに代えて、３．３’−ジアミノジフェニルスルホンを
用いた以外は実施例１と同様にして、厚み３０μ−のポ
リイミドフィルム製基板がガラス製支持体上に形成され
た支持体付き基板を得た。Example 5 A polyimide film substrate with a thickness of 30 μ- A substrate with a support formed on a glass support was obtained.
この基板に対する波長５００ｎｍでの光線透過率は８５
．４％、イエａ−ネスインデックスは１１゜８であった
。The light transmittance for this substrate at a wavelength of 500 nm is 85
．． 4%, and the house aness index was 11°8.
また、ポリイミドに転化する前のポリアミド酸の対数粘
度は１．０７であった。Moreover, the logarithmic viscosity of the polyamic acid before being converted into polyimide was 1.07.
この支持体付き基板上に、実施例１と同様の手順を用い
て非晶質シリコン太陽電池を作製した。On this substrate with a support, an amorphous silicon solar cell was produced using the same procedure as in Example 1.
得られた非晶質シリコン太陽電池の光電変換効率を実施
例１と同様の方法で測定し、その結果を第２表に示した
。The photoelectric conversion efficiency of the obtained amorphous silicon solar cell was measured in the same manner as in Example 1, and the results are shown in Table 2.
実施例６
３．３ ’、４．４ ’−ビフェニルテトフカルポン酸
二無水物に代えて２．２−ビス（３，４−ノカルボキシ
フェニル）へキサフルオロプロパンニ無水物を用いた以
外は実施例１と同様にして、厚み３０μｍのポリイミド
フィルム製基板がガラス製支持体上に形成された支持体
付き基板を得た。Example 6 Except that 2,2-bis(3,4-nocarboxyphenyl)hexafluoropropanide dianhydride was used in place of 3.3′,4.4′-biphenyltetophylcarboxylic dianhydride. In the same manner as in Example 1, a substrate with a support was obtained in which a polyimide film substrate having a thickness of 30 μm was formed on a glass support.
この基板に対する波長５００ｎｍでの光線透過率は８６
．８％、イエローネスインデックスは９゜１であった。The light transmittance for this substrate at a wavelength of 500 nm is 86
．． 8%, and the yellowness index was 9°1.
また、ポリイミドに転化する前のポリアミド酸の対数粘
度は０．９８であった。Moreover, the logarithmic viscosity of the polyamic acid before being converted into polyimide was 0.98.
この支持体付き基板上に、実施例１と同様の手順を用い
て非晶質シリコン太陽電池を作製した。On this substrate with a support, an amorphous silicon solar cell was produced using the same procedure as in Example 1.
得られた非晶質シリコン太陽電池の充電変換効率を実施
例１と同様の方法で測定し、その結果を第２表に示した
。The charge conversion efficiency of the obtained amorphous silicon solar cell was measured in the same manner as in Example 1, and the results are shown in Table 2.
比較例１〜３
実施例１〜３で得られた支持体付き基板から当該基板を
剥離し、この基板のみを用い、実施例１と同様の手順に
より非晶質シリコン太陽電池を作製した（この場合、当
然のことながらガラス製支持体は設けられていないので
その剥離工程は削除される）。Comparative Examples 1 to 3 The substrates with supports obtained in Examples 1 to 3 were peeled off, and using only these substrates, amorphous silicon solar cells were produced in the same manner as in Example 1. In this case, of course, a glass support is not provided, so the peeling step is omitted).
得られた太陽電池の充電変換効率を実施例１と同様の方
法で測定し、その結果を第２表に示した。The charge conversion efficiency of the obtained solar cell was measured in the same manner as in Example 1, and the results are shown in Table 2.
ところで、比較例１は実施例１と、又、比較例２は実施
例５と、更に比較例３は実施例６と各々対応する。By the way, Comparative Example 1 corresponds to Example 1, Comparative Example 2 corresponds to Example 5, and Comparative Example 3 corresponds to Example 6.
第２表
！：Ａ１表より、適当な表面剥離処理を施したがフス等
の耐熱性支持体上に形成した非晶質シリコン太陽電池は
、表面剥離処理を施されていない耐熱性支持体上に形成
した太陽電池と比べ、同等の工程中での密着性を持ち、
更に工程終了後に優れた離型性を有することがわかる。Table 2! :From Table A1, amorphous silicon solar cells formed on a heat-resistant support such as fluorine, which has been subjected to an appropriate surface peeling treatment, are different from solar cells formed on a heat-resistant support that has not been subjected to a surface peeling treatment. Compared to batteries, it has the same adhesion during the process,
Furthermore, it can be seen that it has excellent mold releasability after the completion of the process.
この理由としては、表面剥離処理剤の耐熱性支持体及び
無色透明なポリイミドフィルム製基板との密着・反発の
バランスが保たれているためであり、離型性が向上する
のは、温水中に浸漬することにより、水の浸透が起こり
、密着力く反発力の関係になるためと解される。The reason for this is that the adhesion and repulsion of the surface release treatment agent to the heat-resistant support and the colorless transparent polyimide film substrate are maintained in a well-balanced manner. This is understood to be due to the fact that immersion causes water to penetrate, creating a relationship between adhesion and repulsion.
又、第２表より、ガラス製支持体をｍいた本発明の方法
で得られた非晶質シリコン太陽電池は、フィルム単体を
基板として用いた比較例の太陽電池に比べて高い光電変
換効率を有することがわかる。Furthermore, from Table 2, the amorphous silicon solar cell obtained by the method of the present invention using a glass support has higher photoelectric conversion efficiency than the comparative solar cell using a single film as a substrate. It turns out that it has.
この理由としては、無色透明のポリイミドフィルム製基
板を熱変形させないように、当該基板を支持体上に密着
したまま大Ｆ！電池を作製するために、ポリイミドフィ
ルム製基板が熱変形せず、従って基板上のＩＴＯ膜（透
明電極／１１＞及び非晶質シリコン層各層の膜質が非常
に向上し、そのため光電変換効率がアップしたものと解
される。The reason for this is that in order to prevent the colorless and transparent polyimide film substrate from deforming due to heat, the large F. In order to manufacture batteries, the polyimide film substrate does not undergo thermal deformation, and therefore the film quality of the ITO film (transparent electrode / 11) and amorphous silicon layer on the substrate is greatly improved, which increases photoelectric conversion efficiency. It is understood that
また、本発明の方法を用いてアルミニウム、ステンレス
等の金属箔をロール状に巻回し、このロール体から金Ｒ
箔を繰り出しつつ連続的に非晶質シリコンを作製する場
合には、具体的【一実施例の手順に従って行えばよく、
このとき金属Ｍ（支持体）としでは鏡面仕上げしたもの
、或いは場合によっては更にシリコーン処理などの離型
処理を施したものを用いるのが好ましい。In addition, using the method of the present invention, metal foil such as aluminum or stainless steel is wound into a roll, and gold R is rolled from this roll.
When continuously producing amorphous silicon while drawing out the foil, it is sufficient to follow the specific procedure of [one example].
At this time, it is preferable to use a metal M (support) that has been mirror-finished, or that has been further subjected to a mold release treatment such as silicone treatment depending on the case.
（ｇ）発明の効果
本発明は、以上説明したように講成されているので、以
下に記載されるような効果を奏する。(g) Effects of the Invention Since the present invention has been taught as explained above, it produces the effects as described below.
請求項１の非晶質シリコン太陽電池の製造方法において
は、耐熱性の支持体上に無色透明なポリイミドフィルム
製の基板を形成し、該基板上に光エネルギーを電気エネ
ルギーに変換する充電変換素子を設けた後、上記支持体
を上記基板から分離するようにすると、加熱雰囲気下で
もポリイミドフィルム製基板の膨張、収縮或いは変形、
カーリングといったことが起こらず、従って、ポリイミ
ドフィルム製基板に起因する非晶質シリコン層の破壊等
が生じず太陽電池の性能低下が起こらず、安定して製造
することができる効果を有するのである。In the method for manufacturing an amorphous silicon solar cell according to claim 1, a substrate made of a colorless and transparent polyimide film is formed on a heat-resistant support, and a charging conversion element for converting light energy into electrical energy is provided on the substrate. If the support is separated from the substrate after the support is provided, the polyimide film substrate will not expand, contract or deform even under a heated atmosphere.
Curling does not occur, and therefore, the amorphous silicon layer is not destroyed due to the polyimide film substrate, and the performance of the solar cell does not deteriorate, resulting in stable production.
また、本発明の方法は所謂バッチ式で打うこともできる
し、又は、金属箔を支持体とし、これをロール状に巻回
し、このロール体から金属箔（支持体）を繰り出しつつ
連続的に非晶質シリコン層を製造し、生産性を向上させ
る効果を有するのである。In addition, the method of the present invention can be applied in a so-called batch method, or by using a metal foil as a support, winding it into a roll, and continuously rolling out the metal foil (support) from this roll. This has the effect of manufacturing an amorphous silicon layer and improving productivity.
請求項２の非晶質シリコン太陽電池において、その基板
が、一般式
で示される繰り返し単位を有するポリイミドを主成分と
する無色透明なポリイミドフィルムで形成されでいるこ
とにより、透明度が極めて高く充電変換効率が一層高く
、又、耐熱性が良好で熱収縮率が小さ（信頼性が高くな
る効果を有するのである。In the amorphous silicon solar cell according to claim 2, the substrate is formed of a colorless and transparent polyimide film containing polyimide as a main component having a repeating unit represented by the general formula, so that it has extremely high transparency and is effective in charge conversion. It has higher efficiency, good heat resistance, and low heat shrinkage (which has the effect of increasing reliability).
請求項３の非晶質シリコン太陽電池の製造方法において
は、支持体が表面剥離処理を施したものであることより
、太Ｆ！電池製造工程中での無色透明なポリイミドフィ
ルム製基板と支持体との密着性を保ちつつ、工程終了後
には該基板と該支持体の離型性を向上させ、分離工程時
間の短縮化と全工程時間の安定性を向上させる効果を有
するものである。In the method for manufacturing an amorphous silicon solar cell according to claim 3, since the support is subjected to surface peeling treatment, the thick F! While maintaining the adhesion between the colorless and transparent polyimide film substrate and the support during the battery manufacturing process, it improves the releasability of the substrate and the support after the process, shortening the separation process time and improving overall performance. This has the effect of improving the stability of process time.
請求項４の非晶質シリコン太陽電池の製造方法において
は、表面剥離処理剤としてシリコーン系剥離剤を用い、
該シリコーン系剥離剤を１００〜３５０℃の加熱雰囲気
下で耐熱性の支持体に焼付けられていることにより、支
持体と基板の剥離性が一層良好であり、しかも品質の安
定した剥離層が得られる効果を有するのである。In the method for manufacturing an amorphous silicon solar cell according to claim 4, a silicone release agent is used as a surface release treatment agent,
By baking the silicone release agent onto a heat-resistant support in a heated atmosphere of 100 to 350°C, the peelability between the support and the substrate is even better, and a release layer with stable quality can be obtained. It has the effect of
第１図及び第２図は各々構造の異なる非晶質シリコン太
陽電池を示す断面図である。
（１）・・・ポリイミドフィルム製基板、（２）・・・
背面電極層、（３）・・・ｐ型非晶質シリコン層、（４
）・・・真性非晶質シリコン層、（５）・・・ｎ型非晶
質シリコン層、（６）・・・透明１！極層、（７）・・
・透明樹脂層、（８）・・・無色透明ポリイミドフィル
ム製基板、（９）・・・表面保護用樹脂層。
第１図 ７
筒２図
］パがリイミＹニアＬＩＬム５Ｌ４．’Ｊｃ２−・・責
面也Ｊｋ、噌
３・−・ρシ側晶貢シー１コニ、マ
乙・−・ｊ、地針品′１．シリコ；層
５・・・汽翌ノＰ５２ノ」コシ漕
６−“＝Ｌ稍シ勉４
７− 仕組７シ４４ Ａｔ管
８ − 、堰２．己辻絹２ツｚリイミトフイ・弘般１良
９・・表シ、ｉ、ｉｔ租罪ｔ、１FIGS. 1 and 2 are cross-sectional views showing amorphous silicon solar cells having different structures. (1)...Polyimide film substrate, (2)...
Back electrode layer, (3)... p-type amorphous silicon layer, (4
)...Intrinsic amorphous silicon layer, (5)...N-type amorphous silicon layer, (6)...Transparent 1! Extreme layer, (7)...
- Transparent resin layer, (8)...Colorless transparent polyimide film substrate, (9)...Resin layer for surface protection. Fig. 1 7 Cylinder 2] Pa is Liimi Y Near LIL M5L4. 'Jc2--Zenmenya Jk, 噌3--ρshi side crystal tribute Sea 1koni, Maoto--j, ground needle item'1. Silico; Layer 5...Next steam P52ノ" Koshi row 6-"=L-Koshiben 4 7- Mechanism 7shi 44 At pipe 8-, Weir 2. Self-suji silk 2 Tsuzuriimitofui Kohan 1 quality 9...front shi, i, it tax t, 1
Claims (4)
ム製の基板を形成し、該基板上に光エネルギーを電気エ
ネルギーに変換する光電変換素子を設けた後、上記支持
体を上記基板から分離することを特徴とする非晶質シリ
コン太陽電池の製造方法。(1) After forming a colorless and transparent polyimide film substrate on a heat-resistant support and providing a photoelectric conversion element that converts light energy into electrical energy on the substrate, the support is separated from the substrate. A method for manufacturing an amorphous silicon solar cell, characterized by:
置換である１〜４核体成分、又はパーフルオロ基を含む
メタ置換又はパラ置換である２〜４核体成分である。〕 で示される繰り返し単位を有するポリイミドを主成分と
する無色透明なポリイミドフィルムで形成されている請
求項１記載の非晶質シリコン太陽電池の製造方法。(2) The substrate is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [However, R_1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , and R_2 is an aromatic nucleus bonded to the nitrogen atom is a mono- to tetra-nuclear component which is meta-substituted, or a di- to tetra-nuclear component which is meta-substituted or para-substituted containing a perfluoro group. ] The method for manufacturing an amorphous silicon solar cell according to claim 1, wherein the amorphous silicon solar cell is formed of a colorless and transparent polyimide film containing polyimide as a main component having a repeating unit represented by the following.
１又は２記載の非晶質シリコン太陽電池の製造方法。(3) The method for manufacturing an amorphous silicon solar cell according to claim 1 or 2, wherein the support is subjected to a surface peeling treatment.
、該シリコーン系剥離剤を１００〜３５０℃の加熱雰囲
気下で耐熱性の支持体に焼付けられている請求項３記載
の非晶質シリコン太陽電池の製造方法。(4) The amorphous silicon solar cell according to claim 3, wherein a silicone-based release agent is used as the surface release treatment agent, and the silicone-based release agent is baked onto a heat-resistant support in a heated atmosphere of 100 to 350°C. How to manufacture batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091576A JPH0249475A (en) | 1988-05-19 | 1989-04-10 | Manufacture of amorphous silicon solar cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-122791 | 1988-05-19 | ||
| JP12279188 | 1988-05-19 | ||
| JP1091576A JPH0249475A (en) | 1988-05-19 | 1989-04-10 | Manufacture of amorphous silicon solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0249475A true JPH0249475A (en) | 1990-02-19 |
Family
ID=26433014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1091576A Pending JPH0249475A (en) | 1988-05-19 | 1989-04-10 | Manufacture of amorphous silicon solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0249475A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256566A (en) * | 1991-05-08 | 1993-10-26 | Texas Instruments Incorporated | Method for in-situ doping of deposited silicon |
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| JPH06334204A (en) * | 1993-05-21 | 1994-12-02 | Ind Technol Res Inst | Preparation of flexible amorphous silicon solar cell |
| US5902650A (en) * | 1995-07-11 | 1999-05-11 | Applied Komatsu Technology, Inc. | Method of depositing amorphous silicon based films having controlled conductivity |
| US6352910B1 (en) | 1995-07-11 | 2002-03-05 | Applied Komatsu Technology, Inc. | Method of depositing amorphous silicon based films having controlled conductivity |
| JP2010202729A (en) * | 2009-03-02 | 2010-09-16 | Hitachi Chemical Dupont Microsystems Ltd | Polyimide precursor resin composition for flexible device substrates and method for producing flexible device using the same, and flexible device |
| JP2010283262A (en) * | 2009-06-08 | 2010-12-16 | Toyobo Co Ltd | Lamination body and manufacturing method thereof |
| CN104952780A (en) * | 2014-03-31 | 2015-09-30 | 新日铁住金化学株式会社 | Method of manufacturing a flexible device, a flexible device, a flexible device manufacturing apparatus and a resin solution for forming a flexible substrate |
| JP2020026525A (en) * | 2018-08-08 | 2020-02-20 | 協立化学産業株式会社 | Thermosetting resin composition and method for producing processing resin varnish curing film |
-
1989
- 1989-04-10 JP JP1091576A patent/JPH0249475A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256566A (en) * | 1991-05-08 | 1993-10-26 | Texas Instruments Incorporated | Method for in-situ doping of deposited silicon |
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| JPH07233325A (en) * | 1991-10-25 | 1995-09-05 | Internatl Business Mach Corp <Ibm> | Radiation-reactive composition |
| US5780199A (en) * | 1991-10-25 | 1998-07-14 | International Business Machines Corporation | Polyamic acid and polyimide from fluorinated reactant |
| JPH06334204A (en) * | 1993-05-21 | 1994-12-02 | Ind Technol Res Inst | Preparation of flexible amorphous silicon solar cell |
| US6352910B1 (en) | 1995-07-11 | 2002-03-05 | Applied Komatsu Technology, Inc. | Method of depositing amorphous silicon based films having controlled conductivity |
| US5902650A (en) * | 1995-07-11 | 1999-05-11 | Applied Komatsu Technology, Inc. | Method of depositing amorphous silicon based films having controlled conductivity |
| JP2010202729A (en) * | 2009-03-02 | 2010-09-16 | Hitachi Chemical Dupont Microsystems Ltd | Polyimide precursor resin composition for flexible device substrates and method for producing flexible device using the same, and flexible device |
| JP2010283262A (en) * | 2009-06-08 | 2010-12-16 | Toyobo Co Ltd | Lamination body and manufacturing method thereof |
| CN104952780A (en) * | 2014-03-31 | 2015-09-30 | 新日铁住金化学株式会社 | Method of manufacturing a flexible device, a flexible device, a flexible device manufacturing apparatus and a resin solution for forming a flexible substrate |
| KR20150113926A (en) * | 2014-03-31 | 2015-10-08 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method of manufacturing a flexible device, a flexible device, a flexible device manufacturing apparatus and a resin solution for forming a flexible substrate |
| JP2015199349A (en) * | 2014-03-31 | 2015-11-12 | 新日鉄住金化学株式会社 | Method of producing flexible device and flexible device, and production apparatus for flexible device |
| JP2020026525A (en) * | 2018-08-08 | 2020-02-20 | 協立化学産業株式会社 | Thermosetting resin composition and method for producing processing resin varnish curing film |
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