JPH04326577A - Photoelectric transducer - Google Patents
Photoelectric transducerInfo
- Publication number
- JPH04326577A JPH04326577A JP3096568A JP9656891A JPH04326577A JP H04326577 A JPH04326577 A JP H04326577A JP 3096568 A JP3096568 A JP 3096568A JP 9656891 A JP9656891 A JP 9656891A JP H04326577 A JPH04326577 A JP H04326577A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- film
- forming
- photoelectric conversion
- thickness
- 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.)
- Granted
Links
- 239000010409 thin film Substances 0.000 claims abstract description 109
- 239000010408 film Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 abstract description 38
- 150000002500 ions Chemical class 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 28
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 37
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 238000010884 ion-beam technique Methods 0.000 description 12
- -1 boron halide Chemical class 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000012010 growth Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000005566 electron beam evaporation Methods 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910052743 krypton Inorganic materials 0.000 description 5
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 5
- 229910052754 neon Inorganic materials 0.000 description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000078 germane Chemical class 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- VJFOQKOUHKDIGD-UHFFFAOYSA-N [GeH3][SiH3] Chemical compound [GeH3][SiH3] VJFOQKOUHKDIGD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 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
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YDLQKLWVKKFPII-UHFFFAOYSA-N timiperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(N2C(NC3=CC=CC=C32)=S)CC1 YDLQKLWVKKFPII-UHFFFAOYSA-N 0.000 description 1
- 229950000809 timiperone Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000011787 zinc oxide 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
Landscapes
- Photovoltaic Devices (AREA)
- Recrystallisation Techniques (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は非晶質太陽電池の高性能
化に関し、特に、導電性薄膜に極薄膜状態で結晶性を有
する半導体薄膜を適用し、開放端電圧、光電変換効率を
改善する技術に関する。[Industrial Application Field] The present invention relates to improving the performance of amorphous solar cells, and in particular, improves open circuit voltage and photoelectric conversion efficiency by applying a crystalline semiconductor thin film in an extremely thin film state to a conductive thin film. related to technology.
【０００２】0002
【従来の技術】非晶質太陽電池は、電卓や時計を駆動す
るための出力の小さいエネルギー供給源として既に実用
化されている。しかしながら、太陽光発電用途のように
、 ０．１Ｗ以上のような出力の大きいエネルギー供給
源としては、性能および安定性に関しては十分とはいえ
ず、性能向上をめざして、各種の検討が実施されている
。しかして、太陽電池の光電変換効率は開放端電圧、短
絡光電流ならびに曲線因子の積で表される。各種の検討
の結果、短絡光電流ならびに曲線因子については、現在
の達成値は理論的に予想される値に近づいてきたが、こ
と開放端電圧は未だ充分改善されていない。2. Description of the Related Art Amorphous solar cells have already been put into practical use as a low-output energy supply source for driving calculators and watches. However, as an energy supply source with a large output of 0.1W or more, such as in photovoltaic power generation applications, it cannot be said that the performance and stability are sufficient, and various studies have been carried out with the aim of improving performance. ing. Therefore, the photoelectric conversion efficiency of a solar cell is expressed as the product of open circuit voltage, short circuit photocurrent, and fill factor. As a result of various studies, the currently achieved values for the short-circuit photocurrent and fill factor are approaching the theoretically expected values, but the open-circuit voltage, in particular, has not yet been sufficiently improved.
【０００３】太陽電池の信頼性向上のために、近年、光
入射側にｐ層を設けたｐｉｎ型非晶質太陽電池が検討さ
れている。この非晶質太陽電池において、開放端電圧を
改善するためには、ｐ型半導体薄膜の光電特性を改善せ
ねばならず、特に、光学的バンドギャップの拡大と電気
導電率の向上を同時に行わねばならないところに、技術
の困難性があった。In order to improve the reliability of solar cells, pin-type amorphous solar cells in which a p-layer is provided on the light incident side have been studied in recent years. In order to improve the open circuit voltage of this amorphous solar cell, it is necessary to improve the photoelectric properties of the p-type semiconductor thin film, and in particular, it is necessary to expand the optical band gap and improve the electrical conductivity at the same time. This was not possible due to technical difficulties.
【０００４】これらを満足する材料として、微結晶薄膜
が提案されているが、プラズマＣＶＤ法などの従来技術
を用いて、透明電極上にｐ型微結晶薄膜を形成すべき成
膜条件で薄膜の形成を試みても、結果的には非晶質太陽
電池の開放端電圧は向上していない。この理由として、
ｐｉｎ型非晶質太陽電池のｐ層として必要十分な５０〜
３００Åの膜厚において、透明電極上にｐ型微結晶薄膜
を形成することが困難なためであることが報告されてい
る（例えば、ビー．ゴールドスタイン他「通常のＲＦグ
ロー放電によって成膜されたｐ型 ＳｉＣ：Ｈ微結晶薄
膜の特性」、アプライドフィジックス レター、５３
巻、２６７２〜２６７４頁、１９８８年発行（Ｂ．Ｇｏ
ｌｄｓｔｅｉｎ ｅｔ ａｌ．，”Ｐｒｏｐｅｒｔｉｅ
ｓ ｏｆ Ｐ＋ ｍｉｃｒｏｃｒｙｓｔａｌｌｉｎｅ
ｆｉｌｍｓ ｏｆ ＳｉＣ：Ｈ ｄｅｐｏｓｉｔｅｄ
ｂｙ ｃｏｎｖｅｎｔｉｏｎａｌ ｒｆ ｇｌｏｗ ｄ
ｉｓｃｈａｒｇｅ”， Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃ
ｓ ｌｅｔｔｅｒｓ， ５３， ｐ２６７２〜２６７４
（１９８８））。つまり、５０〜３００ Åの膜厚に
おいては結晶化せず、高抵抗化しており、曲線因子も低
く、開放端電圧の改善も得られない。一方、ＥＣＲ（Ｅ
ｌｅｃｔｒｏｎ ＣｙｃｌｏｔｒｏｎＲｅｓｏｎａｎｅ
） プラズマＣＶＤ法を用いてｐ層を形成した場合は、
開放端電圧の改善および光電変換効率の向上が報告され
ているが、本法ではイオン衝撃による下地材料への損傷
が激しく、本法によって得られるｐ型微結晶薄膜の特性
を十分に引き出せていないのが現状である（例えば、ユ
タカ．ハットリ他「ＥＣＲ−ＣＶＤで形成したｐ型微結
晶 ＳｉＣ膜を用いた高効率アモルファスヘテロ接合太
陽電池」テクニカル ダイジェスト オブ イン
ターナショナル ＰＶＳＥＣ−３、 １７１〜１７４頁
、１９８７年発行（Ｙ．Ｈａｔｔｏｒｉ ｅｔ ａｌ．
， ”Ｈｉｇｈ Ｅｆｆｉｃｉｅｎｃｙ Ａｍｏｒｐｈ
ｏｕｓ Ｈｅｔｅｒｏｊｕｎｃｔｉｏｎ Ｓｏｌａｒ
ｃｅｌｌ Ｅｍｐｌｏｙｉｎｇ ＥＣＲ−ＣＶＤ Ｐｒ
ｏｄｕｃｅｄ ｐ−Ｔｙｐｅ Ｍｉｃｒｏｃｒｙｓｔａ
ｌｌｉｎｅ ＳｉＣ Ｆｉｌｍ”， Ｔｅｃｈｎｉｃａ
ｌ Ｄｉｇｅｓｔ ｏｆ ｔｈｅ Ｉｎｔｅｒｎａｔｉ
ｏｎａｌ ＰＶＳＥＣ−３、ｐ．１７１ 〜１７４（１
９８７））。A microcrystalline thin film has been proposed as a material that satisfies these requirements, but it is difficult to form a thin film using conventional techniques such as plasma CVD under film-forming conditions to form a p-type microcrystalline thin film on a transparent electrode. Despite attempts to form amorphous solar cells, the open-circuit voltage of amorphous solar cells has not improved. The reason for this is
50~ which is necessary and sufficient for the p layer of a pin type amorphous solar cell
It has been reported that this is because it is difficult to form a p-type microcrystalline thin film on a transparent electrode at a film thickness of 300 Å (for example, B. Goldstein et al. “Characteristics of p-type SiC:H microcrystalline thin films”, Applied Physics Letters, 53
Volume, pp. 2672-2674, published 1988 (B.Go
ldstein et al. ,”Property
s of P+ microcrystalline
films of SiC：H deposited
by conventional rf glow d
Applied Physics
s letters, 53, p2672-2674
(1988)). That is, in a film thickness of 50 to 300 Å, the film does not crystallize, has a high resistance, has a low fill factor, and cannot improve the open circuit voltage. On the other hand, ECR(E
lectron Cyclotron Resonane
) When the p layer is formed using the plasma CVD method,
Improvements in open-circuit voltage and photoelectric conversion efficiency have been reported, but this method causes severe damage to the underlying material due to ion bombardment, and the characteristics of the p-type microcrystalline thin film obtained by this method cannot be fully exploited. (For example, Yutaka Hattori et al., "High-efficiency amorphous heterojunction solar cell using p-type microcrystalline SiC film formed by ECR-CVD," Technical Digest of International PVSEC-3, pp. 171-174, 1987. Published in 2013 (Y. Hattori et al.
, ”High Efficiency Amorph
ous Heterojunction Solar
Cell Employing ECR-CVD Pr
oduced p-Type Microcrysta
lline SiC Film”, Technica
Digest of the International
onal PVSEC-3, p. 171 to 174 (1
987)).
【０００５】近年、成膜後、マイクロ波プラズマや高周
波プラズマ等で発生させた原子状水素で処理することを
繰り返すことにより、微結晶薄膜を得られることが報告
されているが、これらについては、全膜厚が ３００Å
以下でも微結晶化が可能であるかは言及されていない（
例えば、エー．アサノ「水素化アモルファスシリコンお
よび微結晶シリコン薄膜の網目構造に対する水素原子の
影響」、アプライド フィジックス レター、５６
巻、５３３ 〜５３５ 頁、１９９０年発行 （Ａ．Ａ
ｓａｎｏ， ”Ｅｆｆｅｃｔｓ ｏｆｈｙｄｒｏｇｅｎ
ａｔｏｍｓ ｏｎ ｔｈｅ ｎｅｔｗｏｒｋ ｓｔｒ
ｕｃｔｕｒｅ ｏｆ ｈｙｄｒｏｇｅｎａｔｅｄ ａｍ
ｏｒｐｈｏｕｓ ａｎｄｍｉｃｒｏｃｒｙｓｔａｌｌｉ
ｎｅ ｓｉｌｉｃｏｎ ｔｈｉｎ ｆｉｌｍｓ”， Ａ
ｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ ｌｅｔｔｅｒｓ， ５
６， ｐ．５３３〜５３５（１９９０））、イサム．シ
ミズ他「低基板温度での結晶性シリコンの成長に対する
化学反応制御」、マテリアル リサーチ ソサエテ
ィー シンポジウム プロシーディング、１６４
巻、１９５ 〜２０４ 頁、１９９０年発行（Ｉ．Ｓｈ
ｉｍｉｚｕ ｅｔ ａｌ．，”ＣＯＮＴＲＯＬＯＦ Ｃ
ＨＥＭＩＣＡＬ ＲＥＡＣＴＩＯＮＳ ＦＯＲ ＧＲＯ
ＷＴＨ ＯＦ ＣＲＹＳＴＡＬＬＩＮＥ Ｓｉ ＡＴ
ＬＯＷ ＳＵＢＳＴＲＡＴＥ ＴＥＭＰＥＲＡＴＵＲＥ
”， Ｍａｔｅｒｉａｌｓ Ｒｅｓｅａｒｃｈ Ｓｏｃ
ｉｅｔｙ Ｓｙｍｐｏｓｉｕｍ Ｐｒｏｃｅｅｄｉｎｇ
Ｖｏｌ．１６４， ｐ．１９５〜２０４ （１９９０
）））。In recent years, it has been reported that microcrystalline thin films can be obtained by repeating treatment with atomic hydrogen generated by microwave plasma, high-frequency plasma, etc. after film formation. Total film thickness is 300Å
It is not mentioned whether microcrystalization is possible in the following (
For example, A. Asano, “Influence of hydrogen atoms on the network structure of hydrogenated amorphous silicon and microcrystalline silicon thin films,” Applied Physics Letters, 56.
Volume, pages 533-535, published in 1990 (A.A.
sano, ``Effects of hydrogen
atoms on the network str
structure of hydrogenated am
orphous and microcrystalli
ne silicon thin films”, A
pplied Physics letters, 5
6, p. 533-535 (1990)), Isamu. Shimizu et al., “Chemical reaction control for crystalline silicon growth at low substrate temperatures,” Materials Research Society Symposium Proceedings, 164.
Volume, pp. 195-204, published in 1990 (I.Sh
imizu et al. ,” CONTROLOF C
HEMICAL REACTIONS FOR GRO
WTH OF CRYSTALLINE Si AT
LOW SUBSTRATE TEMPERATURE
”, Materials Research Soc.
iety Symposium Proceedings
Vol. 164, p. 195-204 (1990
))).
【０００６】また、９００ 〜１０００Åのシリコン薄
膜を形成後、イオンビームを処理することにより、微結
晶薄膜を得られることも報告されているが、これらの場
合、ｋｅＶ 〜ＭｅＶ オーダーの高エネルギーのイオ
ンを照射しなければならず（例えば、ジェ−．エス．イ
ム他「アモルファスシリコン薄膜内でのイオン照射によ
る結晶核生成」アプライド フィジックス レター
、５７巻、１７６６〜１７６８頁、１９９０年発行 （
Ｊ．Ｓ．Ｉｍｅｔ ａｌ．， ”Ｉｏｎ ｉｒｒａｄｉ
ａｔｉｏｎ ｅｎｈａｎｃｅｄ ｃｒｙｓｔａｌ ｎｕ
ｃｌｅａｔｉｏｎｉｎ ａｍｏｒｐｈｏｕｓ Ｓｉ ｔ
ｈｉｎ ｆｉｌｍｓ”， Ａｐｐｌｉｅｄ Ｐｈｙｓｉ
ｃｓ ｌｅｔｔｅｒｓ， ５７， ｐ．１７６６ 〜１
７６８ （１９９０））、シー．スピネラ他「化学気相
堆積法によるアモルファスシリコンへのイオンビーム照
射下での粒成長機構」アプライド フィジックス
レタ−、５７巻、５５４ 〜５５６ 頁、１９９０年発
行（Ｃ．Ｓｐｉｎｅｌｌａ ｅｔ ａｌ．， ”Ｇｒａ
ｉｎ ｇｒｏｗｔｈ ｋｉｎｅｔｉｃｓ ｄｕｒｉｎｇ
ｉｏｎ ｂｅａｍ ｉｒｒａｄｉａｔｉｏｎ ｏｆ
ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｅｄ
ａｍｏｒｐｈｏｕｓ ｓｉｌｉｃｏｎ”， Ａｐｐｌｉ
ｅｄ Ｐｈｙｓｉｃｓ ｌｅｔｔｅｒｓ， ５７， ｐ
．５５４ 〜５５６ （１９９０）））、下地材料への
損傷が生じること、並びに、装置が極めて大型で高価な
ものになり、実用的でない。It has also been reported that a microcrystalline thin film can be obtained by forming a silicon thin film of 900 to 1000 Å and then treating it with an ion beam, but in these cases, high-energy ions on the order of keV to MeV are used. (For example, J.S. Im et al., "Crystal Nucleation by Ion Irradiation in Amorphous Silicon Thin Films," Applied Physics Letters, Vol. 57, pp. 1766-1768, Published in 1990.
J. S. Imet al. , ”Ion irradi
ation enhanced crystal nu
creationin amorphous sit
hin films”, Applied Physi
cs letters, 57, p. 1766 ~1
768 (1990)), C. Spinella et al. “Grain growth mechanism under ion beam irradiation of amorphous silicon by chemical vapor deposition” Applied Physics
Letter, vol. 57, pp. 554-556, published in 1990 (C. Spinella et al., “Gra
in growth kinetics during
ion beam irradiation of
chemical vapor deposited
amorphous silicon", Appli
ed Physics letters, 57, p.
．． 554-556 (1990))), damage to the underlying material occurs and the device becomes extremely large and expensive, making it impractical.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、導電性薄膜
に結晶性の半導体薄膜を形成して開放端電圧を向上させ
た光電変換素子を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a photoelectric conversion element in which an open-circuit voltage is improved by forming a crystalline semiconductor thin film on a conductive thin film.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため、鋭意検討した結果、成長表面へ１ｋｅ
Ｖ以下の低エネルギ−イオンを照射しながら １００Å
以下の極薄膜を形成後、更に、イオン照射を継続するこ
とにより、膜の結晶化を促進させ、３００ Å以下の膜
厚でも結晶性を有する半導体薄膜を形成できることを見
出し、本発明を完成した。[Means for Solving the Problems] In order to solve the above problems, the present inventors have made extensive studies and have found that
100Å while irradiating with low energy ions below V
After forming the following ultra-thin film, we further discovered that by continuing ion irradiation, the crystallization of the film could be promoted and a semiconductor thin film with crystallinity could be formed even with a film thickness of 300 Å or less, and the present invention was completed. .
【０００９】本結晶性薄膜をｐ層またはｎ層に用いるこ
とにより、極めて高い開放端電圧、光電変換効率を有す
る光電変換素子を得ることが出来る。By using this crystalline thin film in the p-layer or n-layer, a photoelectric conversion element having extremely high open circuit voltage and photoelectric conversion efficiency can be obtained.
【００１０】本発明は、基体上に、第一の電極、第一の
導電性薄膜、より薄い第一の実質的に真性の薄膜、より
厚い第二の実質的に真性の薄膜、第二の導電性薄膜、第
二の電極の順に形成した光電変換素子において、少なく
とも、第一の導電性薄膜を荷電粒子を含む雰囲気で薄膜
形成を行う工程（以下、成膜工程と略称する）と薄膜形
成原料の供給を停止して当該薄膜形成表面に荷電粒子の
みを導く工程（以下、改質工程と略称する）とを繰り返
し、かつ、両工程の一回づつの繰り返しにおいて成膜さ
れる薄膜の厚みが１から １００Åである全膜厚が ３
００Å以下の結晶性半導体薄膜であることを特徴とする
光電変換素子である。The present invention provides a first electrode, a first conductive thin film, a thinner first substantially intrinsic thin film, a thicker second substantially intrinsic thin film, and a second substantially intrinsic thin film on a substrate. In a photoelectric conversion element in which a conductive thin film and a second electrode are formed in this order, at least a step of forming a first conductive thin film in an atmosphere containing charged particles (hereinafter abbreviated as a film forming step) and a thin film forming step are performed. The thickness of the thin film formed by repeating the process of stopping the supply of raw materials and introducing only charged particles to the thin film forming surface (hereinafter referred to as the modification process), and repeating both processes once. is 1 to 100 Å and the total film thickness is 3
This photoelectric conversion element is characterized by being a crystalline semiconductor thin film with a thickness of 00 Å or less.
【００１１】本発明においては、少なくとも、第一の導
電性薄膜に結晶性半導体薄膜を適用することが必須であ
るが、第二の導電性薄膜に同様の結晶性薄膜を適用して
も、なんら本発明の効果を妨げるものではなく、むしろ
好ましい形態である。以下に導電性薄膜の形成の詳細を
説明する。In the present invention, it is essential to apply at least a crystalline semiconductor thin film to the first conductive thin film, but even if a similar crystalline thin film is applied to the second conductive thin film, there will be no problem. This does not hinder the effects of the present invention, but is rather a preferable form. Details of the formation of the conductive thin film will be explained below.
【００１２】導電性薄膜の形成において、第一の導電性
薄膜と第二の導電性薄膜とは、互いに異なる導電型を有
するものである。例えば、第一の導電型をｐ型とすれば
、第二の導電型はｎ型になる。その逆の場合もありえる
ことは云うまでもない。In forming the conductive thin film, the first conductive thin film and the second conductive thin film have conductivity types different from each other. For example, if the first conductivity type is p-type, the second conductivity type is n-type. Needless to say, the opposite case is also possible.
【００１３】成膜工程は、その薄膜成長を荷電粒子を含
む雰囲気で行うことに特徴を有し、薄膜形成原料の供給
手段、即ち成膜手段自体は、特に限定されるものではな
い。具体的には、真空蒸着、スパッタリング、イオンプ
レーティングなどの物理的成膜方法や光ＣＶＤ、プラズ
マＣＶＤなどの化学気相成膜（ＣＶＤ）法により実施さ
れる。イオン照射とは、陽イオンまたは陰イオンを含む
雰囲気を発生させ、基板にバイアス電圧を印加する等の
手段により、基板の薄膜表面に導く（衝突させる） も
のである。The film forming process is characterized in that the thin film is grown in an atmosphere containing charged particles, and the means for supplying the thin film forming raw material, that is, the film forming means itself is not particularly limited. Specifically, this is carried out by a physical film forming method such as vacuum evaporation, sputtering, or ion plating, or a chemical vapor deposition (CVD) method such as optical CVD or plasma CVD. Ion irradiation involves generating an atmosphere containing positive ions or negative ions, and guiding (colliding) the atmosphere onto the thin film surface of the substrate by applying a bias voltage to the substrate.
【００１４】一方、改質工程とは、成膜工程での薄膜形
成原料の供給を停止し、荷電粒子を含む雰囲気のみ継続
させ、基板の薄膜形成表面に導き（衝突させ）、半導体
薄膜の性質を改善する工程である。On the other hand, in the modification process, the supply of the thin film forming raw material in the film forming process is stopped, and only the atmosphere containing charged particles is continued, which is introduced (collided) with the thin film forming surface of the substrate to modify the properties of the semiconductor thin film. It is a process to improve
【００１５】以下に、効果的な物理的成膜方法を説明す
る。前述したように、成膜工程での荷電粒子を含む雰囲
気は、これから説明する物理的成膜方法や化学気相成膜
法と併せて行われるものであるが、独立に制御できるも
のであり、改質工程での荷電粒子を含む雰囲気と同じ発
生方法であるので、効果的な発生法などについては、後
述する改質工程の具体的な項で説明する。An effective physical film forming method will be explained below. As mentioned above, the atmosphere containing charged particles in the film formation process is performed in conjunction with the physical film formation method and chemical vapor deposition method described below, but it can be controlled independently. Since this is the same generation method as the atmosphere containing charged particles in the modification process, effective generation methods will be explained in the specific section on the modification process described later.
【００１６】成膜のための出発原料として、シリコン、
炭化シリコン、窒化シリコン、シリコン−ゲルマニウム
合金または複合粉末、シリコン−錫合金または複合粉末
などの元素や化合物、合金を効果的に用いることができ
る。この他にも炭素、ゲルマニウム、錫等の元素、化合
物、合金を用いることもできる。As starting materials for film formation, silicon,
Elements, compounds, and alloys such as silicon carbide, silicon nitride, silicon-germanium alloy or composite powder, silicon-tin alloy or composite powder can be effectively used. Other than these, elements, compounds, and alloys such as carbon, germanium, and tin can also be used.
【００１７】ｐ型の導電性を付与するには、出発原料に
元素の周期率表第 ＩＩＩ族の元素（例えば、ホウ素）
を含む化合物を用いるか、ジボラン、ハロゲン化ホウ素
、トリメチルホウ素ガス等の雰囲気で成膜することで行
える。また、ｎ型の導電性を付与するには、出発原料に
第Ｖ族の元素（例えば、リン）を含む化合物を用いるか
、ホスフィン、アルシン、ハロゲン化リン、ハロゲン化
砒素、アルキルリン、アルキル砒素ガス等の雰囲気で成
膜することで行える。In order to impart p-type conductivity, an element from group III of the periodic table of elements (for example, boron) is added to the starting material.
This can be done by using a compound containing , or by forming a film in an atmosphere of diborane, boron halide, trimethylboron gas, or the like. In addition, in order to impart n-type conductivity, a compound containing a group V element (for example, phosphorus) is used as a starting material, or phosphine, arsine, phosphorus halide, arsenic halide, alkyl phosphorus, alkyl arsenic This can be done by forming a film in an atmosphere such as gas.
【００１８】成膜条件は、薄膜成長中にイオンを照射す
る以外には、とくに限定されるものではなく、アルゴン
、キセノン、ヘリウム、ネオン、クリプトン等の希ガス
、水素、炭化水素、フッ素、窒素、酸素ガス等の雰囲気
で成膜することができる。具体的な条件として、ガス流
量は、０．１ 〜 １００ｓｃｃｍ、反応圧力は、０．
０００１ｍｔｏｒｒ 〜１００ｍｔｏｒｒの範囲である
。また、成膜速度に応じて、流量、圧力、電力等の成膜
条件は適宜選択される。The film forming conditions are not particularly limited, except that ions are irradiated during thin film growth, and rare gases such as argon, xenon, helium, neon, and krypton, hydrogen, hydrocarbons, fluorine, and nitrogen are used. The film can be formed in an atmosphere of , oxygen gas, or the like. As specific conditions, the gas flow rate is 0.1 to 100 sccm, and the reaction pressure is 0.1 to 100 sccm.
The range is from 0001 mtorr to 100 mtorr. Further, film forming conditions such as flow rate, pressure, and electric power are appropriately selected depending on the film forming rate.
【００１９】成膜温度については、基板温度を管理する
ことで成膜が行われる。温度範囲は、基本的には制約を
うけるものではないが、改質工程に適合させて温度を設
定することが好ましい。具体的には、 ５００℃以下の
温度範囲で選択される。Regarding the film formation temperature, film formation is performed by controlling the substrate temperature. Although the temperature range is basically not subject to any restrictions, it is preferable to set the temperature in accordance with the reforming process. Specifically, it is selected within a temperature range of 500°C or less.
【００２０】次に、効果的な化学気相成膜法の具体的示
例を示す。Next, a specific example of an effective chemical vapor deposition method will be shown.
【００２１】成膜のための原料ガスとして、一般式Ｓｉ
ｎ Ｈ２ｎ＋２（ｎは自然数）で表されるモノシラン、
ジシラン、トリシラン、テトラシランなどシラン化合物
や、フッ化シラン、有機シラン、炭化水素、ゲルマン化
合物などが用いられる。また、水素、重水素、フッ素、
塩素、ヘリウム、アルゴン、ネオン、キセノン、クリプ
トン、窒素などのガスを原料ガスとともに導入しても良
い。これらのガスを用いる場合には、原料ガスに対して
、０．０１〜 １００％（容積比率）の範囲で用いると
効果的であり、成膜速度や膜特性を考慮して適宜選択さ
れるものである。As a raw material gas for film formation, general formula Si
Monosilane represented by n H2n+2 (n is a natural number),
Silane compounds such as disilane, trisilane, and tetrasilane, fluorinated silanes, organic silanes, hydrocarbons, and germane compounds are used. In addition, hydrogen, deuterium, fluorine,
Gases such as chlorine, helium, argon, neon, xenon, krypton, and nitrogen may be introduced together with the source gas. When using these gases, it is effective to use them in a range of 0.01 to 100% (volume ratio) based on the source gas, and the gases should be selected appropriately taking into account the film formation rate and film properties. It is.
【００２２】ｐ型の導電性を付与するには、原料ガスに
ジボラン、ハロゲン化ホウ素、トリメチルホウ素ガス等
を加えて、成膜することで行える。また、ｎ型の導電性
を付与するには、原料ガスにホスフィン、アルシン、ハ
ロゲン化リン、ハロゲン化砒素、アルキルリン、アルキ
ル砒素ガス等を加えて、成膜することで行える。P-type conductivity can be imparted by adding diborane, boron halide, trimethylboron gas, etc. to the raw material gas and forming a film. In addition, n-type conductivity can be imparted by adding phosphine, arsine, phosphorus halide, arsenic halide, alkyl phosphorus, alkyl arsenic gas, etc. to the raw material gas and forming a film.
【００２３】成膜条件については、物理的成膜方法と同
様に、薄膜成長中に荷電粒子を含む雰囲気で行うこと以
外にはとくに限定されるものではない。具体的な条件を
以下に開示する。[0023] As with the physical film-forming method, there are no particular limitations on the film-forming conditions, other than that the thin film is grown in an atmosphere containing charged particles. The specific conditions are disclosed below.
【００２４】光ＣＶＤは、低圧水銀ランプや重水素ラン
プや希ガスランプなどの、波長３５０ｎｍ以下の紫外光
源を用いて原料ガスを分解し成膜が行われる。成膜時の
条件として、ガス流量１〜 １００ｓｃｃｍ、反応圧力
１５ｍｔｏｒｒ 〜大気圧、基板温度 ２００〜 ６０
０℃、基板の耐熱性、成膜速度から考えられる成膜時間
、改質工程の温度等を考慮すると、より好ましくは、
３００〜 ５００℃の範囲において適宜選択される。In optical CVD, film formation is performed by decomposing a source gas using an ultraviolet light source with a wavelength of 350 nm or less, such as a low-pressure mercury lamp, deuterium lamp, or rare gas lamp. Conditions during film formation include gas flow rate of 1 to 100 sccm, reaction pressure of 15 mtorr to atmospheric pressure, and substrate temperature of 200 to 60 mtorr.
0°C, the heat resistance of the substrate, the film formation time considered from the film formation rate, the temperature of the modification process, etc., more preferably,
The temperature is appropriately selected within the range of 300 to 500°C.
【００２５】また、プラズマＣＶＤについて、以下に具
体的に示す。放電の方式として、高周波放電、直流放電
、マイクロ波放電、ＥＣＲ放電等の方式を有効に用いる
ことができる。原料ガスの流量１〜 ９００ｓｃｃｍ、
反応圧力０．００１ｍｔｏｒｒ〜大気圧、電力１ｍＷ／
ｃｍ２〜 １０Ｗ／ｃｍ２の範囲で十分である。これら
の成膜条件は成膜速度、放電方法に応じ適宜変更される
ものである。基板温度は２００ 〜 ６００℃であり、
より好ましくは、 ３００〜 ５００℃である。Further, plasma CVD will be specifically described below. As the discharge method, methods such as high frequency discharge, direct current discharge, microwave discharge, and ECR discharge can be effectively used. Flow rate of raw material gas: 1 to 900 sccm,
Reaction pressure 0.001 mtorr to atmospheric pressure, power 1 mW/
A range of cm2 to 10 W/cm2 is sufficient. These film forming conditions are changed as appropriate depending on the film forming rate and the discharge method. The substrate temperature is 200 to 600°C,
More preferably, it is 300 to 500°C.
【００２６】本発明において、改質工程及び成膜工程に
おける荷電粒子を含む雰囲気とは、非堆積性のガスを用
いた放電により、荷電粒子を発生させ、成長表面に暴露
した雰囲気であり、その雰囲気中にイオン化されていな
いものが存在していても、なんら本発明の効果を妨げる
ものではない。この放電雰囲気に暴露するとともに、基
板にバイアス電圧を印加し、イオン化した成分を効果的
に基板上に導くことは改質方法としてより好ましい手段
である。放電を発生させる方式は高周波放電、直流放電
、マイクロ波放電、ＥＣＲ放電等を有効に利用すること
ができる。又、イオン発生装置により、効果的にイオン
を発生せしめ、これを基板表面に導くことも本発明にお
いては有用な方法である。具体的には、カウフマン型イ
オン銃やＥＣＲイオン銃など種々のイオン発生装置が用
いられる。非堆積性のガスとは、水素、フッ素、フッ素
化合物等の反応性ガス及びアルゴン、ネオン、ヘリウム
、キセノン、クリプトン等の希ガス等であり、水素ガス
、重水素ガス、フッ化水素ガス、フッ素ガス、三フッ化
窒素、四フッ化炭素、アルゴンガス、ネオンガス、ヘリ
ウムガス、キセノンガス、クリプトンガス等を有効に用
いることができる。また、これらのガスの混合物も有効
に用いることができる。In the present invention, the atmosphere containing charged particles in the modification step and the film forming step is an atmosphere in which charged particles are generated by discharge using a non-depositing gas and are exposed to the growth surface. Even if non-ionized substances exist in the atmosphere, this does not impede the effects of the present invention in any way. A more preferable modification method is to expose the substrate to this discharge atmosphere and apply a bias voltage to the substrate to effectively guide the ionized components onto the substrate. As a method for generating discharge, high frequency discharge, direct current discharge, microwave discharge, ECR discharge, etc. can be effectively used. Furthermore, it is also a useful method in the present invention to effectively generate ions using an ion generator and guide them to the substrate surface. Specifically, various ion generators such as a Kauffman ion gun and an ECR ion gun are used. Non-depositional gases include reactive gases such as hydrogen, fluorine, and fluorine compounds, and rare gases such as argon, neon, helium, xenon, and krypton. Gases such as nitrogen trifluoride, carbon tetrafluoride, argon gas, neon gas, helium gas, xenon gas, and krypton gas can be effectively used. Additionally, mixtures of these gases can also be used effectively.
【００２７】次に、改質工程の具体的な条件を開示する
。放電を用いる場合には、放電電力１〜５００Ｗ、非堆
積性のガスの流量５〜 ５００ｓｃｃｍ、圧力０．００
１ｍｔｏｒｒ〜大気圧の範囲において、発生維持される
。イオン銃を用いる場合には、非堆積性ガスの流量 ０
．１〜 ５０ｓｃｃｍ、圧力０．０００１ｍｔｏｒｒ
〜１００ｍｔｏｒｒであり、イオンの発生ならびに十分
の寿命を有する圧力範囲が用いられる。また、イオンエ
ネルギーとしては、１０〜１０００ｅＶの範囲で十分で
あり、好ましくは１００〜６００ｅＶである。イオンの
エネルギーをこの範囲を越えて高くすると、改質の効果
よりも、イオンによる損傷やスパッタリング現象が激し
くなり効果的でない。Next, specific conditions for the modification step will be disclosed. When using discharge, the discharge power is 1 to 500 W, the flow rate of non-depositing gas is 5 to 500 sccm, and the pressure is 0.00.
It is generated and maintained in the range of 1 mtorr to atmospheric pressure. When using an ion gun, the flow rate of non-depositional gas is 0
．． 1~50sccm, pressure 0.0001mtorr
~100 mtorr, a pressure range is used that provides ion generation and sufficient lifetime. Further, the ion energy is sufficient in the range of 10 to 1000 eV, preferably 100 to 600 eV. If the ion energy is increased beyond this range, the damage caused by the ions and the sputtering phenomenon will be more severe than the reforming effect, making it ineffective.
【００２８】改質工程における温度条件は、基板の温度
で管理される。この基板温度は、成膜工程の基板温度と
同じか、あるいはより低い温度であり、室温から ６０
０℃、好ましくは、 ２００〜 ５００℃である。The temperature conditions in the modification step are controlled by the temperature of the substrate. This substrate temperature is the same as or lower than the substrate temperature in the film forming process, and ranges from room temperature to 60°C.
0°C, preferably 200-500°C.
【００２９】一回の成膜工程においては、１ 〜１００
Å、好ましくは３ 〜５０Åの膜厚に形成される。膜
厚が １００Åを越える場合には、本発明の効果が低下
する。また、１Å未満の膜厚においては、実用性の観点
から成膜、改質の繰り返し回数が増加するので好ましく
ない。１サイクルに要する時間は、特に限定される要件
ではないが、１０００秒以内である。[0029] In one film forming process, 1 to 100
The film thickness is preferably 3 to 50 Å. When the film thickness exceeds 100 Å, the effect of the present invention decreases. Further, a film thickness of less than 1 Å is not preferable because the number of repetitions of film formation and modification increases from the viewpoint of practicality. The time required for one cycle is not particularly limited, but is within 1000 seconds.
【００３０】本発明において、実質的に真性の薄膜は、
水素化シリコン薄膜、水素化シリコンゲルマニウム薄膜
、水素化シリコンカーボン薄膜などであり、非晶質太陽
電池の光活性領域を形成するものである。これら実質的
に真性の薄膜は、分子内にシリコンを有する化合物、ゲ
ルマン、シリルゲルマンなどの分子内にゲルマニウムを
有する化合物、メチルシランなどの有機シラン化合物、
炭化水素ガスなどから目的の半導体薄膜に応じて適宜選
択される原料ガスに、プラズマＣＶＤ法や光ＣＶＤ法を
適用することにより容易に形成される。原料ガスを水素
、重水素、ヘリウム、アルゴン、キセノン、ネオン、ク
リプトンなどで希釈して用いることや原料ガスにごく微
量のジボランを添加することなど、実質的に真性の薄膜
形成における従来技術を併用することについては、なん
ら本発明の効果を妨げるものではない。[0030] In the present invention, the substantially intrinsic thin film is
These include hydrogenated silicon thin films, hydrogenated silicon germanium thin films, and hydrogenated silicon carbon thin films, which form the photoactive region of an amorphous solar cell. These substantially intrinsic thin films include compounds containing silicon in the molecule, compounds containing germanium in the molecule such as germane and silylgermane, organic silane compounds such as methylsilane,
It is easily formed by applying a plasma CVD method or a photo-CVD method to a raw material gas appropriately selected from hydrocarbon gas or the like depending on the desired semiconductor thin film. Combined with conventional techniques for forming substantially intrinsic thin films, such as diluting the source gas with hydrogen, deuterium, helium, argon, xenon, neon, krypton, etc., and adding a very small amount of diborane to the source gas. This does not in any way impede the effects of the present invention.
【００３１】形成条件は、温度１５０ 〜 ５００℃、
好ましくは、１７５〜 ３５０℃であり、形成圧力は０
．０１〜５ｔｏｒｒ、好ましくは、０．０３〜１．５ｔ
ｏｒｒ で行われる。実質的に真性の薄膜の膜厚は太陽
電池の用途に応じて適宜決定されるものであり、本発明
の限定条件ではない。本発明の効果を達成するためには
、１０００〜１００００Åで十分である。[0031] The formation conditions were a temperature of 150 to 500°C;
Preferably, the temperature is 175 to 350°C, and the forming pressure is 0.
．． 01 to 5 torr, preferably 0.03 to 1.5 t
It is done in orr. The thickness of the substantially intrinsic thin film is appropriately determined depending on the use of the solar cell, and is not a limiting condition of the present invention. A thickness of 1000 to 10000 Å is sufficient to achieve the effects of the present invention.
【００３２】本発明で用いる基体や電極の材料について
は特に制限されず、従来用いられている物質が有効に用
いられる。たとえば、基体としては、絶縁性または導電
性、透明、不透明のいずれかの性質を有するものでもよ
い。基本的にはガラス、アルミナ、シリコン、ステンレ
ススティール、アルミニウム、モリブデン、クロム、耐
熱性高分子等の物質で形成されるフィルムあるいは板状
の材料を有効に用いることができる。電極材料としては
、光入射側にはもちろん透明あるいは透明性の材料を用
いなければならないが、これ以外の実質的な制限はない
。アルミニウム、銀、クロム、チタン、ニッケル−クロ
ム、金、白金等の金属や酸化スズ、酸化亜鉛、酸化イン
ジウム等の金属酸化物の中から適宜、選択して用いるこ
とができる。The materials for the substrate and electrodes used in the present invention are not particularly limited, and conventionally used materials can be effectively used. For example, the substrate may be insulating or conductive, transparent, or opaque. Basically, film or plate-shaped materials formed from substances such as glass, alumina, silicon, stainless steel, aluminum, molybdenum, chromium, and heat-resistant polymers can be effectively used. As for the electrode material, a transparent or transparent material must of course be used on the light incident side, but there are no other practical limitations. An appropriate material can be selected from among metals such as aluminum, silver, chromium, titanium, nickel-chromium, gold, and platinum, and metal oxides such as tin oxide, zinc oxide, and indium oxide.
【００３３】[0033]
実施例１
本発明を実施するための装置としては、図１に示すよう
な基体挿入室（１）、第一の導電性薄膜形成室（２）、
実質的に真性の薄膜形成室（３）、第二の導電性薄膜形
成室（４）、第二の電極形成室（５）からなり、第一の
導電性薄膜形成室には、シリコンを堆積するための電子
ビーム蒸着装置（１４）およびイオンを発生するための
イオン発生装置（１５）を有していているものを用いた
。第一の電極として、酸化スズ薄膜が形成されたガラス
基体（７）は、基体挿入室で真空中加熱され、第一の導
電性薄膜形成室に移送される。第一の導電性薄膜は出発
原料として、高純度シリコンをるつぼにセッットし、電
子ビームを入射し、蒸発させて形成する。イオン発生装
置に、水素／ジボランを２０／０．１の割合で、圧力
１．５ｘ １０−３ｔｏｒｒ導入し、イオンビーム電圧
３００Ｖ 、加速電圧 ５０Ｖ印加し、イオンビーム
を発生させ、イオンビームのシャッターを開き、基体に
イオンビームを照射した。同時に、電子ビーム蒸着装置
のシャッターを２０秒開き、 ２５０℃に加熱された基
体上に２０Åシリコン薄膜を蒸着した。つぎに、電子ビ
ーム蒸着装置のシャッターを閉じ、イオンビーム照射の
みを１０秒おこなった。こうして、電子ビーム蒸着装置
のシャッターの開閉を各々の時間間隔で繰り返した。１
０回の繰り返しにより約 ２００Åの厚みのｐ型結晶性
シリコン膜を形成した。ついで、実質的に真性の薄膜形
成室に当該基体を移送し、モノシランを１０ｓｃｃｍ導
入して、圧力０．０５ｔｏｒｒ、形成温度 ２５０℃の
条件で、プラズマＣＶＤ法により、アモルファスシリコ
ン薄膜を約６０００Åの膜厚に形成した。プラズマＣＶ
Ｄ法は、１３．５６ＭＨｚのＲＦ放電を利用した。この
ときの、ＲＦ電力は５Ｗ であった。実質的に真性の薄
膜形成後、第二の導電性薄膜形成室に当該基体を移送し
た。第二の導電性薄膜には、ｎ型の導電性を付与するた
めに、原料ガスとして、ジシラン／ホスフィン／水素を
１０／０．０１／１００ の割合で導入し、圧力 ０．
２ｔｏｒｒ、形成温度 ２５０℃、ＲＦ電力 ８０Ｗで
約 ５００Åの厚みのｎ型微結晶シリコン膜を形成した
。ついで、第二電極形成室へ移送し、真空蒸着により、
アルミニウム膜を第二の電極として形成した。Example 1 An apparatus for carrying out the present invention includes a substrate insertion chamber (1), a first conductive thin film forming chamber (2), as shown in FIG.
It consists essentially of an intrinsic thin film forming chamber (3), a second conductive thin film forming chamber (4), and a second electrode forming chamber (5), and the first conductive thin film forming chamber is used for depositing silicon. A device having an electron beam evaporation device (14) for generating ions and an ion generating device (15) for generating ions was used. A glass substrate (7) on which a tin oxide thin film is formed as a first electrode is heated in a vacuum in a substrate insertion chamber, and then transferred to a first conductive thin film forming chamber. The first conductive thin film is formed by setting high-purity silicon as a starting material in a crucible, irradiating it with an electron beam, and evaporating it. Add hydrogen/diborane at a ratio of 20/0.1 to the ion generator under pressure.
A 1.5×10 −3 torr was introduced, an ion beam voltage of 300 V and an acceleration voltage of 50 V were applied to generate an ion beam, the ion beam shutter was opened, and the substrate was irradiated with the ion beam. At the same time, the shutter of the electron beam evaporator was opened for 20 seconds to deposit a 20 Å silicon thin film on the substrate heated to 250°C. Next, the shutter of the electron beam evaporation apparatus was closed, and only ion beam irradiation was performed for 10 seconds. In this way, the shutter of the electron beam evaporator was repeatedly opened and closed at each time interval. 1
By repeating this process 0 times, a p-type crystalline silicon film with a thickness of about 200 Å was formed. Next, the substrate was transferred to a substantially intrinsic thin film forming chamber, monosilane was introduced at 10 sccm, and an amorphous silicon thin film was formed into a film with a thickness of about 6000 Å by plasma CVD under conditions of a pressure of 0.05 torr and a forming temperature of 250°C. Formed thickly. plasma CV
Method D utilized 13.56 MHz RF discharge. At this time, the RF power was 5W. After forming the substantially intrinsic thin film, the substrate was transferred to a second conductive thin film forming chamber. In order to impart n-type conductivity to the second conductive thin film, disilane/phosphine/hydrogen was introduced as raw material gases in a ratio of 10/0.01/100, and the pressure was 0.
An n-type microcrystalline silicon film with a thickness of about 500 Å was formed at 2 torr, a formation temperature of 250° C., and an RF power of 80 W. Then, it is transferred to the second electrode forming chamber, and by vacuum evaporation,
An aluminum film was formed as the second electrode.
【００３４】かくして得られた非晶質太陽電池の光電変
換特性をＡＭ−１．５ 、１００ｍＷ／ｃｍ２ の光を
ソーラーシュミレーターにより、照射して測定した。こ
の結果、開放端電圧０．９７０Ｖと非常に高い値を得た
。短絡光電流１７．７０ｍＡ／ｃｍ２ 、曲線因子 ０
．７４５と大きい値であり、結果として、光電変換効率
１２．８％と極めて優れた性能であった。The photoelectric conversion characteristics of the amorphous solar cell thus obtained were measured by irradiating it with AM-1.5, 100 mW/cm2 light using a solar simulator. As a result, an extremely high open circuit voltage of 0.970V was obtained. Short circuit photocurrent 17.70mA/cm2, fill factor 0
．． This was a large value of 745, and as a result, the photoelectric conversion efficiency was 12.8%, which was an extremely excellent performance.
【００３５】なお、本第一の導電性薄膜の形成条件で作
製した薄膜のみをラマン散乱スペクトルで測定したとこ
ろ、結晶シリコンに特有の ５２０ｃｍ−１のラマン散
乱スペクトルが得られた。[0035] When only the thin film produced under the first conductive thin film formation conditions was measured by Raman scattering spectrum, a Raman scattering spectrum of 520 cm-1, which is characteristic of crystalline silicon, was obtained.
【００３６】実施例２
実施例１において、第一の導電性薄膜の形成の場合の一
回当たりの蒸着厚みならびに改質時間のみ変更し、それ
ぞれ、約４Åおよび６秒として、ｐ型結晶性薄膜を形成
した。蒸着厚みの変更は電子ビーム蒸着装置のシャッタ
ーを開く時間を変更することにより実施した。実施例１
において、電子ビーム蒸着による蒸着速度が約１Å／秒
と判明したので、本実施例においては一回の成膜時間を
４秒とした。蒸着工程−改質工程の５０回の繰り返しに
より約 ２００Åのｐ型結晶性薄膜を得た。実施例１と
同様に光電変換特性を測定した結果、開放端電圧０．９
５０Ｖ、短絡光電流１７．４０ｍＡ／ｃｍ２ 、曲線因
子 ０．７５５と大きい値であり、結果として光電変換
効率１２．５％と極めて優れた性能であった。Example 2 In Example 1, only the deposition thickness and modification time per one time in forming the first conductive thin film were changed to about 4 Å and 6 seconds, respectively, to form a p-type crystalline thin film. was formed. The deposition thickness was changed by changing the opening time of the shutter of the electron beam evaporator. Example 1
In this example, the deposition rate by electron beam evaporation was found to be about 1 Å/sec, so in this example, the time for one film formation was set to 4 seconds. By repeating the vapor deposition process and the modification process 50 times, a p-type crystalline thin film with a thickness of about 200 Å was obtained. As a result of measuring the photoelectric conversion characteristics in the same manner as in Example 1, the open circuit voltage was 0.9
50V, short-circuit photocurrent 17.40 mA/cm2, fill factor 0.755, which were large values, and as a result, the photoelectric conversion efficiency was 12.5%, which was extremely excellent performance.
【００３７】比較例１
実施例１において、第一の導電性薄膜の形成の場合に、
イオン照射のみで、改質工程を経ることなく ２００Å
の厚みにまで形成した。すなわち、イオンビーム蒸着装
置と電子ビーム蒸着装置のシャッターを同時に開き、実
施例１において、電子ビーム蒸着による蒸着速度が約１
Å／秒と判明したので、 ２００秒後に両方のシャッタ
ーを閉じて、第一の導電性薄膜の形成を終了した。本試
料も実施例と同様の光電変換特性を測定したところ、開
放端電圧０．８３０Ｖ、短絡光電流１５．６７ｍＡ／ｃ
ｍ２ 、曲線因子 ０．７０２、光電変換効率９．１３
％と実施例に比べ低い性能であった。特に、開放端電圧
、短絡光電流は低いものであった。このような第一の導
電性薄膜の形成条件で形成した薄膜のみをラマン散乱ス
ペクトルで測定したところ、結晶化しておらず、開放端
電圧、短絡光電流の低下は、この結晶化の有無に対応し
ていることが判明した。Comparative Example 1 In Example 1, when forming the first conductive thin film,
200Å with only ion irradiation and no modification process
It was formed to a thickness of . That is, the shutters of the ion beam evaporator and the electron beam evaporator were opened simultaneously, and in Example 1, the deposition rate by electron beam evaporation was approximately 1
Å/sec, so both shutters were closed after 200 seconds to complete the formation of the first conductive thin film. When this sample was also measured for photoelectric conversion characteristics similar to those in the example, the open circuit voltage was 0.830V, and the short circuit photocurrent was 15.67mA/c.
m2, fill factor 0.702, photoelectric conversion efficiency 9.13
%, which was lower performance than the example. In particular, the open circuit voltage and short circuit photocurrent were low. When only the thin film formed under these conditions for forming the first conductive thin film was measured using Raman scattering spectroscopy, it was found that it was not crystallized, and the decrease in open-circuit voltage and short-circuit photocurrent corresponds to the presence or absence of this crystallization. It turned out that it was.
【００３８】比較例２
実施例１において、第一の導電性薄膜の形成の場合に、
Ｓｉ薄膜を ２００Åの厚みにまで形成した後、イオン
照射のみを継続した。照射のみの時間は、１０００秒と
した。本条件により得られた素子の光電変換特性は、開
放端電圧０．８２５ Ｖ 、短絡光電流１５．７５ｍＡ
／ｃｍ２ 、曲線因子 ０．６９８、光電変換効率９．
０７％と比較例１とほとんど同じ特性であった。このよ
うな第一の導電性薄膜の形成条件でも、該薄膜が結晶化
していないため、開放端電圧、短絡光電流の改善が得ら
れていない。Comparative Example 2 In Example 1, when forming the first conductive thin film,
After forming the Si thin film to a thickness of 200 Å, only ion irradiation was continued. The time for irradiation alone was 1000 seconds. The photoelectric conversion characteristics of the device obtained under these conditions are an open circuit voltage of 0.825 V and a short circuit photocurrent of 15.75 mA.
/cm2, fill factor 0.698, photoelectric conversion efficiency 9.
07%, which was almost the same characteristic as Comparative Example 1. Even under such conditions for forming the first conductive thin film, since the thin film is not crystallized, improvements in open circuit voltage and short-circuit photocurrent cannot be obtained.
【００３９】比較例３
実施例１において、第一の導電性薄膜の形成の場合に、
成膜工程でイオン照射を行わずに膜形成を実施した。す
なわち、電子ビーム蒸着装置のシャッターを２０秒開き
、基板上に２０Åシリコン薄膜を蒸着後、電子ビーム蒸
着装置のシャッターを閉じるとともに、イオンビームの
シャッターを開き、イオンビーム照射を１０秒行った。
次に、イオンビームのシャッターを閉じるとともに、電
子ビーム蒸着装置のシャッターを再び開けて成膜を行う
。この成膜と改質の繰り返しを１０回繰り返すことによ
り、約 ２００Åのｐ型結晶性薄膜を得た。本条件によ
り得られた素子の光電変換特性は、開放端電圧０．８３
２ Ｖ 、短絡光電流１５．５７ｍＡ／ｃｍ２ 、曲線
因子 ０．７０１、光電変換効率９．０８％と比較例１
とほとんど同じ特性であった。このような第一の導電性
薄膜の形成条件でも、該薄膜が結晶化していないため、
開放端電圧、短絡光電流の改善が得られていない。Comparative Example 3 In Example 1, when forming the first conductive thin film,
Film formation was performed without ion irradiation in the film formation process. That is, the shutter of the electron beam evaporator was opened for 20 seconds to deposit a 20 Å silicon thin film on the substrate, and then the shutter of the electron beam evaporator was closed, the ion beam shutter was opened, and ion beam irradiation was performed for 10 seconds. Next, the shutter of the ion beam is closed, and the shutter of the electron beam evaporation apparatus is opened again to form a film. By repeating this process of film formation and modification 10 times, a p-type crystalline thin film of about 200 Å was obtained. The photoelectric conversion characteristics of the device obtained under these conditions are that the open circuit voltage is 0.83
2 V, short circuit photocurrent 15.57 mA/cm2, fill factor 0.701, photoelectric conversion efficiency 9.08%, and comparative example 1
had almost the same characteristics. Even under such conditions for forming the first conductive thin film, the thin film is not crystallized, so
Improvements in open-circuit voltage and short-circuit photocurrent have not been achieved.
【００４０】[0040]
【発明の効果】以上の実施例ならびに比較例から明らか
なように、本方法を用いて作製した半導体薄膜は、 ３
００Å以下の膜厚においても、結晶性を有しており、こ
のことは、従来、困難であった微結晶半導体薄膜の非晶
質太陽電池のｐ層への適用を可能にするものであり、開
放端電圧、短絡光電流の大幅な改善につながるものであ
る。
したがって、本発明は電力用太陽電池に要求される高変
換効率ならびに高信頼性を可能にする技術を提供できる
ものであり、エネルギー産業にとって、きわめて有用な
発明である。[Effects of the Invention] As is clear from the above Examples and Comparative Examples, the semiconductor thin film produced using the present method has 3
It has crystallinity even at a film thickness of 00 Å or less, which makes it possible to apply microcrystalline semiconductor thin films to the p-layer of amorphous solar cells, which has been difficult in the past. This leads to significant improvements in open-circuit voltage and short-circuit photocurrent. Therefore, the present invention can provide a technology that enables high conversion efficiency and high reliability required for power solar cells, and is an extremely useful invention for the energy industry.
【図１】図１は、本発明の素子を形成するために好まし
い装置の一例を示す模式図である。FIG. 1 is a schematic diagram showing an example of a preferred apparatus for forming the element of the present invention.
１ 基体挿入室 ２ 第一の導電性薄膜形成室 ３ 実質的に真性の薄膜形成室 ４ 第二の導電性薄膜形成室 ５ 第二電極形成室 ６ 基体取り出し室 ７ 基体 ８ 放電電力印加電極 ９ 基体加熱電極 １０ メタルマスク １１ 第二電極材料蒸着源 １２ 真空排気ライン １３ 原料ガス導入ライン １４ シリコン蒸着源 １５ イオン発生装置 １６ ゲ−ト弁 1 Base insertion chamber 2 First conductive thin film formation chamber 3. Substantially intrinsic thin film formation chamber 4 Second conductive thin film formation chamber 5 Second electrode formation chamber 6 Substrate removal chamber 7 Base 8 Discharge power application electrode 9 Substrate heating electrode 10 Metal mask 11 Second electrode material deposition source 12 Vacuum exhaust line 13 Raw material gas introduction line 14 Silicon vapor deposition source 15 Ion generator 16 Gate valve
Claims (1)
薄膜、実質的に真性の薄膜、第二の導電性薄膜、第二の
電極の順に形成した光電変換素子において、少なくとも
第一の導電性薄膜が、荷電粒子を含む雰囲気で薄膜形成
を行う工程と薄膜形成原料の供給を停止して、荷電粒子
を含む雰囲気で当該薄膜形成表面を、さらに改質する工
程とを繰り返し、かつ、その一回の繰り返しにおいて成
膜される薄膜の厚みが１から １００Åである全膜厚が
３００Å以下の結晶性半導体薄膜であることを特徴と
する光電変換素子。1. A photoelectric conversion element in which a first electrode, a first conductive thin film, a substantially intrinsic thin film, a second conductive thin film, and a second electrode are formed on a substrate in this order, wherein at least the One conductive thin film repeats the step of forming a thin film in an atmosphere containing charged particles, and the step of stopping the supply of the thin film forming raw material and further modifying the thin film forming surface in an atmosphere containing charged particles, A photoelectric conversion element characterized in that the thin film formed in one repetition is a crystalline semiconductor thin film having a thickness of 1 to 100 Å and a total film thickness of 300 Å or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096568A JP2896247B2 (en) | 1991-04-26 | 1991-04-26 | Photoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096568A JP2896247B2 (en) | 1991-04-26 | 1991-04-26 | Photoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04326577A true JPH04326577A (en) | 1992-11-16 |
| JP2896247B2 JP2896247B2 (en) | 1999-05-31 |
Family
ID=14168617
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3096568A Expired - Fee Related JP2896247B2 (en) | 1991-04-26 | 1991-04-26 | Photoelectric conversion element |
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| Country | Link |
|---|---|
| JP (1) | JP2896247B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6566594B2 (en) | 2000-04-05 | 2003-05-20 | Tdk Corporation | Photovoltaic element |
-
1991
- 1991-04-26 JP JP3096568A patent/JP2896247B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6566594B2 (en) | 2000-04-05 | 2003-05-20 | Tdk Corporation | Photovoltaic element |
| US6960718B2 (en) | 2000-04-05 | 2005-11-01 | Tdk Corporation | Method for manufacturing a photovoltaic element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2896247B2 (en) | 1999-05-31 |
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