JP3690807B2 - 薄膜太陽電池の製法 - Google Patents
薄膜太陽電池の製法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010409 thin film Substances 0.000 title claims description 7
- 239000011734 sodium Substances 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims 3
- 238000004544 sputter deposition Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 40
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VZZSRKCQPCSMRS-UHFFFAOYSA-N dipotassium;selenium(2-) Chemical compound [K+].[K+].[Se-2] VZZSRKCQPCSMRS-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Description
CuInSe2(セレン化銅インジウム)薄膜太陽電池は通常モリブデン(Mo)バック接点を基体、例えばガラス基体上に付着させて製造する。次いで、銅と、インジウムと、セレン化物とをバック接点(back contact)上に付着させてCuInSe2層を形成する。このCuInSe2はセレン含有雰囲気内での化学反応で生成する。この製造段階でこの構造体は350°〜600℃の範囲の温度にさらされる。
このCuInSe2層はp型半導体である。n型半導体をこのCuInSe2層上に付着させてpn接合を形成し、事実上の太陽電池が形成される。n型半導体はCaSの薄い層とZnOの厚い層から成ることが一番多い。このZnO層は同時に前面接点となる。
この種の太陽電池は効率を向上させることが望ましい。
本発明は太陽電池の製法を提供し、太陽電池製品の効率を大きく向上させる。
従って、本発明は太陽電池内に電気的バック接点をなす金属層を含む構造体に1つの製造段階でセレン化銅インジウム(CuInSe2)の層を被覆し、上記バック接点を基体に被覆した薄膜太陽電池の製法に関し、CuInSe2層の被覆前に構造体をアルカリ金属層で被覆することを特徴とする。
本発明の特に好ましい態様では、CuInSe2層被覆前に構造体に被覆するアルカリ金属はナトリウム(Na)又はカリウム(K)である。
本明細書と請求項で用いた「セレン化銅インジウム層」は各種合金物質、主にガリウムと硫黄とを含有する各種組成のセレン化銅インジウムを意味する。ここで使用する用語「セレン化銅インジウム」は主にCuInSe2、CuInxGa1-xSex、CuInxGa1-xSySe2-yの化合物に関する。
本発明を式CuInSe2のセレン化銅インジウム層について以下説明する。
太陽電池を示す単一図である添付図面に図示の本発明の例示態様を部分的に参照しながら本発明を詳述する。
本発明はCuInSe2層を形成させる面、例えばモリブデン層に単体カリウム又はナトリウム又はこれらの基本的物質が存在する化合物の形で単体ナトリウム又はカリウムを被覆するときは、多結晶性CuInSe2膜中の粒子は柱状構造で配向することが多い。又、これらの粒子は寸法が一層大きく、その構造はより緻密である。又、CuInSe2層の抵抗率は低下する。これはより効果的なpドーピングが得られること、これにより電池電圧が高くなることを意味する。
ナトリウムとカリウム以外のアルカリ金属も同一の効果を与える。少くとも原子量が低いリチウムが該当する。
図1は薄膜太陽電池の概略断面図である。薄膜太陽電池がその上に形成される基体は寸法が大きく、例えば1×0.4mの大きさである。基体表面は電気的に互に接続された多数の電池を担持する。図1はかかる1つの電池の部分を示すもので、基体上に多数の独立した、但し電気的に接続した電池を形成することは技術的に公知であり、本明細書では詳述しない。
本発明が適用される太陽電池は次のようにして構成する。基体1は通常適切な厚さ、例えば2.0mmの厚さのガラスシートの形状である、はじめに、モリブデン(Mo)層2をこのガラスシート上にスパッターして付着させる。このモリブデン層はバック接点となり、最終電池の正端子となる。モリブデン層の厚さは1,000nmである。次いで、CuInSe2層3を被覆し、これは厚さが例えば2,500nmである。この層3に硫化カドミウム(CaS)層4を被覆し、これは厚さが例えば50nmであり、次いで透明なドーピング処理した酸化亜鉛(ZnO)層5の形で電気接点層を被覆する、この層厚は例えば500nmである。
太陽光が電池に当ると、電圧が負の端子である電気接点5(ZnO)と電気的バック接点2との間に生ずる。
1例としてナトリウムを用いたものについて本発明を以下に説明するが、他のアルカリ金属も使用することができ、同等の効果が得られる。図示の太陽電池の層6はナトリウムであるが、ナトリウム以外のアルカリ金属を用いるときは、この層6はかかるアルカリ金属からなる。
本発明ではアルカリ金属(この場合ナトリウム(Na)である)を含有する層6はCuInSe2層3被覆前に金属層2の表面に即ち例示の実施例ではモリブデン層であるが、この表面に形成する。
本発明の1つの好ましい態様ではナトリウムを電気的バック接点即ち金属層の上にセレン化ナトリウム(Na2Se)を蒸着させて被覆する。
本発明の別の好ましい態様では、カリウムをバック接点即ち金属層の上にセレン化カリウム(K2Se)を蒸着させて被覆する。
別の好ましい態様では、電気的バック接点がモリブデンから成るとき、アルカリ金属(この場合ナトリウム)をこの電気的バック接点と同時に被覆する。
本発明の別の好ましい態様ではアルカリ金属(この場合ナトリウム)を含む層は50〜500nmの厚さに被覆する。
別の態様では、この層は酸素(O)をも含有する。
CuInSe2層をナトリウム又はカリウム含有層の表面上に被覆したときは、ナトリウム又はカリウムは金属接点の表面から本質的に消失することが判った。CuInSe2層を被覆したときは、ナトリウム又はカリウムはCuInSe2層内の粒界とこの層の表面上に再び見出される。次いでCaS層を湿式法で被覆するときはこのナトリウム又はカリウム化合物はこの湿式法で用いる液に可溶性のときはこのナトリウム又はカリウム化合物はその表面から消失する。
本方法により、実施例として説明し図示した太陽電池の効率が極めて驚異的に即ち約25%向上する。本発明を適用しなかったこの種の太陽電池の典型的な効率は12%である。本発明を適用したとき、この効率は15%に向上する。
本発明と特定の太陽電池構造体について記載してきたが、本発明は電気的バック接点がモリブデンでなく、いくつかのその他の適切な金属、例えばタングステン、ニッケル、チタン又はクロムから成るその他の構造体に適用できる。
更に、ナトリウム含有ガラス以外の基体も使用できる。例えばナトリウムを含有しないガラスが使用でき、ナトリウムを含有し電気的バック接点を形成する表面上に抗ナトリウム拡散障壁を有するガラスも使用できる。
本発明は以下の請求の範囲内で改変が可能であり、従って本発明は上記の本発明の例示態様に限定されるものではない。
Claims (6)
- 太陽電池の電気的バック接点をなす金属層(2)を含む構造体にセレン化銅インジウム(CuInSe2)(3)を1回の製造工程で被覆し、このバック接点が基体(1)上に被覆されている薄膜太陽電池の製法において、
CuInSe2層(3)を被覆する前にナトリウム又はカリウムの層(6)を電気的バック接点上に形成することを特徴とする、上記製法。 - バック接点がモリブデンから成るときスパッターリングでナトリウム又はカリウムをバック接点と同時に被覆する、請求項1に記載の製法。
- ナトリウム又はカリウムの層は厚さ50〜500nmに被覆する、請求項1又は2に記載の製法。
- ナトリウム又はカリウムの層が酸素(O)をも含有する、請求項1〜3のいずれか1項に記載の製法。
- バック接点がモリブデン(Mo)から成る、請求項1〜4のいずれか1項に記載の製法。
- セレン化銅インジウム層表面上に硫化カドミウム(CdS)を被覆し、硫化カドミウム層の表面上に電気的接点層を被覆し、この電気的接点層は好ましくはドープした酸化亜鉛(ZnO)の層である、請求項1〜5のいずれか1項に記載の製法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9403609A SE508676C2 (sv) | 1994-10-21 | 1994-10-21 | Förfarande för framställning av tunnfilmssolceller |
SE9403609-2 | 1994-10-21 | ||
PCT/SE1995/001242 WO1996013063A1 (en) | 1994-10-21 | 1995-10-20 | A method of manufacturing thin-film solar cells |
Publications (2)
Publication Number | Publication Date |
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JPH10512096A JPH10512096A (ja) | 1998-11-17 |
JP3690807B2 true JP3690807B2 (ja) | 2005-08-31 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51383596A Expired - Lifetime JP3690807B2 (ja) | 1994-10-21 | 1995-10-20 | 薄膜太陽電池の製法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5994163A (ja) |
EP (1) | EP0787354B1 (ja) |
JP (1) | JP3690807B2 (ja) |
AU (1) | AU3820595A (ja) |
DE (1) | DE69529529T2 (ja) |
ES (1) | ES2191716T3 (ja) |
SE (1) | SE508676C2 (ja) |
WO (1) | WO1996013063A1 (ja) |
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US5730852A (en) * | 1995-09-25 | 1998-03-24 | Davis, Joseph & Negley | Preparation of cuxinygazsen (X=0-2, Y=0-2, Z=0-2, N=0-3) precursor films by electrodeposition for fabricating high efficiency solar cells |
-
1994
- 1994-10-21 SE SE9403609A patent/SE508676C2/sv not_active IP Right Cessation
-
1995
- 1995-10-20 US US08/817,693 patent/US5994163A/en not_active Expired - Lifetime
- 1995-10-20 AU AU38205/95A patent/AU3820595A/en not_active Abandoned
- 1995-10-20 EP EP95936166A patent/EP0787354B1/en not_active Expired - Lifetime
- 1995-10-20 ES ES95936166T patent/ES2191716T3/es not_active Expired - Lifetime
- 1995-10-20 DE DE69529529T patent/DE69529529T2/de not_active Expired - Lifetime
- 1995-10-20 JP JP51383596A patent/JP3690807B2/ja not_active Expired - Lifetime
- 1995-10-20 WO PCT/SE1995/001242 patent/WO1996013063A1/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
DE69529529D1 (de) | 2003-03-06 |
SE9403609L (sv) | 1996-04-22 |
EP0787354B1 (en) | 2003-01-29 |
JPH10512096A (ja) | 1998-11-17 |
WO1996013063A1 (en) | 1996-05-02 |
EP0787354A1 (en) | 1997-08-06 |
AU3820595A (en) | 1996-05-15 |
US5994163A (en) | 1999-11-30 |
SE508676C2 (sv) | 1998-10-26 |
DE69529529T2 (de) | 2003-12-11 |
ES2191716T3 (es) | 2003-09-16 |
SE9403609D0 (sv) | 1994-10-21 |
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