JP6103525B2 - Cigs膜およびそれを用いたcigs太陽電池 - Google Patents
Cigs膜およびそれを用いたcigs太陽電池 Download PDFInfo
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- 239000000758 substrate Substances 0.000 claims description 27
- 230000007423 decrease Effects 0.000 claims description 19
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 230000031700 light absorption Effects 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000010408 film Substances 0.000 description 157
- 239000010410 layer Substances 0.000 description 79
- 238000006243 chemical reaction Methods 0.000 description 26
- 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 26
- 239000011669 selenium Substances 0.000 description 22
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 16
- 238000007740 vapor deposition Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 229910052711 selenium Inorganic materials 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052717 sulfur 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
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- H—ELECTRICITY
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- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H01L31/03928—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
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Description
(A)インジウム(In)の原子数濃度とガリウム(Ga)の原子数濃度の和に対するそのガリウム(Ga)の原子数濃度の比であるGa/(In+Ga)比。
(A)インジウム(In)の原子数濃度とガリウム(Ga)の原子数濃度の和に対するそのガリウム(Ga)の原子数濃度の比であるGa/(In+Ga)比。
<基板の準備,裏面電極層の形成>
上記実施の形態と同様にして、CIGS太陽電池を製造した。すなわち、まず、ソーダ石灰ガラスからなる基板〔30mm×30mm×0.55mm(厚み)〕を準備し、その表面に、モリブデン製の裏面電極層(厚み500nm)をスパッタリング法により形成した。
ついで、蒸着装置を用い、上記基板を、330℃に保持した状態で、上記裏面電極層の表面に、セレン化ガリウム膜(厚み130nm)を形成した。その後、そのセレン化ガリウム膜の表面に、セレン化インジウム膜(厚み330nm)を形成した。そして、そのセレン化インジウム膜の表面に、Cu,Seを蒸着し、セレン化銅からなる蒸着層(厚み1400nm)を形成した。このようにして、セレン化ガリウム膜およびセレン化インジウム膜ならびにセレン化銅(蒸着層)からなる積層体を作製した。その後、その積層体を、微量のSe蒸気を供給しつつ加熱し、基板保持温度が550℃の状態を5分間保持して、結晶成長させ、第1領域を形成した。
つぎに、微量のSeガスを供給しつつ、基板を550℃に保持した状態で、上記第1領域の表面に、上記と同様にして、セレン化ガリウム膜を形成した後、その表面に、セレン化インジウム膜を形成した。このとき、各膜の厚みは、基板を330℃にした際に、セレン化ガリウム膜の厚みが30nm、セレン化インジウム膜の厚みが80nmとなるように形成した。
つぎに、微量のSeガスを供給しつつ、基板を550℃に保持した状態で、上記第2領域の表面に、1層のセレン化インジウム膜(厚み10nm)を、上記と同様にして蒸着形成し、第3領域を形成した。この第3領域の形成では、ガリウムを含む膜が形成されないことから、Ga/(In+Ga)比は、上記第2領域上から表面に向かって徐々に減少している。このようにして、上記第1〜第3領域からなるCIGS膜(厚み2.0μm)を形成した。
上記実施例1の第3領域の形成において、蒸着形成するセレン化インジウム膜の厚みを20nmとした。それ以外は、上記実施例1と同様とした。
上記実施例1の第3領域の形成において、蒸着形成するセレン化インジウム膜の厚みを25nmとした。それ以外は、上記実施例1と同様とした。
上記実施例1の第2領域の形成において、蒸着形成するセレン化ガリウム膜およびセレン化インジウム膜の厚みを、基板を330℃にした際に、セレン化ガリウム膜の厚みが25nm、セレン化インジウム膜の厚みが85nmとなるように形成した。それ以外は、上記実施例1と同様とした。
上記実施例1において、CIGS膜を、従来の3段階法により形成し、それ以外は、上記実施例1と同様とした。すなわち、まず、上記実施例1と同様にして、基板の表面に、裏面電極層を形成した。ついで、基板の保持温度を350℃にした状態で、In、Ga、Seを一度に蒸着し、In、Ga、Seからなる層を形成した。つぎに、基板の保持温度が550℃の状態となるよう加熱した状態で、この層の上に、Cu、Seを蒸着させ、結晶成長させてCIGS膜中間体を得た。さらに、このCIGS膜中間体に、微量のSe蒸気を供給しつつ、基板保持温度を550℃に保った状態で、In、Ga、Seを一度に蒸着し、CIGS膜(厚み2.0μm)を得た。
上記実施例1〜4および従来例のCIGS膜を、それぞれ2個作製し、そのうちの1個については、上記CIGS膜を形成した後、2時間以内(CIGS膜を空気に晒す時間が2時間以内)に、そのCIGS膜の表面に、化学浴堆積法により、CdS層(厚み50nm)を形成した後、その表面に、スパッタリング法により、ZnO層(厚み70nm) を形成し、上記CdS層とZnO層とからなるバッファ層を形成した。そして、そのバッファ層の表面に、スパッタリング法により、ITOからなる透明電極層(厚み200nm)を形成し、CIGS太陽電池を得た。残りの1個については、上記CIGS膜を形成した後、そのCIGS膜を24時間空気に晒してから、そのCIGS膜の表面に、上記と同様にして、バッファ層と透明電極層とを形成し、CIGS太陽電池を得た。
上記実施例1〜4および従来例の、CIGS膜形成後、2時間以内にバッファ層を形成したCIGS太陽電池と、24時間後にバッファ層を形成したCIGS太陽電池とに対し、表面面積以上の領域に、擬似太陽光(AM1.5)を照射し、変換効率を、ソーラーシミュレーター(セルテスターYSS150、山下電装社製)によって測定した。その結果を下記の表1に示した。
上記実施例1〜4および従来例の各CIGS膜について、ダイナミックシムス評価装置(アルバック・ファイ社製)を用いて、厚み方向のGa/(In+Ga)比を測定した。そして、第2領域におけるGa/(In+Ga)比のピーク値、そのピーク値を示す部分のCIGS膜の表面からの深さ(第3領域の厚み)、第3領域におけるGa/(In+Ga)比の、上記第2領域におけるピーク値から上記CIGS膜の表面での値までの減少値を下記の表1に示した。
Claims (4)
- CIGS太陽電池の光吸収層として用いられ、その裏面から所定の厚みまで厚くなるにつれて下記(A)のGa/(In+Ga)比が徐々に減少する第1領域と、この第1領域上に位置し、表面側に向かって上記Ga/(In+Ga)比が徐々に増加する第2領域とを有するCIGS膜であって、上記第2領域上から表面まで、表面に向かって上記Ga/(In+Ga)比が徐々に減少する第3領域が形成されており、上記第2領域におけるGa/(In+Ga)比の最大ピーク値が、0.3〜0.6の範囲内であり、上記第3領域におけるGa/(In+Ga)比の、上記最大ピーク値から上記表面での値までの減少値が、0.02〜0.3の範囲内であることを特徴とするCIGS膜。
(A)インジウム(In)の原子数濃度とガリウム(Ga)の原子数濃度の和に対するそのガリウム(Ga)の原子数濃度の比であるGa/(In+Ga)比。 - 上記CIGS膜のGa/(In+Ga)比が、0.10を上回り0.40未満の範囲内である請求項1記載のCIGS膜。
- 上記第3領域の厚みが、30〜200nmの範囲内である請求項1または2記載のCIGS膜。
- 基板,裏面電極,光吸収層,バッファ層および透明導電膜がこの順で積層されているCIGS太陽電池であって、上記光吸収層が、上記請求項1〜3のいずれか一項に記載のCIGS膜であり、そのCIGS膜の裏面が、上記裏面電極側に位置する面であることを特徴とするCIGS太陽電池。
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US14/766,552 US9614111B2 (en) | 2013-02-12 | 2014-01-24 | CIGS film, and CIGS solar cell employing the same |
PCT/JP2014/051505 WO2014125898A1 (ja) | 2013-02-12 | 2014-01-24 | Cigs膜およびそれを用いたcigs太陽電池 |
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