JP4620105B2 - Cis系薄膜太陽電池の光吸収層の製造方法 - Google Patents
Cis系薄膜太陽電池の光吸収層の製造方法 Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 64
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
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- 239000011669 selenium Substances 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 239000011593 sulfur Substances 0.000 claims description 25
- 239000010408 film Substances 0.000 claims description 22
- 229910052711 selenium Inorganic materials 0.000 claims description 22
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- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 150000003346 selenoethers Chemical class 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
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- 240000002329 Inga feuillei Species 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 238000009792 diffusion process Methods 0.000 description 3
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
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- 230000003595 spectral effect Effects 0.000 description 1
- QXTCFDCJXWLNAP-UHFFFAOYSA-N sulfidonitrogen(.) Chemical compound S=[N] QXTCFDCJXWLNAP-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- 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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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—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
- 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
- H01L31/072—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
- 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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- 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
- Y02E10/541—CuInSe2 material PV cells
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- 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
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Description
図1に、本発明の光吸収層の製造方法を用いて作製したCIS系薄膜太陽電池の基本構造を示す。
p型CIS系光吸収層3は、例えば、ガラス基板1上の金属裏面電極層2に、Cu、In、Gaを含む積層構造または混晶の金属プリカーサ膜を、スパッタ法や蒸着法等により製膜した後(以下、金属裏面電極層2上に金属プリカーサ膜が製膜されたガラス基板を「処理対象物」ということがある。)、この処理対象物をセレン化及び/又は硫化することによって製造することができる。
上記セレン化物には、CuInSe2、Cu(InGa)Se2、CuGaSe2等が挙げられる。
以上のセレン化工程及び硫化工程を経て製膜されたp型CIS系光吸収層3は、CuIn(SSe)2、Cu(InGa)(SSe)2、CuGa(SSe)2、等からなる膜となる。
また、比較例として、図5に示すような、従来の温度プロファイルに従い、第2の硫化工程の無い比較例による結果も併せて表1に示す。
2 金属裏面電極層
3 p型CIS系光吸収層
3A 処理対象物
3a 金属プリカーサ膜
4 n型高抵抗バッファ層
5 n型透明導電膜窓層(透明導電膜層)
6 炉体
7 ヒータ
10 CIS系薄膜太陽電池
13 p型CIS系光吸収層
20 CIS系薄膜太陽電池
Claims (20)
- 処理対象物を、硫黄源を有する雰囲気中にて、所定の温度で一定時間保持して硫化を行う第1の熱処理を施した後、前記第1の熱処理の保持温度よりも低い温度で前記第1の熱処理の保持時間よりも長い時間保持して硫化を行う第2の熱処理を施す2段階熱処理工程により硫化することを特徴とするCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記2段階熱処理工程の前に、処理対象物を、セレン源及び/又は硫黄源を有する雰囲気中にて、前記第1の熱処理の保持温度よりも低い温度で一定時間保持してセレン化又は硫化を行う前段階熱処理工程を備えることを特徴とする請求項1記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記2段階熱処理工程における第1の熱処理の保持温度が500℃〜650℃であることを特徴とする請求項1又は2記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記2段階熱処理工程における第1の熱処理の保持時間が5分〜120分であることを特徴とする請求項1乃至3のいずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記2段階熱処理工程における第2の熱処理の保持温度が480℃〜600℃であることを特徴とする請求項1乃至4いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記2段階熱処理工程における第2の熱処理の保持時間が20分〜300分であることを特徴とする請求項1乃至5いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記前段階熱処理工程における保持温度が350℃〜550℃であることを特徴とする請求項2乃至6いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記前段階熱処理工程における保持時間が10分〜240分であることを特徴とする請求項2乃至7いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記処理対象物は、基板に形成された金属裏面電極層上に、金属プリカーサ膜を積層したものであることを特徴とする請求項1乃至8いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記金属プリカーサ膜は、Cu/Ga、Cu/In、Cu-Ga合金/In、Cu-In-Ga合金のいずれか一つを含むことを特徴とする請求項9記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記金属プリカーサ膜中にセレン及び/又は硫黄を含むことを特徴とする請求項10記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記セレン源がセレン化水素であることを特徴とする請求項2項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記硫黄源が硫化水素であることを特徴とする請求項1乃至12いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- Cu/Ga、Cu/In、Cu-Ga合金/In、Cu-In-Ga合金のいずれか一つを金属プリカーサ膜として含む処理対象物を、セレン源を有する雰囲気中にて所定の温度で保持する前段階熱処理工程でセレン化物とするセレン化工程と、
前記セレン源を有する雰囲気から硫黄源を有する雰囲気に変更後、前記セレン化物を昇温し、2段階の硫化を行う工程と
を備え、前記2段階の硫化を行う工程は、
前記前段階熱処理工程の保持温度よりも高い第1の熱処理温度で処理対象物を一定時間保持して硫化する第1硫化工程と、
前記第1の熱処理温度よりも低い温度で前記第1の熱処理温度の保持時間よりも長い時間保持することにより硫化する第2硫化工程と、
を備えることを特徴とするCIS系薄膜太陽電池の光吸収層の製造方法。 - 前記第1の熱処理の保持温度が500℃〜650℃であることを特徴とする請求項14記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記第1の熱処理の保持時間が5分〜120分であることを特徴とする請求項14又は15記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記第2の熱処理の保持温度が480℃〜600℃であることを特徴とする請求項14乃至16いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記第2の熱処理の保持時間が20分〜300分であることを特徴とする請求項14乃至17いずれか1項に記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記前段階熱処理工程における保持温度が350℃〜550℃であることを特徴とする請求項14記載のCIS系薄膜太陽電池の光吸収層の製造方法。
- 前記前段階熱処理工程における保持時間が10分〜240分であることを特徴とする請求項14又は19記載のCIS系薄膜太陽電池の光吸収層の製造方法。
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PCT/JP2008/071617 WO2009069729A1 (ja) | 2007-11-30 | 2008-11-28 | Cis系薄膜太陽電池の光吸収層の製造方法 |
US12/745,116 US8614114B2 (en) | 2007-11-30 | 2008-11-28 | Process for producing light absorbing layer in CIS based thin-film solar cell |
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TWI373851B (en) * | 2008-11-25 | 2012-10-01 | Nexpower Technology Corp | Stacked-layered thin film solar cell and manufacturing method thereof |
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WO2014002796A1 (ja) * | 2012-06-25 | 2014-01-03 | 京セラ株式会社 | 光電変換装置および光電変換装置の製造方法 |
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JP5985459B2 (ja) * | 2013-08-12 | 2016-09-06 | 本田技研工業株式会社 | 太陽電池の製造方法 |
KR101582121B1 (ko) * | 2014-04-03 | 2016-01-05 | 한국과학기술연구원 | 이종 적층형 cis계 광활성층 박막의 제조방법, 이로부터 제조된 cis계 광활성층 박막 및 상기 박막을 포함하는 박막 태양전지 |
JP7068798B2 (ja) * | 2017-10-26 | 2022-05-17 | 出光興産株式会社 | 光電変換素子の製造方法 |
CN110571155B (zh) * | 2019-09-12 | 2022-07-12 | 深圳先进技术研究院 | 薄膜太阳能电池的光吸收层的制备方法 |
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JP2009135299A (ja) | 2009-06-18 |
US8614114B2 (en) | 2013-12-24 |
WO2009069729A1 (ja) | 2009-06-04 |
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