JP6619484B2 - ナノ粒子から作られた薄膜中のカーボンを低減するためのh2s反応性アニーリング - Google Patents
ナノ粒子から作られた薄膜中のカーボンを低減するためのh2s反応性アニーリング Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims description 80
- 238000000137 annealing Methods 0.000 title claims description 66
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- 229910052799 carbon Inorganic materials 0.000 title claims description 8
- 239000010409 thin film Substances 0.000 title description 7
- 238000000034 method Methods 0.000 claims description 63
- 239000011669 selenium Substances 0.000 claims description 39
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- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 17
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- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
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- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
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- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/0248—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02601—Nanoparticles
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/042—PV modules or arrays of single PV cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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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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- Surface Treatment Of Glass (AREA)
Description
この出願は、2014年1月31日に出願された米国仮特許出願第61/934495号の利益を主張する。
本発明は、概して、薄膜光起電力デバイスに関する。より具体的には、銅インジウムガリウムジセレニド/ジスルフィド(CIGS)をベースとする薄膜光起電力デバイスに関する。
本発明は、光起電力デバイスのCIGS吸収体層の作製を、CIGSナノ粒子前駆体の膜を堆積し(depositing)、アニーリングすることによって行なうシステム及び方法を提供する。開示される方法の利点は、膜からのカーボン成分の除去が向上し、より良好なデバイス性能が得られることである。開示される方法は、堆積されたCIGSナノ粒子膜を、反応性H2S雰囲気、及び/又は、H2SとH2Seの混合物を含む雰囲気中でアニーリングすることを含む。
この明細書で用いられる「CIGS」という用語は、周期表11族、13族及び16族の元素を含む材料のことを言う。一般的に、CIGS材料は、式Cu(In、Ga)(S,Se)2を有する。但し、化学量論は異なることがある。また、「CIGS」とは、例えば、Gaを含まない場合、CuInS2のような材料のことを言うものとする。この明細書で用いられる「CIGSナノ粒子インキ」という用語は、CIGS材料を成分として有するナノ粒子を含むインキのことを言う。
Claims (19)
- 一般式Cu(In,Ga)(S,Se)2を有するCIGS結晶を含有する膜を製造する方法であって、
CIGS前駆体の溶液又は懸濁液を基板上に堆積して膜を形成することであって、前記CIGS前駆体が、銅と、インジウム及びガリウムのうちの少なくとも一種と、イオウ及びセレニウムのうちの少なくとも一種と、を含む、膜を形成することと、
前記膜を反応性セレニウム含有雰囲気の中でアニーリングすることと、
反応性セレニウム含有雰囲気の中でアニーリングした後、前記膜を反応性イオウ含有雰囲気の中でアニーリングすることと、を含む、方法。 - 反応性イオウ含有雰囲気での前記膜のアニーリング中に、前記膜からカーボンを反応除去すること、をさらに含む、請求項1に記載の方法。
- 反応性イオウ含有雰囲気は、硫化水素ガス(H2S)を含む、請求項1に記載の方法。
- 反応性セレニウム含有雰囲気は、セレン化水素ガス(H2Se)を含む、請求項1に記載の方法。
- 反応性イオウ含有雰囲気中でのアニーリングは、200〜500℃の温度で行われる請求項1に記載の方法。
- アニーリング温度は、反応性イオウ含有雰囲気中でのアニーリング中に変動する、請求項1に記載の方法。
- アニーリング温度は、第1の温度から、選択された変化率で、第2の温度へ変化される、請求項6に記載の方法。
- アニーリング温度を第2の温度で選択された時間保持し、次に、アニーリング温度を第3の温度に変化させることをさらに含む、請求項7に記載の方法。
- 複数層の膜を形成するために、追加の堆積ステップ及びアニーリングステップをさらに含む、請求項1に記載の方法。
- 複数層の膜におけるインジウムとガリウムの比率は、膜内部の深さの関数として変動する、請求項9に記載の方法。
- CIGS前駆体は、銅と、インジウム及び/又はガリウムと、イオウ及び/又はセレニウムと、を含むナノ粒子である、請求項1に記載の方法。
- CIGS前駆体は、CuSe2ナノ粒子とInSe2ナノ粒子を含む、請求項1に記載の方法。
- CIGS前駆体は、CuSe2ナノ粒子とInSe2ナノ粒子である、請求項1に記載の方法。
- CIGS前駆体は、単一種のナノ粒子にて懸濁溶液で供給される、請求項1に記載の方法。
- ナノ粒子は、前記溶液又は懸濁液の最大約50%w/vである、請求項11乃至14の何れかに記載の方法。
- 前記基板は、ガラスを含む、請求項1に記載の方法。
- 前記ガラスは、モリブデンがコートされたガラスである、請求項16に記載の方法。
- 前記基板は、ポリマーである、請求項1に記載の方法。
- 前記アニーリングは、チューブ炉で行われる、請求項1に記載の方法。
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US (1) | US9887304B2 (ja) |
EP (1) | EP3100306A1 (ja) |
JP (2) | JP2017511782A (ja) |
KR (1) | KR101822147B1 (ja) |
CN (1) | CN105940500A (ja) |
TW (1) | TWI560891B (ja) |
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KR101939114B1 (ko) * | 2016-09-27 | 2019-01-17 | 재단법인대구경북과학기술원 | 셀렌화 및 황화 열처리를 통한 셀렌 및 황의 조성이 조절된 박막 태양전지 광흡수층의 제조방법 및 상기 광흡수층을 함유한 박막 태양전지 |
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US6127202A (en) * | 1998-07-02 | 2000-10-03 | International Solar Electronic Technology, Inc. | Oxide-based method of making compound semiconductor films and making related electronic devices |
US8563348B2 (en) * | 2007-04-18 | 2013-10-22 | Nanoco Technologies Ltd. | Fabrication of electrically active films based on multiple layers |
KR101144807B1 (ko) * | 2007-09-18 | 2012-05-11 | 엘지전자 주식회사 | 태양전지 박막조성용 잉크와 그 제조방법, 이를 이용한cigs 박막형 태양전지, 및 그 제조 방법 |
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US8784701B2 (en) | 2007-11-30 | 2014-07-22 | Nanoco Technologies Ltd. | Preparation of nanoparticle material |
US8802977B2 (en) * | 2008-05-09 | 2014-08-12 | International Business Machines Corporation | Techniques for enhancing performance of photovoltaic devices |
US8889469B2 (en) * | 2009-12-28 | 2014-11-18 | Aeris Capital Sustainable Ip Ltd. | Multi-nary group IB and VIA based semiconductor |
US7998789B1 (en) * | 2010-04-16 | 2011-08-16 | Jenn Feng New Energy Co., Ltd. | Method and system for forming copper indium gallium sulfur selenide absorption layer and cadmium sulfide buffer layer under non-vacuum condition |
WO2013033729A1 (en) * | 2011-09-02 | 2013-03-07 | Alliance For Sustainable Energy, Llc | Electrodepostion of gallium for photovoltaics |
US8551802B2 (en) * | 2011-09-12 | 2013-10-08 | Intermolecular, Inc. | Laser annealing for thin film solar cells |
US20130157407A1 (en) | 2011-12-20 | 2013-06-20 | Intermolecular, Inc. | APPARATUS FOR INLINE PROCESSING OF Cu(In,Ga)(Se,S)2 EMPLOYING A CHALCOGEN SOLUTION COATING MECHANISM |
US9018032B2 (en) * | 2012-04-13 | 2015-04-28 | Tsmc Solar Ltd. | CIGS solar cell structure and method for fabricating the same |
US9243340B2 (en) * | 2013-03-07 | 2016-01-26 | Nano And Advanced Materials Institute Limited | Non-vacuum method of manufacturing light-absorbing materials for solar cell application |
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US20150221795A1 (en) | 2015-08-06 |
JP2018197188A (ja) | 2018-12-13 |
US9887304B2 (en) | 2018-02-06 |
TWI560891B (en) | 2016-12-01 |
EP3100306A1 (en) | 2016-12-07 |
WO2015114356A1 (en) | 2015-08-06 |
JP2017511782A (ja) | 2017-04-27 |
KR20160103077A (ko) | 2016-08-31 |
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