JP2019024106A - 銅リッチな銅インジウム(ガリウム)ジセレニド/ジスルフィドの調製 - Google Patents
銅リッチな銅インジウム(ガリウム)ジセレニド/ジスルフィドの調製 Download PDFInfo
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- JP2019024106A JP2019024106A JP2018179883A JP2018179883A JP2019024106A JP 2019024106 A JP2019024106 A JP 2019024106A JP 2018179883 A JP2018179883 A JP 2018179883A JP 2018179883 A JP2018179883 A JP 2018179883A JP 2019024106 A JP2019024106 A JP 2019024106A
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- Prior art keywords
- cigs
- nanoparticles
- film
- photovoltaic device
- copper
- Prior art date
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- Pending
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- 239000010949 copper Substances 0.000 title claims abstract description 80
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229910052733 gallium Inorganic materials 0.000 title description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title description 2
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 128
- 238000000034 method Methods 0.000 claims abstract description 72
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 49
- 239000011669 selenium Substances 0.000 claims description 39
- 229910052711 selenium Inorganic materials 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000005361 soda-lime glass Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 150000004770 chalcogenides Chemical group 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 238000005486 sulfidation Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000001510 limonene Nutrition 0.000 claims description 3
- 229940087305 limonene Drugs 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 65
- 229910052798 chalcogen Inorganic materials 0.000 abstract description 41
- 150000001787 chalcogens Chemical class 0.000 abstract description 39
- 239000003446 ligand Substances 0.000 abstract description 12
- 230000004907 flux Effects 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract description 3
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000009877 rendering Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 50
- 150000003839 salts Chemical class 0.000 description 47
- 239000002243 precursor Substances 0.000 description 42
- 239000000976 ink Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 150000002258 gallium Chemical class 0.000 description 8
- 150000002471 indium Chemical class 0.000 description 8
- 150000001879 copper Chemical class 0.000 description 7
- -1 copper chalcogenide compound Chemical class 0.000 description 7
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- QWDGPLAREJUSJA-UHFFFAOYSA-N octane-1-selenol Chemical compound CCCCCCCC[SeH] QWDGPLAREJUSJA-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003958 selenols Chemical class 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- ZTPZXOVJDMQVIK-UHFFFAOYSA-N dodecane-1-selenol Chemical compound CCCCCCCCCCCC[SeH] ZTPZXOVJDMQVIK-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZAKSIRCIOXDVPT-UHFFFAOYSA-N trioctyl(selanylidene)-$l^{5}-phosphane Chemical compound CCCCCCCCP(=[Se])(CCCCCCCC)CCCCCCCC ZAKSIRCIOXDVPT-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- PIOZWDBMINZWGJ-UHFFFAOYSA-N trioctyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCCCCCP(=S)(CCCCCCCC)CCCCCCCC PIOZWDBMINZWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910005543 GaSe Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
-
- 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
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
- H01L31/036—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
- H01L31/0392—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
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Abstract
Description
本願は、2013年11月13日に出願された米国仮出願第61/904,780号の利益を主張する。
銅インジウムジセレニド(CulnSe2)は、その独特な構造的及び電気的特性から、薄膜PV用途の最も有望な候補の一つである。1.0eVのバンドギャップは、太陽スペクトルに良く合っている。CulnSe2太陽電池は、CulnS2のセレン化によって作られる。なぜならば、セレン化プロセス中、SeがSと置き換わって、この置換が、体積膨張を生じるからである。体積膨張は、空隙を減少させ、高質で高密度のCulnSe2吸収層を再現性良く与える(Q. Guo, G.M. Ford, H.W. Hillhouse and R. Agrawal, Nano Lett., 2009, 9, 3060)。SeがSと完全に置換すると仮定すると、その結果の格子体積膨張は約14.6%であり、この値は、黄銅鉱(正方晶系)CulnS2(a=5.52Å,c=11.12Å)及びCulnSe2(a=5.78Å,c=11.62Å)の格子定数に基づいて計算されている。このことは、CulnS2ナノ結晶膜は、セレンリッチな雰囲気中にて膜をアニールすることで、セレンを主とする材料に容易に変換できることを意味している。それ故に、CulnS2は、CulnSe2又はCuln(S,Se)2吸収層を作製する代替的な前駆体として有望である。
a)溶媒中のCu塩、In塩及び/又はGa塩を第1温度で加熱する(102)。
b)有機カルコゲン前駆体を添加する(104)。
c)反応溶液を第2温度に加熱して、第1時間間隔撹拌する(106)。
d)随意選択的に、反応溶液を第3温度に冷却して、第2時間間隔撹拌する(108)。
e)反応溶液を室温に冷却する(110)。
f)ナノ粒子を単離する(112)。
a)Cu塩、In塩及び/又はGa塩を溶媒中で混合する(202)。
b)有機カルコゲン前駆体を添加する(204)。
c)反応溶液を第1温度に加熱して、第1時間間隔撹拌し、揮発性副産物を蒸留除去する(206)。
d)反応溶液を第2温度に加熱して、第2時間間隔に亘って第2のカルコゲン前駆体を加える(208)。
e)第3時間間隔、第2温度にて反応溶液を撹拌する(210)。
f)反応溶液を第3温度に冷却し、第4時間間隔撹拌する(212)。
g)反応溶液を室温に冷却する(214)。
h)ナノ粒子を単離する(216)。
a)溶媒にナノ粒子を溶解/分散させて、インクAを作る(302)。
b)インクAを基板に堆積させて膜を作る(304)。
c)不活性雰囲気中でアニールする(306)。
d)アニールされた膜が所望の厚さに至るまで、工程b)及び工程c)を繰り返す(309)。
e)必要に応じて、アニール、焼結、セレン化、KCNエッチングのような更なる膜処理工程を実行する(308)。
f)n型半導体層を堆積させて、ジャンクションを形成する(310)。
g)真性の(intrinsic)ZnOを堆積させて、拡張欠乏層を形成する(312)。
h)窓層を堆積する(314)。
i)金属グリッドを堆積する(316)。
j)デバイスを封じ込める(318)。
ln(OAc)3(32.057g、120.0mmol)と、Cu(OAc)(19.157g、156.3mmol)と、240mLのベンジルエーテルとを、リービヒ冷却器及びコレクタが付いた1−Lの丸底フラスコにて混合した。混合物を90分間、100℃で脱ガスし、その後N2を充填した。脱ガスした1−オクタンチオール(192mL、1.10mol)を加えて、混合物を200℃に加熱し、2時間撹拌し、その後、160℃まで冷まして、約18時間撹拌した。混合物を室温に冷却した。
ln(OAc)3(3.995g、13.7mmol)と、Cu(OAc)(2.422g、19.8mmol)と、100mLのベンジルエーテルとを、リービヒ冷却器及びコレクタが付いた100mLの丸底フラスコにて混合し、N2でパージした。脱ガスした30mLのベンジルエーテルを加えて、その後、混合物を100℃に加熱した。脱ガスした1−オクタンチオール(24mL、138mmol)を加えて、混合物を200℃に加熱し、6時間撹拌し、室温まで冷ました。
リービヒ冷却器及びコレクタが付いた丸底フラスコにて、15mLの1−オクタデセンを、約110℃で45分間脱ガスし、N2下で室温まで冷却した。Cu(OAc)(0.79g、6.4mmol)と、ln(OAc)3(1.54g、5.3mmol)とを加えて、更に10分間、140℃で脱ガスした。混合物を室温まで冷却した。1−オクタンセレノール(12mL、68mmol)を加えて、溶液を加熱した。酢酸が120℃で蒸留し始めて、シリンジを用いてコレクタから除去した。溶液を135乃至145℃で30分間加熱して、酢酸の残留物を蒸留させて、その後、トリオクチルホスフィンセレニド(1.71M、8mL、14mmol)を、10分間にわたって加えた。溶液を、140℃で1時間撹拌した。溶液を90℃に冷却し、その後、4時間半アニールして、室温まで冷却した。
1−オクタンチオールでキャッピングされた銅リッチなCuInS2ナノ粒子(Cu:In=1:0.76)をトルエンに溶解させて、200mg/mLの溶液Bを作った。
1−オクタンチオールでキャッピングされた銅リッチなCuInS2ナノ粒子(Cu:In=1:0.85)をトルエンに溶解して、インクCを作った。
Claims (22)
- a.ナノ粒子を溶媒に混合してインクを作る工程であって、ナノ粒子は、式CuInwGaxSeySz(CIGS)であって、0≦w、x<1、w+x<1、y,z≧0、y+z≒2である三元、四元、五元カルコゲニド、それらのドープされた種、合金、及び組合せからなる群から選択される、工程と、
b.インクを基板に堆積させてCIGS膜を形成する工程と、
c.不活性雰囲気中にてCIGS膜をアニールして、アニールされた膜を作る工程と、
d.アニールされたCIGS膜が予め決めされた厚さを得るまで、工程b及び工程cを繰り返す工程と、
を含むプロセスによって作られるCIGSを用いた光起電力デバイス。 - アニール、焼結、セレン化、及び、KCNを用いたエッチングからなる膜処理工程の群から選択された少なくとも1つの膜処理工程を工程dに続いて実行する工程を更に含む、請求項1に記載のCIGSを用いた光起電力デバイス。
- 0.7≦w+x<1である、請求項1に記載のCIGSを用いた光起電力デバイス。
- 溶媒は、トルエン、アルカン、ジクロロメタン、クロロホルム、イソホロン、アニソール、α−テルピネン、及びリモネンからなる群から選択される、請求項1に記載のCIGSを用いた光起電力デバイス。
- インクは更に、インク調合物全体の2乃至5wt%の濃度のオレイン酸を含む、請求項1に記載のCIGSを用いた光起電力デバイス。
- 基板は、インジウムスズ酸化物(ITO)、モリブデンコーティングされたベアガラス、及び、モリブデンコーティングされたソーダライムガラス(SLG)からなる群から選択される、請求項1に記載のCIGSを用いた光起電力デバイス。
- CIGSの膜厚が少なくとも1μmとなるまで、工程dにおいて工程b及び工程cが繰り返される、請求項1に記載のCIGSを用いた光起電力デバイス。
- 少なくとも1つのバッファ層が基板に堆積して処理された後に、インクが堆積する、請求項1に記載のCIGSを用いた光起電力デバイス。
- 少なくとも1つのバッファ層は、インクを調製するのに使用されるナノ粒子とは化学量論組成が異なっているCIGSナノ粒子を含む、請求項8に記載のCIGSを用いた光起電力デバイス。
- インジウムに対する銅の比(Cu/In)は、1未満である、請求項9に記載のCIGSを用いた光起電力デバイス。
- バッファ層の厚さは、≦100nmである、請求項8に記載のCIGSを用いた光起電力デバイス。
- 膜は、3乃至7分間、250乃至300℃である低い第1温度でアニールされ、その後、3乃至7分間、400乃至430℃である高い第2温度でアニールされる、請求項1に記載のCIGSを用いた光起電力デバイス。
- 作製プロセスは更に、硫化プロセスを含む少なくとも1つの更なる膜処理工程を、工程dの後に実行する工程を含んでおり、硫化プロセス中、CIGS膜は、硫黄リッチな雰囲気中でアニールされる、請求項1に記載のCIGSを用いた光起電力デバイス。
- 硫黄リッチな雰囲気は、不活性のキャリアガス中のH2Sガスによって与えられる、請求項13に記載のCIGSを用いた光起電力デバイス。
- 作製プロセスは更に、セレン化プロセスを含む少なくとも1つの更なる膜処理工程を、工程dの後に実行する工程を含んでおり、セレン化プロセス中、CIGS膜は、セレンリッチな雰囲気中でアニールされる、請求項1に記載のCIGSを用いた光起電力デバイス。
- セレンリッチな雰囲気は、不活性のキャリアガス中のH2Seガスによって与えられる、請求項15に記載のCIGSを用いた光起電力デバイス。
- セレン化プロセスは、CIGSナノ粒子中の過剰な銅をセレン化銅に変換する、請求項15に記載のCIGSを用いた光起電力デバイス。
- セレン化プロセスは更に、CuInS2層をCuInSe2へと少なくとも部分的に変換する、請求項15に記載のCIGSを用いた光起電力デバイス。
- 作製プロセスは更に、KCN溶液中におけるCIGS層のエッチングを含んでおり、CIGS膜から過剰なセレン化銅相及び/又は硫化銅相が選択的に除去される、請求項1に記載のCIGSを用いた光起電力デバイス。
- 作製プロセスは、
e.アニールされた膜にn型半導体層を堆積させてジャンクションを形成する工程と、
f.真性のZnOを堆積させて、拡張欠乏層を形成する工程と、
g.拡張欠乏層上に窓層を堆積する工程と、
h.窓層上に金属グリッドを堆積させてアセンブリを形成する工程と、
i.アセンブリを封じ込めて光起電力デバイスを形成する工程と、
を更に含む、請求項1に記載のCIGSを用いた光起電力デバイス。 - n型半導体層は、CdS、Zn(O,S)、ZnO、及びZnSからなる群から選択された材料を含んでいる、請求項21に記載のCIGSを用いた光起電力デバイス。
- 窓層は、インジウムスズ酸化物(ITO)、アルミニウム酸化亜鉛(AZO)及びボロンドープ酸化亜鉛からなる群から選択された材料で構成される、請求項21に記載のCIGSを用いた光起電力デバイス。
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CN (2) | CN108840312A (ja) |
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US20180355201A1 (en) | 2017-06-07 | 2018-12-13 | Nanoco Technologies Ltd. | CIGS Nanoparticle Ink Formulation with a High Crack-Free Limit |
CN110373641A (zh) * | 2019-07-10 | 2019-10-25 | 桂林理工大学 | 一种太阳能电池cigs靶材的快速制备方法 |
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CN108840312A (zh) | 2018-11-20 |
TWI595680B (zh) | 2017-08-11 |
JP2017501952A (ja) | 2017-01-19 |
CN105899462B (zh) | 2018-06-22 |
WO2015071671A1 (en) | 2015-05-21 |
US20180248057A1 (en) | 2018-08-30 |
KR101815277B1 (ko) | 2018-01-05 |
CN105899462A (zh) | 2016-08-24 |
US20150136213A1 (en) | 2015-05-21 |
TW201733153A (zh) | 2017-09-16 |
TW201526277A (zh) | 2015-07-01 |
US9960298B2 (en) | 2018-05-01 |
HK1222836A1 (zh) | 2017-07-14 |
KR20160086915A (ko) | 2016-07-20 |
EP3068729A1 (en) | 2016-09-21 |
JP6411499B2 (ja) | 2018-10-24 |
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