CN108840312A - 富铜的铜铟(镓)二硒化物/二硫化物纳米粒子的制备 - Google Patents
富铜的铜铟(镓)二硒化物/二硫化物纳米粒子的制备 Download PDFInfo
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- CN108840312A CN108840312A CN201810528285.4A CN201810528285A CN108840312A CN 108840312 A CN108840312 A CN 108840312A CN 201810528285 A CN201810528285 A CN 201810528285A CN 108840312 A CN108840312 A CN 108840312A
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- nanoparticle
- copper
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 131
- 239000010949 copper Substances 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 24
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 19
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 title claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 title description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 63
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 31
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 31
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 19
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 13
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 51
- 239000002243 precursor Substances 0.000 claims description 43
- 150000003839 salts Chemical class 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 17
- 125000001741 organic sulfur group Chemical group 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 11
- -1 gallium salt salt Chemical class 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 7
- 150000004770 chalcogenides Chemical class 0.000 claims description 7
- 150000002471 indium Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000058 selane Inorganic materials 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
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- 239000011669 selenium Substances 0.000 description 27
- 229910052711 selenium Inorganic materials 0.000 description 21
- 230000008569 process Effects 0.000 description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 8
- 150000003958 selenols Chemical class 0.000 description 8
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- 239000007789 gas Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 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 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- ZDABWEJSXJTEDB-UHFFFAOYSA-N decane-1-selenol Chemical compound C(CCCCCCCCC)[SeH] ZDABWEJSXJTEDB-UHFFFAOYSA-N 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- ZTPZXOVJDMQVIK-UHFFFAOYSA-N dodecane-1-selenol Chemical compound CCCCCCCCCCCC[SeH] ZTPZXOVJDMQVIK-UHFFFAOYSA-N 0.000 description 4
- 239000013529 heat transfer fluid Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
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- 235000012431 wafers Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001388 alpha-terpinene derivatives Chemical class 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000001743 benzylic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
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- 239000011541 reaction mixture Substances 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004544 sputter deposition Methods 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
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PHPKKGYKGPCPMV-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] PHPKKGYKGPCPMV-UHFFFAOYSA-N 0.000 description 1
- IBQKNIQGYSISEM-UHFFFAOYSA-N [Se]=[PH3] Chemical class [Se]=[PH3] IBQKNIQGYSISEM-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation 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
- 239000006071 cream Substances 0.000 description 1
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- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 238000007701 flash-distillation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01L31/0248—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
-
- 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
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Abstract
一种用于制备铜铟(镓)二硒化物/二硫化物(CIGS)纳米粒子的方法,其利用富铜化学计量法。将富铜CIGS纳米粒子用有机硫族元素配体覆盖,使得纳米粒子适合在有机溶剂中处理。可以将纳米粒子沉积在衬底上并在富硫族元素气氛中热处理以促使过量的铜向硒化铜或硫化铜的转化,所述硒化铜或硫化铜可以充当烧结助熔剂以促进液相烧结并因此促进大晶粒的生长。如此制备的纳米粒子可用于制造基于CIGS的光伏器件。
Description
本申请是申请日为2014年11月23日、国际申请号为PCT/GB2014/053371、中国国家阶段申请号为201480072862.3且发明名称为《富铜的铜铟(镓)二硒化物/二硫化物纳米粒子的制备》的发明申请的分案申请。
相关申请的交叉引用
本申请要求2013年11月15日提交的美国临时申请No.61/904,780的权益。
关于联邦政府发起的研究或开发的声明:不适用。
发明背景
1、发明领域
本发明总体上涉及用于光伏电池的材料。更具体地,涉及制备铟镓二硒化物/二硫化物(CIGS)纳米粒子的方法。本发明还涉及由基于纳米粒子的前体墨形成的基于CIGS的器件。
2、包括在37CFR 1.97和1.98下公开的信息的相关技术的描述
对于商业生命力而言,光伏(PV)电池必须以可与化石燃料竞争的成本发电。为了满足这些成本,PV电池必须包含低成本材料,连同价廉的器件制造工艺和中等到高的太阳光至电力的转化效率。为了使器件-构造方法成功,材料合成和器件制造必须能够在商业上放大规模。
目前的光伏市场依然由基于硅晶片的太阳能电池(第一代太阳能电池)主导。然而,这些太阳能电池的活性层由厚度跨度从微米至几百微米的硅晶片制成,因为硅是相对差的光吸收剂。这些单晶晶片的制备是非常昂贵的,因为该方法包括制造和切片高纯度单晶硅锭,并且也非常浪费。
结晶硅晶片的高成本使得工业界寻求更便宜的材料来制造太阳能电池,为此许多开发工作集中在制备高效薄膜太阳能电池,其中材料成本与硅相比显著降低。
半导体材料如铜铟镓二硒化物和二硫化物(Cu(In,Ga)(S,Se)2,本文中称作“CIGS”)是强吸光剂并且具有与PV应用的最佳光谱范围匹配良好的带隙。此外,因为这些材料具有强吸收系数,太阳能电池中的活性层只需要几微米的厚度。
铜铟二硒化物(CuInSe2)由于其独特的结构和电性质是最有希望用于薄膜PV应用的候选者之一。其1.0eV的带隙与太阳光谱匹配良好。CuInSe2太阳能电池可以通过CuInS2膜的硒化制造,因为在硒化过程中,Se替代S并且该取代产生体积膨胀,这减小空隙空间并且可再生产地产生高质量的致密CuInSe2吸收剂层[Q.Guo,G.M.Ford,H.W.Hillhouse和R.Agrawal,Nano Lett.,2009,9,3060]。假设S完全被Se取代,所得的晶格体积膨胀为~14.6%,这是基于黄铜矿(四方晶系)CuInS2的晶格参数和CuInSe2的晶格参数计算的。这意味着CuInS2纳米晶体膜可以通过将该膜在富硒气氛中退火而容易地转化为占优势的硒化物材料。因此,CuInS2是有希望的用于制备CuInSe2或CuIn(S,Se)2吸收剂层的备选前体。
吸收剂材料的理论最佳带隙在1.2-1.4eV范围内。通过将镓掺合到CuIn(S,Se)2纳米粒子中,可以操纵带隙使得在硒化后以太阳能吸收的最佳带隙形成CuxInyGazSaSeb吸收剂层。
按照惯例,采用高成本的气相或蒸发技术(例如金属-有机化学气相沉积(MO-CVD),射频(RF)溅射和闪蒸)将CIGS膜沉积在衬底上。尽管这些技术提供高质量膜,它们难以并且代价昂贵地放大至更大面积沉积和更高工艺生产量。
使用CIGS纳米粒子的一个主要优点在于,它们可以分散在介质中形成墨,该墨可以以与类似报纸工艺中的墨相似的方式印刷在衬底上。纳米粒子墨或膏可以使用低成本印刷技术如旋涂、狭缝涂布和刮刀式涂布(doctor blading)来沉积。可印刷的太阳能电池可以代替太阳能电池制造的标准的常规真空沉积方法,因为印刷工艺,尤其是在辊-至-辊加工框架中执行时,能够带来非常高的生产量。
迄今为止开发的合成方法提供对粒子形态的有限控制,并且粒子溶解性通常差,造成墨配制困难。
挑战在于制备这样的纳米粒子,其总体上是小的,具有低熔点,窄的尺寸分布并且结合挥发性覆盖剂(capping agent),使得它们可以分散在介质中并且覆盖剂可以在膜烘焙过程中容易地消除。另一挑战是避免夹杂杂质,无论是来自合成前体还是有机配体,其可能累及最终器件的总效率。申请人的共同未决的美国专利申请,公开号为2009/0139574和2014/0249324,描述了用有机硫族元素配体覆盖(cap with)的CIGS纳米粒子(其用作形成光伏器件的前体)的可放大合成,它们通过引用以其全文形式结合在此。
与基于纳米粒子的CIGS沉积方法相关的挑战之一在于在热处理后获得大晶粒。在膜厚度数量级上的粒度是所希望的,因为晶粒边界起到电子-空穴复合中心的作用。
已经报道元素掺杂剂,如钠[R.Kimura,T.Mouri,N.Takuhai,T.Nakada,S.Niki,A.Yamada,P.Fons,T.Matsuzawa,K.Takahashi和A.Kunioka,Jpn.J.Appl.Phys.,1999,38,L899]和锑[M.Yuan,D.B.Mitzi,W.Liu,A.J.Kellock,S.J.Chey和V.R.Deline,Chem.Mater.,2010,22,285]提高CIGS膜的粒度并且因此提高所得器件的功率转化效率(PCE)。
在另一种途径中,将二元铜硫族元素化物添加到一种或多种CIGS前体以促进晶粒生长。熔点低于CIGS的铜硫族元素化物化合物可以充当烧结助熔剂以在远低于其熔点的温度促进CIGS层的晶粒生长。据认为,在烧结温度,烧结助熔剂是液体,其湿润CIGS晶粒使得它们溶解在液体中。据信这促进粒子结合,导致更高的致密化率和更低的烧结温度,并且被称作“液相烧结”。
Casteleyn等人研究了Cu、CuSe、Cu2Se和Se添加剂对CuInSe2膜的影响[M.Casteleyn,M.Burgelman,B.Depuydt,A.Niemegeers和I.Clemminck,IEEE First WorldConference on Photovoltaic Energy Conversion,1994,1,230]。据发现,在富硒气氛中,富Cu相形成CuSe,CuSe在其熔点(523℃)之上充当助熔剂以促进液相烧结,并且因此促进晶粒生长。
Kim等将一层溅射的Cu2Se应用到溅射的Cu-In-Ga膜的表面上,随后硒化以形成CIGS层[M.S.Kim,R.B.V.Chalapathy,K.H.Yoon和B.T.Ahn,J.Electrochem Soc.,2010,157,B154]。发现当总的Cu/(In+Ga)比例大于0.92时Cu2Se促进晶粒生长。
在硫化之前已经将Cu2S粉末(熔点:435℃)添加至Cu2In2O5纳米粒子,以促进向黄铜矿CuInS2的转化并且推动晶粒生长。[C.-Y.Su,D.K.Mishra,C.-Y.Chiu和J.-M.Ting,Surf.Coat.Technol.,2013,231,517]。
申请人的共同未决的美国专利申请号61/847,639描述了硒化铜纳米粒子的制备,所述硒化铜纳米粒子可以作为助熔剂添加至CIGS材料以促进晶粒生长。纳米粒子熔点低于相应的主体硒化铜相的熔点,使得硒化铜纳米粒子能够在降低的温度进行液相烧结。
在使用二元铜硫族元素化物前体促进晶粒生长的现有技术方法中,采用预先制备的铜硫族元素化物化合物。因此,需要一种原位形成铜硫族元素化物相的方法,以降低与形成具有大晶粒的CIGS膜相关的处理要求。本文中,描述了一种使用基于纳米粒子的沉积途径提高CIGS膜的粒度的方法,其中CIGS纳米粒子是富铜的。可以将纳米粒子在富硫族元素气氛中处理以促进过量的铜向硒化铜或硫化铜的转化,所述硒化铜或硫化铜充当烧结助熔剂促进液相烧结并且因此促进大晶粒的生长。所得CIGS吸收剂层的化学计量可以通过纳米粒子化学计量法和退火后处理步骤如KCN蚀刻两者控制。
发明概述
在某些实施方案中,本发明包括一种合成富铜CIGS纳米粒子的方法。将富铜CIGS纳米粒子用有机硫族元素配体覆盖,使得纳米粒子可在有机溶剂中处理。可以将纳米粒子沉积到衬底上并在富硫族元素气氛中热处理以促进过量的铜向硒化铜或硫化铜的转化,所述硒化铜或硫化铜可以充当烧结助熔剂促进液相烧结,并且因此促进大晶粒的生长。所得CIGS吸收剂层的化学计量可以通过纳米粒子化学计量法和退火后处理步骤如KCN蚀刻两者控制,其可用于选择性地消除过量的二元铜硫族元素化物相。CIGS吸收剂层可以随后结合到光伏器件中。
附图中几幅视图的简述
图1是显示根据本发明的某些实施方案制备富Cu的CIGS纳米粒子的第一种方法的流程图。
图2是显示根据本发明的某些实施方案制备富Cu的CIGS纳米粒子的第二种方法的流程图。
图3是显示根据本发明的某些实施方案使用富Cu的CIGS纳米粒子制备光伏器件的方法的流程图。
图4比较了根据实施例用富Cu的CIGS纳米粒子制备的CIGS膜X-射线衍射图401与用近化学计量的CIGS纳米粒子制备的CIGS膜的X-射线衍射图402。
图5是由根据实施例制备的富Cu的CIGS纳米粒子制备的CIGS膜的扫描电子显微镜检图片。
发明详述
此处,描述一种制备CIGS纳米粒子的方法。还描述了纳米粒子的处理形成墨,该墨可以被沉积以形成基于CIGS的膜,并且随后处理以形成PV器件。在器件处理过程中,纳米粒子中过量的铜可以与硫族元素源反应以形成二元硫族元素化物,其可以充当助熔剂以促进CIGS层的液相烧结。术语“CIGS”在本文中应理解为描述CuxInyGazSaSeb形式的任何物质。典型地,x≈y+z≈1,并且a+b≈2,但是该物质不需要是化学计量的。例如,在一些实施方案中,描述CIGS纳米粒子,其中x>y+z。
在器件处理过程中,纳米粒子中过量的铜与硫族元素源反应以原位形成一种或多种二元硫族元素化物相,这些二元硫族元素化物相可以充当促进大晶粒生长的烧结助熔剂。过量的铜与之反应的硫族元素源可以由纳米粒子(例如,来自有机硫族元素覆盖(capping)配体)和/或由外部硫族元素化过程例如硒化提供。
在第一实施方案中,制备CuxInyGazSa形式的纳米粒子,其中x>y+z,并且a≈2,并且包括其掺杂的衍生物。纳米粒子用一种或多种有机-硫醇配体,例如1-辛硫醇覆盖。
在第二实施方案中,制备CuxInvGazSeb形式的纳米粒子,其中x>y+z,并且b≈2,并且包括其掺杂的衍生物。纳米粒子用一种或多种有机-硒醇配体,例如1-辛硒醇覆盖。
在第三实施方案中,制备CuxInyGazSaSeb形式的纳米粒子,其中x>y+z,并且a+b≈2,并且包括其掺杂的衍生物。纳米粒子用一种或多种有机-硫醇和/或有机-硒醇配体,例如1-辛硫醇、1-辛硒醇等覆盖。
根据本发明的某些实施方案,制备富Cu的CIGS纳米粒子的第一种方法如下(附图标记为图1中的流程图100):
a)在溶剂中在第一温度加热Cu、In和/或Ga盐(102)。
b)添加有机硫族元素前体(104)。
c)将反应溶液加热至第二温度并且搅拌持续第一时程(106)。
d)任选地,将反应溶液冷却到第三温度并且搅拌持续第二时程(108)。
e)将反应溶液冷却到室温(110)。
f)分离纳米粒子(112)。
Cu、In和Ga盐可以包括,但不限于:乙酸盐,乙酰丙酮化物,和卤化物,例如氯化物,溴化物,碘化物。利用所述盐的相对比例来控制所得纳米粒子的化学计量。本领域技术人员将认识到:要添加的前体盐的摩尔比率取决于所需的纳米粒子化学计量和前体的相对反应性两者。在某些优选实施方案中,Cu盐与组合的全部In和Ga盐的摩尔比率在约1∶0.65至约1∶0.85之间。
将Cu、In和Ga盐在溶剂中合并。在一些实施方案中,溶剂是非配位溶剂。实例包括,但不限于:1-十八烯,苄基醚,二苯醚,以及传热流体(例如,66)。
将Cu、In和Ga盐在溶剂中加热至第一温度。在一些实施方案中,第一温度位于室温和150℃之间,例如100℃。
将有机硫族元素前体在第一温度添加至反应混合物。有机硫族元素前体既充当硫族元素源又充当覆盖纳米粒子表面以提供溶解性的配体。在一些实施方案中,有机硫族元素前体可以具有低于约250℃的熔点以促进其在器件处理过程中从纳米粒子表面的除去。这是所希望的,因为在处理之前保留在CIGS层中的碳残留物可能对器件性能有不利影响。合适的有机硫族元素前体可以是R-X-H的形式,其中R是烷基或芳基基团并且X是S或Se。实例包括但不限于:1-辛硫醇,1-辛硒醇,以及1-十二烷硒醇。
在添加有机硫族元素前体之后,将反应溶液加热到第二温度并且搅拌持续第一时程。在一些实施方案中,第二温度高于第一温度。例如,第二温度可以落在160-240℃范围内,更具体地,约200℃。在某些实施方案中,第一时程跨度为30分钟-10小时,更具体地约2-6小时。
任选地,将反应溶液冷却到低于第二温度的第三温度并且将反应溶液退火持续第二时程,例如约4-24小时,更具体地约18小时。
在冷却到室温后,将纳米粒子与反应溶液分离。纳米粒子可以通过现有技术中已知的任何方法分离,例如添加一种或多种溶剂以将纳米粒子从溶液沉淀出来,随后经由离心或过滤进行收集。本领域技术人员将认识到用以分离纳米粒子的一种或多种溶剂的选择取决于在其中进行纳米粒子合成的溶剂的化学性质。
根据某些实施方案,制备富Cu的CIGS纳米粒子的第二种方法如下(附图标记为图2中的流程图200):
a)在溶剂中混合Cu、In和/或Ga盐(202)。
b)添加有机硫族元素前体(204)。
c)将反应溶液加热到第一温度并且搅拌持续第一时程以蒸馏出任何挥发性的副产物(206)。
d)将反应溶液加热到第二温度并且添加第二硫族元素前体,历时第二时程(208)。
e)反应溶液在第二温度搅拌持续第三时程(210)。
f)将反应溶液冷却到第三温度并且搅拌持续第四时程(212)。
g)将反应溶液冷却到室温(214)。
h)分离纳米粒子(216)。
Cu、In和Ga盐可以包括,但不限于:乙酸盐,乙酰丙酮化物,和卤化物,例如,氯化物,溴化物,碘化物。利用所述盐的相对比例来控制所得纳米粒子的化学计量。本领域技术人员将认识到:要添加的前体盐的摩尔比率取决于所需的纳米粒子化学计量和前体的相对反应性两者。
将Cu、In和Ga盐在溶剂中合并。在一些实施方案中,溶剂是非配位溶剂。实例包括但不限于:1-十八烯,苄基醚,二苯醚,和传热流体如66(Solutia,Inc.,St.Louis,Missouri 63141)。
将有机硫族元素前体添加到反应混合物中。有机硫族元素前体既充当硫族元素源又充当覆盖纳米粒子表面以提供溶解性的配体。在一些实施方案中,有机硫族元素前体可以具有低于约250℃的熔点以促进其在器件处理过程中从纳米粒子表面的除去。这是所希望的,因为在处理之前保留在CIGS层中的碳残留物可能对器件性能有不利影响。合适的有机硫族元素前体可以是R-X-H的形式,其中R是烷基或芳基基团并且X是S或Se。实例包括但不限于:1-辛硫醇,1-辛硒醇,以及1-十二烷硒醇。
在添加有机硫族元素前体之后,将反应溶液加热到第一温度并且搅拌持续第一时程以蒸馏出任何挥发性的副产物。本领域技术人员将认识到:第一温度取决于金属前体盐的化学性质和如此形成的副产物的沸点。例如,有机硫族元素前体可以与金属乙酸盐反应以形成作为副产物的乙酸;乙酸可以在超过其沸点(117-118℃)的第一温度被蒸馏。第一时程应当足以充分进行全部挥发性副产物的蒸馏。在一些实施方案中,第一时程为30分钟。
随后将反应溶液加热到第二温度,在此温度加入第二硫族元素前体,历时第二时程。在某些实施方案中,第二温度位于120-160℃范围内,例如140℃。在特定的实施方案中,第二硫族元素前体是溶解在配位溶剂(例如但不限于三辛基膦硫化物(TOP/S)或三辛基膦硒化物(TOP/Se))中的元素硫族元素(elemental chalcogen)。第二硫族元素前体可以逐滴加入,例如以每分钟0.5mmol-1mol,更具体地每分钟约1-10mmol,例如每分钟约1.4mmol的速率。
将反应溶液在第二温度搅拌持续第三时程。在一些实施方案中,第三时程位于30分钟-2小时范围内,例如约1小时。
将反应溶液冷却到低于第二温度的第三温度,然后搅拌持续第四时程。在一些实施方案中,第三温度位于80-120℃范围内,例如约90℃。在某些实施方案中,第四时程在3至6小时之间,例如41/2小时。
在冷却到室温后,将纳米粒子与反应溶液分离。纳米粒子可以通过现有技术中已知的任何方法分离,例如添加一种或多种溶剂以将纳米粒子从溶液沉淀出来,随后经由离心或过滤进行收集。本领域技术人员将认识到用以分离纳米粒子的一种或多种溶剂的选择取决于在其中进行纳米粒子合成的溶剂的化学性质。
根据某些实施方案,CIGS器件由富Cu纳米粒子如下制备(附图标记为图3中的流程图300):
a)将纳米粒子溶解/分散在溶剂中,形成墨A(302)。
b)将墨A沉积到衬底上以形成膜(304)。
c)在惰性气氛中退火(306)。
d)重复步骤b)和c),直至退火的膜达到所需厚度(309)。
e)根据需要,进行进一步的膜处理步骤,例如,退火,烧结,硒化,KCN蚀刻(308)。
f)沉积n-型半导体层以形成结(junction)(310)。
g)沉积本征(intrinsic)ZnO以形成扩展的耗尽层(312)。
h)沉积窗口层(314)。
i)沉积金属栅极(316)。
j)包封所述器件(318)。
在特定的实施方案中,纳米粒子是CuInwGaxSeySz形式的三元、四元或五元硫族元素化物,其中0≤w,x<1,w+x<1,y,z≥0并且y+z≈2,包括掺杂的种类、合金和它们的组合,但不限于这些,并且可以包括其非化学计量的衍生物。在某些实施方案中,0.7≤w+x<1,例如0.7≤w+x≤0.8。纳米粒子必须在溶剂中可溶或可分散。
溶剂必须能够溶解或分散纳米粒子。本领域技术人员将认识到:溶剂的选择取决于纳米粒子的表面涂层,例如覆盖配体的化学性质。优选地,溶剂是有机溶剂。具体实例是甲苯,但是也可以使用本领域技术人员已知的其他溶剂,包括但不限于:烷烃(例如,己烷),氯化溶剂(例如,二氯甲烷,氯仿等),酮(例如,异佛尔酮),醚(例如,茴香醚),萜类(例如,α-萜品烯,柠檬烯等)等。
任选地,可以将另外的添加剂结合到纳米粒子墨中,例如用于改性涂层性质如流变性。在一些实施方案中,将油酸以总墨制剂的2-5重量%的浓度加入。
可以采用任何合适的方法沉积纳米粒子墨A。实例包括但不限于:旋涂、窄缝涂布、刮刀式涂布和喷墨印刷。
可以将纳米粒子墨A沉积在任何合适的衬底上。实例包括但不限于:铟锡氧化物(ITO),涂钼的原玻璃(bare glass),和涂钼的钠钙玻璃(SLG)。
在一些实施方案中,在沉积墨A之前,将一个或多个阳极缓冲层沉积在衬底上并且加工。阳极缓冲层可以例如由具有与用于配制墨A的纳米粒子的化学计量不同的化学计量的CIGS纳米粒子组成。在特定的实施方案中,阳极缓冲层是富铟的,即,比例Cu/In<1。在某些实施方案中,每个阳极缓冲层的厚度≤100nm,例如在50-70nm之间。
在特定的实施方案中,重复步骤b)和c)直至CIGS膜厚度大于或等于1μm。例如,膜厚度可以位于1.0-2.0μm的范围。
本领域技术人员将认识到:沉积每一CIGS层后的退火温度和时间将取决于墨制剂的溶剂和有机成分的性质。在某些实施方案中,将膜在250-300℃范围内的较低的第一温度退火,例如在约270℃,退火3-7分钟,例如约5分钟,然后将膜在400-430℃范围内的较高的第二温度,例如约415℃,退火3-7分钟,例如约5分钟。
在一些实施方案中,膜处理步骤可以包括硫化步骤,在该步骤中将CIGS膜在富硫气氛中退火。可以使用任何合适的硫源以提供富硫气氛,例如可以蒸发的固体或液体硫化合物,或气体硫源。在特定的实施方案中,由在惰性载气中的浓度≤10%,例如2-5%的H2S气体提供富硫气氛,所述惰性载气例如但不限于N2。
膜处理步骤包括硒化步骤,在硒化步骤期间将CIGS膜在富硒气氛中退火。硒化步骤可以促进CIGS纳米粒子中过量的铜向硒化铜的转化,形成用以促进液相烧结和大晶粒生长的助熔剂。当使用Cu(In,Ga)S2纳米粒子时,硒化步骤还可以进行CuInS2层至CuInSe2的部分或完全转化。可以使用任何合适的硒源以提供富硒气氛,例如可以蒸发的固体或液体硒化合物,或气体硒源。在特定的实施方案中,由在惰性载气中的浓度≤10%,例如2-5%的H2Se气体提供富硒气氛,所述惰性载气例如但不限于N2。
膜处理步骤可以进一步包括KCN蚀刻。CIGS膜在KCN溶液中的蚀刻可用于从CIGS吸收剂层选择性地除去过量的硒化铜和/或硫化铜相。蚀刻步骤可以在5-15%KCN溶液,例如10%KCN溶液中,进行30秒-5分钟的时间,例如3分钟。
可以沉积任何合适的n-型半导体层。实例包括但不限于:CdS,Zn(O,S),ZnO和ZnS。
在一些实施方案中,窗口层由铝锌氧化(AZO)组成,但是可以使用本领域技术人员已知的其他透明的导电氧化物,例如铟锡氧化物(ITO)和掺硼的氧化锌(BZO)。
本发明的一个方面提供一种用于制备CIGS纳米粒子的方法,包括:将铜盐与选自由铟盐和镓盐组成的组的至少一种盐一起在溶剂中在第一温度加热,以产生反应溶液;将有机硫族元素前体加入到反应溶液;将反应溶液加热到第二温度同时搅拌持续第一时程;将反应溶液冷却到室温;并且将纳米粒子从反应溶液分离。
Cu盐与组合的全部In和Ga盐的摩尔比率可以在约1∶0.65至约1∶0.85之间。该方法可以进一步包括:在将反应溶液加热到第二温度后将反应溶液冷却到第三温度并且搅拌持续第二时程。由铜盐、铟盐和镓盐组成的组可以包括选自由乙酸盐、乙酰丙酮化物、氯化物、溴化物和碘化物组成的组的盐。溶剂可以是非配位溶剂,其可以选自由1-十八烯、苄基醚、二苯醚和包括氢化三联苯的传热流体组成的组。第一温度可以在室温和约100℃之间。有机硫族元素前体可以是R-X-H的形式,其中R是烷基或芳基基团,并且X是硫或硒。有机硫族元素前体可以选自由1-辛硫醇、1-辛硒醇和1-十二烷硒醇组成的组。第二温度可以高于第一温度。第二温度可以在约160℃至约240℃之间。该方法还可以包括将反应溶液在低于第二温度的温度退火约4小时至约24小时的时间。纳米粒子的分离可以包括通过添加至少一种其它溶剂将纳米粒子从溶液中沉淀出来。
本发明的另一方面提供由包括以下步骤的方法制备的CIGS纳米粒子:将铜盐与选自由铟盐和镓盐组成的组的至少一种盐一起在溶剂中在第一温度加热以产生反应溶液;将有机硫族元素前体添加到反应溶液中;将反应溶液加热到第二温度同时搅拌持续第一时程;将反应溶液冷却到室温;并且从反应溶液分离纳米粒子。
Cu盐与组合的全部In和Ga盐的摩尔比率可以在约1∶0.65至约1∶0.85之间。制备方法可以进一步包括:在将反应溶液加热到第二温度之后将反应溶液冷却到第三温度并且搅拌持续第二时程。
本发明的另一方面提供一种制备CIGS纳米粒子的方法,包括:将选自由铜盐、铟盐和镓盐组成的组的盐在溶剂中在第一温度混合以产生反应溶液;将有机硫族元素前体加入到反应溶液中;将反应溶液加热到第一温度同时搅拌持续第一时程;将反应溶液加热到第二温度并且加入第二硫族元素前体,历时第二时程;将反应溶液在第二温度搅拌持续第三时程;将反应溶液冷却到第三温度并且搅拌持续第四时程;将反应溶液冷却到室温;并且分离纳米粒子。
Cu盐与组合的全部In和Ga盐的摩尔比率可以在约1∶0.65至约1∶0.85之间。由铜盐、铟盐和镓盐组成的组可以包括选自由乙酸盐、乙酰丙酮化物、氯化物、溴化物和碘化物组成的组的盐。溶剂可以是非配位溶剂,其可以选自由1-十八烯、苄基醚、二苯醚和包括氢化三联苯的传热流体组成的组。有机硫族元素前体可以是R-X-H的形式,其中R是烷基或芳基基团,并且X是硫或硒。有机硫族元素前体可以具有低于约250℃的沸点。有机硫族元素前体可以选自由1-辛硫醇、1-辛硒醇和1-十二烷硒醇组成的组。第一时程可以足以进行基本上所有挥发性副产物的蒸馏。第二温度可以在约120℃至约160℃之间。第二硫族元素前体可以包括溶解在配位溶剂中的元素硫族元素,所述溶剂可以选自由三辛基膦硫化物和三辛基膦硒化物组成的组。第二温度可以在约120℃至约160℃之间。第三时程可以在约30分钟至约2小时之间。第三温度可以在约80℃至约120℃之间。第四时程可以在约3小时至约6小时之间。纳米粒子的分离可以包括通过添加至少一种其它溶剂将纳米粒子从溶液沉淀出来。
本发明的另一方面提供由包括以下步骤的方法制备的CIGS纳米粒子:将选自由铜盐、铟盐和镓盐组成的组的盐在溶剂中在第一温度混合以产生反应溶液;将有机硫族元素前体加入到反应溶液中;将反应溶液加热到第一温度同时搅拌持续第一时程;将反应溶液加热到第二温度并且加入第二硫族元素前体,历时第二时程;将反应溶液在第二温度搅拌第三时程;将反应溶液冷却到第三温度并且搅拌持续第四时程;将反应溶液冷却到室温;并且分离纳米粒子。
Cu盐与组合的全部In和Ga盐的摩尔比率在约1∶0.65至约1∶0.85之间。
本发明的再一方面提供一种由包括以下步骤的方法制备的基于CIGS的光伏器件:将纳米粒子在溶剂中混合以形成墨;将墨沉积到衬底上以形成膜;将该膜在惰性气氛中退火以产生退火的膜;重复步骤b和c直至退火的膜达到预定厚度;将n-型半导体层沉积到退火的膜上以形成结;将本征ZnO沉积到所述结上以形成扩展的耗尽层;将窗口层沉积到扩展的耗尽层上;将金属栅极沉积到窗口层上以形成组装体;并且包封该组装体以形成光伏器件。
所述制备方法可以还包括:在步骤d之后进行至少一个进一步膜处理步骤,其选自由退火、烧结、硒化和用KCN蚀刻组成的膜处理步骤组。纳米粒子可以选自由CuInwGaxSeySz形式的三元、四元和五元硫族元素化物组成的组,其中0≤w,x<1,w+x<1,y,z≥0并且y+z≈2,包括掺杂的种类、合金和它们的组合。任选地,0.7≤w+x<1。纳米粒子可以溶解在溶剂中。纳米粒子可以分散在溶剂中。溶剂可以选自由甲苯、烷烃、二氯甲烷、氯仿、异佛尔酮、茴香醚、α-萜品烯和柠檬烯组成的组。墨可以另外包含浓度为总的墨制剂的约2-5重量%的油酸。衬底可以选自由铟锡氧化物(ITO)、涂钼的原玻璃和涂钼的钠钙玻璃(SLG)组成的组。可以重复步骤b和c直至CIGS膜厚度为至少1μm。可以在沉积墨之前将至少一个缓冲层沉积到衬底上并且处理。至少一个缓冲层可以包含化学计量与用于配制墨的纳米粒子的化学计量不同的CIGS纳米粒子。铜与铟的比例(Cu/In)可以小于1。缓冲层的厚度可以≤100nm。可以将膜在约250℃-300℃的较低的第一温度退火约3-7分钟,然后在约400℃-430℃的较高的第二温度退火约3-7分钟。制备方法可以进一步包括:在步骤d之后进行至少一个进一步膜处理步骤,包括硫化步骤,在所述硫化步骤期间将CIGS膜在富硫气氛中退火。由在惰性载气中的H2S气体提供富硫气氛。制备方法可以进一步包括:在步骤d之后进行至少一个进一步膜处理步骤,包括硒化步骤,在所述硒化步骤期间将CIGS膜在富硒气氛中退火。由在惰性载气中的H2Se气体提供富硒气氛。硒化步骤可以进行CIGS纳米粒子中过量的铜向硒化铜的转化。硒化步骤还可以进行CuInS2层至CuInSe2的至少部分转化。制备方法可以进一步包括在KCN溶液中蚀刻CIGS膜,以从CIGS吸收剂层选择性地除去过量的硒化铜和/或硫化铜相。n-型半导体层可以包含选自由CdS、Zn(O,S)、ZnO和ZnS组成的组的材料。窗口层可以由选自由铝锌氧化(AZO)和掺硼的氧化锌组成的组的材料组成。窗口层可以由铟锡氧化物(ITO)组成。纳米粒子可以是如上所述的根据本发明的该方面的纳米粒子,其涉及由包括以下步骤的方法制备的CIGS纳米粒子:将铜盐与选自由钢盐和镓盐组成的组的至少一种盐一起在溶剂中在第一温度加热以产生反应溶液;将有机硫族元素前体添加至反应溶液;将反应溶液加热到第二温度同时搅拌持续第一时程;将反应溶液冷却到室温;并且从反应溶液分离纳米粒子。纳米粒子可以是如上所述的根据本发明该方面的纳米粒子,其涉及由包括以下步骤的方法制备的CIGS纳米粒子:将选自由铜盐、铟盐和镓盐组成的组的盐在溶剂中在第一温度混合以产生反应溶液;将有机硫族元素前体添加至反应溶液;将反应溶液加热到第一温度同时搅拌持续第一时程;将反应溶液加热到第二温度并且加入第二硫族元素前体,历时第二时程;将反应溶液在第二温度搅拌持续第三时程;将反应溶液冷却到第三温度并且搅拌持续第四时程;将反应溶液冷却到室温;并且分离纳米粒子。
实施例
实施例1:用1-辛硫醇覆盖的富铜CuInS2纳米粒子(Cu∶In=1∶0.75)的合成
将In(OAc)3(32.057g,120.0mmol)、Cu(OAc)(19.157g,156.3mmol)和240mL的苄基醚在配备Liebig冷凝器和收集器的1-L圆底烧瓶中混合。将混合物在100℃脱气90分钟,然后用N2回填。加入脱气的1-辛硫醇(192mL,1.10mol),将混合物加热到200℃并且搅拌2小时,之后允许其冷却到160℃并且留置搅拌大约18小时。将混合物冷却到室温。
通过添加溶剂接着离心,在空气中分离纳米粒子。
纳米粒子由CPS盘式离心分析(CPS Instruments Inc.,Prairieville,Pennsylvania)的表征显示粒度在3nm数量级。
实施例2:用1-辛硫醇覆盖的富铜CuInS2纳米粒子(Cu∶In=1∶0.84)的合成
将In(OAc)3(3.995g,13.7mmol)和Cu(OAc)(2.422g,19.8mmol)在配备Liebig冷凝器和收集器、用N2吹扫的100mL圆底烧瓶中混合。加入30mL脱气的苄基醚,然后将混合物加热到100℃。加入脱气的1-辛硫醇(24mL,138mmol),将混合物加热到200℃并且搅拌6小时,之后使其冷却到室温。
通过添加溶剂接着离心,在空气中分离纳米粒子。
实施例3:用1-辛硒醇覆盖的富铜CuInSe2纳米粒子(Cu∶In=1∶0.84)的合成
将15mL的1-十八烯在配备Liebig冷凝器和收集器的圆底烧瓶中在大约110℃脱气45分钟,然后在N2下冷却到室温。加入Cu(OAc)(0.79g,6.4mmol)和In(OAc)3(1.54g,5.3mmol),然后将混合物在140℃进一步脱气10分钟。将混合物冷却到室温。加入1-辛硒醇(12mL,68mmol)并且加热溶液。乙酸在120℃开始蒸馏并且用注射器从收集器除去。将溶液在135-145℃之间加热30分钟以允许剩余的乙酸蒸馏,然后在10分钟内加入三辛基膦硒化物(1.71M,8mL,14mmol)。将溶液在140℃搅拌1小时。将溶液冷却到90℃,然后退火41/2小时,之后冷却到室温。
通过添加溶剂接着离心,在空气中分离纳米粒子。
实施例4:从富铜CuInS2纳米粒子制备的薄膜
将用1-辛硫醇覆盖的富铜CuInS2纳米粒子(Cu∶In=1∶0.76)溶解在甲苯中以形成200mg/mL的溶液B。
通过旋涂,以3000rpm的旋转速度,将CuInS2阳极缓冲层沉积在涂钼的SLG衬底上。将阳极缓冲层在270℃退火5分钟并且在415℃退火5分钟以除去配体,得到~50nm的层厚度。
通过旋涂,以1500rpm的旋转速度,将墨B沉积到阳极缓冲层的上部。将该膜在270℃退火5分钟,然后在415℃退火5分钟,以除去墨制剂中的有机成分。将该过程进一步重复4次,直至膜厚度大于1μm。
使用在N2中的2.18体积%H2Se,将该膜在富硒气氛下、在500℃退火60分钟。
图4比较了膜的X-射线衍射(XRD)图401与根据相同程序使用近化学计量的CuInS2纳米粒子以1∶0.95的Cu∶In比例制备的膜的X-射线衍射图402。(112)反射的半峰值全宽度(FWHM)分析显示:与采用近化学计量纳米粒子制备的膜的峰宽(2θ=0.36°)相比,用富Cu纳米粒子制备的膜的峰宽(2θ=0.17°)明显更窄。由于峰FWHM与粒度成反比,这些结果表明富Cu纳米粒子促进晶粒生长。
实施例5:具有富铟缓冲层的从富铜CuInS2纳米粒子制备的薄膜
将用1-辛硫醇覆盖的富铜CuInS2纳米粒子(Cu∶In=1∶0.85)溶解在甲苯中以形成墨C。
通过旋涂,以3000rpm的旋转速度,将用1-十二烷硫醇覆盖的富In的Cu(In,Ga)S2纳米粒子(Cu∶In∶Ga=1∶1.13∶0.16)的缓冲层沉积到涂Mo的SLG衬底上。将该阳极缓冲层在270℃退火5分钟并且在415℃退火5分钟,以除去配体。将该过程再重复一次。
通过旋涂,以3000rpm的旋转速度,将墨C沉积到缓冲层的上部。将该膜在270℃退火5分钟,然后在415℃退火5分钟,以除去墨制剂中的有机成分。将该过程重复7次,以获得大于1μm的总膜厚度。
使用在N2中的2.18体积%的H2Se,将该膜在富硒气氛下在500℃退火60分钟。
图5显示了该膜的扫描电子显微镜检(SEM)图片。例如,CIGS层显示全结晶,粒度在1.1μm数量级。
尽管已经显示和描述了本发明的具体实施方案,但是它们不意在限制本专利的覆盖范围。本领域技术人员将理解:如后附权利要求文字或等价覆盖的,可以在不背离本发明范围的情况下进行各种变化和修改。
Claims (10)
1.一种组合物,所述组合物包含:
溶剂;
溶解或分散在所述溶剂中的多个纳米粒子,所述纳米粒子具有化学式CuInwGaxSeySz,其中0≤w,x<1,w+x<1,y,z≥0并且y+z=2;和
用于改性流变性的另外的添加剂。
2.权利要求1所述的组合物,其中所述纳米粒子具有在1∶0.65至1∶0.85之间的Cu盐与组合的In盐+Ga盐的总量的比率(铜盐∶[In盐+Ga盐])。
3.根据前述权利要求中任一项所述的组合物,其中所述纳米粒子用有机-硒醇或有机-硫醇覆盖。
4.根据前述权利要求中任一项所述的组合物,其中所述溶剂是甲苯、烷烃、氯化溶剂、酮、醚和萜中的任一种,并且所述另外的添加剂是油酸。
5.一种形成光伏器件吸收剂层的方法,所述方法包括:
将墨组合物沉积在衬底上以形成墨膜,所述膜组合物包含:
溶剂;
多个富铜的铜铟镓二硒化物/二硫化物(CIGS)纳米粒子;和
流变性改性剂;
将所述墨膜在富硫族元素气氛中退火以将过量的铜转化为硒化铜或硫化铜;和
在退火的同时,烧结所述墨膜以形成具有CIGS晶体的吸收剂层;其中
所述硒化铜或硫化铜充当烧结助熔剂。
6.权利要求5所述的方法,其中所述富硫族元素气氛包含惰性载气和H2S,并且所形成的硫族元素化铜是硫化铜。
7.根据权利要求5至6中任一项所述的方法,其中所述富硫族元素气氛包含惰性载气和H2Se,并且所形成的硫族元素化铜是硒化铜。
8.根据权利要求5至7中任一项所述的方法,所述方法还包括:
在沉积所述墨组合物之前,将富In的Cu(In,Ga)S2纳米粒子的缓冲层沉积在所述衬底上;和
将所述缓冲层退火。
9.一种用于制备CIGS纳米粒子的方法,所述方法包括:
将铜盐与选自由铟盐和镓盐组成的组中的至少一种盐一起在溶剂中在第一温度加热以产生反应溶液;
将有机硫族元素前体加入到所述反应溶液中;
将所述反应溶液加热到第二温度,同时搅拌持续第一时程;
将所述反应溶液冷却到室温;以及
从所述反应溶液分离纳米粒子。
10.一种基于CIGS的光伏器件,其通过包括以下步骤的方法制备:
a.将纳米粒子在溶剂中混合以形成墨;
b.将所述墨沉积在衬底上以形成膜;
c.将所述膜在惰性气氛中退火以产生退火的膜;
d.重复步骤b和c直至所述退火的膜达到预定厚度;
e.将n-型半导体层沉积在退火的膜上以形成结;
f.将本征ZnO沉积在所述结上以形成扩展的耗尽层;
g.将窗口层沉积在所述扩展的耗尽层上;
h.将金属栅极沉积在所述窗口层上以形成组装体;以及
i.将所述组装体包封以形成光伏器件。
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2014
- 2014-11-13 JP JP2016531670A patent/JP6411499B2/ja not_active Expired - Fee Related
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- 2014-11-13 EP EP14802108.2A patent/EP3068729A1/en not_active Withdrawn
- 2014-11-13 CN CN201810528285.4A patent/CN108840312A/zh active Pending
- 2014-11-13 KR KR1020167015842A patent/KR101815277B1/ko active IP Right Grant
- 2014-11-13 WO PCT/GB2014/053371 patent/WO2015071671A1/en active Application Filing
- 2014-11-14 TW TW106120360A patent/TW201733153A/zh unknown
- 2014-11-14 TW TW103139658A patent/TWI595680B/zh not_active IP Right Cessation
- 2014-11-14 US US14/541,861 patent/US9960298B2/en not_active Expired - Fee Related
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2016
- 2016-09-22 HK HK16111133.7A patent/HK1222836A1/zh unknown
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2018
- 2018-04-27 US US15/964,924 patent/US20180248057A1/en not_active Abandoned
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KR20160086915A (ko) | 2016-07-20 |
JP6411499B2 (ja) | 2018-10-24 |
WO2015071671A1 (en) | 2015-05-21 |
EP3068729A1 (en) | 2016-09-21 |
CN105899462B (zh) | 2018-06-22 |
US20180248057A1 (en) | 2018-08-30 |
KR101815277B1 (ko) | 2018-01-05 |
CN105899462A (zh) | 2016-08-24 |
TW201526277A (zh) | 2015-07-01 |
TWI595680B (zh) | 2017-08-11 |
US20150136213A1 (en) | 2015-05-21 |
TW201733153A (zh) | 2017-09-16 |
JP2019024106A (ja) | 2019-02-14 |
US9960298B2 (en) | 2018-05-01 |
JP2017501952A (ja) | 2017-01-19 |
HK1222836A1 (zh) | 2017-07-14 |
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