CN106379931A - 一种快速制备铜锌锡硫纳米颗粒的方法 - Google Patents
一种快速制备铜锌锡硫纳米颗粒的方法 Download PDFInfo
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- CN106379931A CN106379931A CN201610868601.3A CN201610868601A CN106379931A CN 106379931 A CN106379931 A CN 106379931A CN 201610868601 A CN201610868601 A CN 201610868601A CN 106379931 A CN106379931 A CN 106379931A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 37
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 229960001124 trientine Drugs 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- VVHXYVGAMODMHK-UHFFFAOYSA-N copper nitric acid hydrate Chemical compound [Cu].[N+](=O)(O)[O-].O VVHXYVGAMODMHK-UHFFFAOYSA-N 0.000 claims description 2
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000035484 reaction time Effects 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- -1 copper chloride dihydrates Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 229910000238 buergerite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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 2
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, 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
- H01L31/04—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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- Y02E10/52—PV systems with concentrators
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明公开一种快速制备铜锌锡硫纳米颗粒的方法,属于太阳能电池材料与器件技术领域,将铜源、锌源、锡源、硫源混入有机溶剂,再加入表面活性剂然后置于微波炉中微波加热合成铜锌锡硫Cu2ZnSnS4纳米颗粒;本发明制备铜锌锡硫纳米颗粒反应速度快,原料来源丰富、无毒、价低,可重复性高、反应装置简单、反应过程可控、产物较纯,并且能够通过改变反应时间方便快速的控制物相。
Description
技术领域
本发明涉及一种快速制备铜锌锡硫(Cu2ZnSnS4)纳米颗粒的方法,属于太阳能电池材料与器件技术领域。
背景技术
铜锌锡硫Cu2ZnSnS4(CZTS)作为一种直接带隙半导体,适用于太阳能电池及其他光学材料,CZTS是与CIGS有类似结构的半导体材料,虽然CIGS的薄膜太阳能电池转化效率达到20.3%,但其原材料In和Ga是稀缺元素,价格昂贵,此外Se既是稀有又是有毒元素,面向大规模生产时受到元素稀缺的制约,CZTS具有无毒、环保的优势作为太阳能电池吸收层是较为理想的半导体材料。
铜锌锡硫常见的结构有锌黄锡矿、黝锡矿和纤锌矿三种,锌黄锡矿CZTS和黝锡矿CZTS的区别在于Cu和Zn的位置不同,纤锌矿CZTS为亚稳态超晶格结构。目前制备合成CZTS半导体材料的方法有真空热蒸发法、电子束蒸发法、溅射法、喷雾热解法、电沉积法、溶剂热法、水热法、溶胶凝胶法、热注入法等。文献Journal of Alloys & Compounds, 2015, 642:140-147.采用溅射法制备CZTS,但反应装置设备比较复杂,对设备要求较高,工艺较为繁琐;文献J Mater Sci:Mater Electron 2015, 26(10):1-10.采用溶剂热法制备锌黄锡矿CZTS,但反应需要在高温高压条件下进行才能得到所需产物,并且反应不易控制。上述方法都未能快速有效的制备铜锌锡硫CZTS纳米颗粒,甚至有些方法所需反应环境与反应条件较为苛刻。除了以上叙述了一些制备某一种物相的CZTS方法,目前越来越多的人也开始关注着相选择的问题。文献Journal of Materials Chemistry, 2012, 22(15):7502-7506.利用水热法通过调配乙二胺与水的比例和改变不同退火温度控制相选择;文献Chemistry AnAsian Journal, 2014, 9(8):2309–2316.采用热注入法通过控制退火温度和有机溶剂混合进行相选择;以上方法通过改变退火温度或者改变溶剂配比来实现相选择,过程比较复杂且时间较长。
本发明公开了一种以乙二醇和三乙烯四胺的混合液为溶剂,利用微波辅助快速制备铜锌锡硫CZTS纳米颗粒的方法,该方法具有反应速度快、反应装置简单、反应周期短、反应过程可控等优点,并且能够通过改变反应时间方便快速的控制物相。
发明内容
本发明的目的在于提供一种快速制备铜锌锡硫纳米颗粒的方法,该方法反应速度快、可重复性高、反应装置简单、反应过程可控、生产成本低、生产原料无毒、产物较纯,并且能够通过改变反应时间方便快速的控制物相,具有良好的应用前景,具体包括以下步骤:
(1)将铜源、锌源、锡源、硫源加入到有机溶剂中,搅拌混合均匀得到澄清溶液,其中铜源、锌源、锡源、硫源的摩尔比为(1.6~2):(1~1.5):(1~1.5):(4~6);
(2)将表面活性剂加入到步骤(1)得到的前驱体中,混合均匀,其中表面活性剂与铜源质量比为1:(0.1~10);
(3)将步骤(2)的混合液进行微波处理,微波功率为40~680W,处理时间为1~4 min,自然冷却;
(4)将步骤(3)微波处理后的混合液离心弃上层液,收集下层反应产物,离心洗涤后所得产物60~90℃下真空干燥6~10 h,即得到铜锌锡硫纳米颗粒。
步骤(1)所述铜源为二水氯化铜、硝酸铜水合物、乙酰丙酮铜、氧化铜、无水乙酸铜中的一种或几种任意比例混合,锌源为二水乙酸锌、硝酸锌、硫酸锌、氯化锌、氧化锌中的一种或几种任意比例混合,锡源为二水氯化锡、乙酸锡、四碘化锡、双乙酰丙酮氯化锡、二氧化锡中的一种或几种混合,硫源为硫脲、硫化钠、硫氰酸铵、硫代乙酰胺中的一种或几种任意比例混合。
步骤(1)所述有机溶剂为乙二醇和三乙烯四胺按体积配比(1~3):(4~10)混合的混合物。
步骤(1)所述搅拌为磁力搅拌和超声依次进行,磁力搅拌速度为500~800rpm;超声处理频率为40 KHz,超声5~20 min。
步骤(2)所述表面活性剂为聚乙二醇、聚乙烯吡咯烷酮、乙醇胺、十六烷基三甲基溴化铵、十二烷基磺酸钠中的一种或几种任意比例混合。
步骤(4)所述离心是在转速为10000~12000 rpm条件下离心4~10 min;所述的离心洗涤是在转速为8000~10000 rpm条件下,异丙醇、无水乙醇、去离子水依次分别离心洗涤4~10 min,弃上层液。
本发明的有益效果:
(1)本发明反应时间短,能够在几分钟快速高效反应合成铜锌锡硫纳米颗粒,并且能够通过控制反应时间控制不同物相CZTS,产物较纯,反应装置设备简单,反应更容易控制。
(2)本发明生产效率高,便于大量制备高效率、低成本铜锌锡硫纳米颗粒,通过改变前驱体配比、微波输出功率、处理时间等条件以保证较高成核速率、良好颗粒尺寸分布及形貌、组分的可控性。
(3)本发明加入表面活性剂能够有效改善铜锌锡硫纳米颗粒形貌,从而有利于提高其太阳能电池性能。
(4)本发明利用乙二醇和三乙烯四胺的混合有机溶剂更有效的合成较高纯度CZTS,乙二醇作为表面活性剂可以有效的控制产物的形貌;三乙烯四胺作为主要的回流溶剂具有强还原性、强碱性,容易同过渡元素阳离子形成络合物,具有一定螯合作用。
(5)本发明产物禁带宽度为1.5eV是最大量转换太阳能为电能的理想禁带宽度,为其作为太阳能电池吸收层的最佳半导体材料奠定基础。
附图说明
图1为本发明实施例1合成CZTS纳米颗粒的XRD衍射图;
图2为本发明实施例1合成CZTS纳米颗粒的SEM形貌图;
图3为本发明实施例2合成CZTS纳米颗粒的XRD衍射图;
图4为本发明实施例2合成CZTS纳米颗粒的SEM形貌图;
图5为本发明实施例2合成CZTS纳米颗粒的吸收光谱图谱和(αhν)2~ hν图谱;
图6为本发明实施例3合成CZTS纳米颗粒的XRD衍射图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1
本实施例提供一种快速制备铜锌锡硫纳米颗粒的方法,具体包括以下步骤:
(1)将1.6 mmol二水氯化铜(CuCl2•2H2O)、1.5 mmol二水乙酸(Zn(CH3COO)2•2H2O)、1.25 mmol二水氯化锡(SnCl2•2H2O)、6 mmol硫脲(CS(NH2)2)溶于盛有6 mL乙二醇和60 mL三乙烯四胺的混合溶液的烧杯中,加入搅拌磁子,用磁力搅拌器和超声波清洗仪依次搅拌,磁力搅拌速度为800 rpm,超声处理频率为40 KHz,超声10min,使溶液充分混合均匀得到澄清溶液;
(2)将0.5g表面活性剂聚乙二醇加入到步骤(1)得到的前驱体中,均匀混合后待用;
(3)将步骤(2)获得的溶液放入微波炉中,设置反应系统参数如下:微波功率为680 W,微波反应时间为3min;
(4)将步骤(3)微波加热所得产物自然冷却后用离心机从溶液中分离出来固体产物,离心是在转速10000rpm条件下离心4min,再用异丙醇、无水乙醇、去离子水依次分别离心洗涤3次,离心洗涤是在转速8000 rpm条件下离心8min,所得产物置于真空干燥箱内60 °C下真空干燥8 h即制得铜锌锡硫纳米颗粒。
本实施例制备得到产物进行检测,图1 所示,XRD图谱显示的2θ=16.33, 18.20°,23.13°, 28.41°, 32.92°, 37.97°, 47.30°, 56.15°, 58.91°, 69.23°, 76.46°分别对应锌黄锡矿CZTS晶体(002), (101), (110), (112), (200), (211), (220), (312),(224), (008), (332)晶面[JCPDS 26-0575],表明该物相为四方晶型锌黄锡矿CZTS晶体。
由图2的SEM照片可观察到该CZTS颗粒为大小在100-300nm的块状颗粒。
实施例2
本实施例提供一种快速制备铜锌锡硫纳米颗粒的方法,具体包括以下步骤:
(1)将2 mmol硝酸铜水合物(Cu(NO3)2•2.5H2O)、1.25 mmol硝酸锌(Zn(NO3)2•6H2O)、1mmol乙酸锡(C4H6O4Sn)、6 mmol硫化钠(Na2S•9H2O)溶于盛有6 mL乙二醇和24mL三乙烯四胺的混合溶液的烧杯中,加入搅拌磁子,用磁力搅拌器和超声波清洗仪依次搅拌,磁力搅拌速度为600 rpm,超声处理频率为40 KHz,超声5min,使溶液充分混合均匀得到澄清溶液;
(2)将1g表面活性剂聚乙烯吡咯烷酮加入到步骤(1)得到的上述前驱体中,均匀混合后待用;
(3)将步骤(2)获得的溶液放入微波炉中,设置反应系统参数如下:微波功率为600W,微波反应时间为1 min;
(4)将步骤(3)微波加热所得产物自然冷却后用离心机从溶液中分离出来固体产物,离心是在转速11000rpm条件下离心6min,再用异丙醇、无水乙醇、去离子水依次分别离心洗涤3次,离心洗涤是在转速9000 rpm条件下离心10min,所得产物置于真空干燥箱内80 °C下真空干燥10h即制得铜锌锡硫纳米颗粒。
本实施例制备得到产物进行检测,图3所示,XRD图谱显示的2θ=18.21°, 23.13°,28.47°, 32.93°, 47.36°, 56.15°, 58.91°, 69.17°, 76.50°分别对应锌黄锡矿CZTS晶体(101), (110), (112), (200), (220), (312), (224), (008), (332)晶面[JCPDS 26-0575],表明该物相为四方晶型锌黄锡矿CZTS晶体纳米颗粒。
图4的SEM照片表明该CZTS颗粒为大小在100-300nm的块状颗粒。
图5为CZTS纳米颗粒的吸收光谱图谱和(αhν)2~ hν图谱,图5(a)是测得的原始数据图,从中推倒出图5(b),结合两图从图中可知,该纳米颗粒禁带宽度为1.5eV,与直接带隙半导体禁带宽度相符,对制备得到的太阳能薄膜电池的性能提高是有利的。
实施例3
本实施例提供一种快速制备铜锌锡硫纳米颗粒的方法,具体包括以下步骤:
(1)将2mmol乙酰丙酮铜(Cu(acac)2)、1 mmol氯化锌(Zn(Cl)2)、1 mM双乙酰丙酮氯化锡(Sn(acac)2Cl2)、5mmol硫代乙酰胺(C2H5NS)溶于盛有18 mL乙二醇和24mL三乙烯四胺的混合溶液的烧杯中,加入搅拌磁子,用磁力搅拌器和超声波清洗仪依次搅拌,磁力搅拌速度为500 rpm,超声处理频率为40 KHz,超声20min,使溶液充分混合均匀得到澄清溶液;
(2)将表面活性剂0.026g聚乙二醇和0.026g乙醇胺的混合物加入到步骤(1)得到的前驱体中,均匀混合后待用;
(3)将步骤(2)获得的溶液放入微波炉中,设置反应系统参数如下:微波功率为40 W,微波反应时间为4min;
(4)将步骤(3)微波加热所得产物自然冷却后用离心机从溶液中分离出来固体产物,离心是在转速12000rpm条件下离心5min,再用异丙醇、无水乙醇、去离子水依次分别离心洗涤3次,离心洗涤是在转速9000 rpm条件下离心4min,所得产物置于真空干燥箱内90 °C下真空干燥7 h即制得铜锌锡硫纳米颗粒。
本实施例制备得到产物进行检测,图6所示, XRD图谱显示的2θ=27.09°, 28.34°,30.57°,39.58°,47.16°, 51.65°, 56.32°, 72.74°分别对应纤锌矿CZTS晶体(100),(002), (101), (102), (110), (103), (112), (203)晶面,表明该物相为六方纤锌矿CZTS晶体纳米颗粒。
实施例4
本实施例提供一种快速制备铜锌锡硫纳米颗粒的方法,具体包括以下步骤:
(1)将0.9 mmol二水氯化铜(CuCl2•2H2O)和0.9 mmol乙酰丙酮铜(Cu(acac)2)、0.6mmol二水乙酸(Zn(CH3COO)2•2H2O)和0.6mmol氯化锌(Zn(Cl)2)、0.75mmol二水氯化锡(SnCl2•2H2O)和0.75mmol双乙酰丙酮氯化锡(Sn(acac)2Cl2)、2mmol硫脲(CS(NH2)2)和2mmol硫代乙酰胺(C2H5NS)溶于盛有6 mL乙二醇和20mL三乙烯四胺的混合溶液的烧杯中,加入搅拌磁子,用磁力搅拌器和超声波清洗仪依次搅拌,磁力搅拌速度为700rpm,超声处理频率为40 KHz,超声15min,使溶液充分混合均匀得到澄清溶液;
(2)将3.9g表面活性剂聚乙烯吡咯烷酮加入到步骤(1)得到的前驱体中,均匀混合后待用;
(3)将步骤(2)获得的溶液放入微波炉中,设置反应系统参数如下:微波功率为560W,微波反应时间为2 min;
(4)将步骤(3)微波加热所得产物自然冷却后用离心机从溶液中分离出来固体产物,离心是在转速12000rpm条件下离心5min,再用异丙醇、无水乙醇、去离子水依次分别离心洗涤3次,离心洗涤是在转速10000 rpm条件下离心6min,所得产物置于真空干燥箱内70 °C下真空干燥9 h即制得铜锌锡硫纳米颗粒。
Claims (7)
1.一种快速制备铜锌锡硫纳米颗粒的方法,其特征在于,具体包括以下步骤:
(1)将铜源、锌源、锡源、硫源加入到有机溶剂中,搅拌混合均匀得到澄清溶液,其中铜源、锌源、锡源、硫源的摩尔比为(1.6~2):(1~1.5):(1~1.5):(4~6);
(2)将表面活性剂加入到步骤(1)得到的前驱体中,混合均匀,其中表面活性剂与铜源质量比为1:(0.1~10);
(3)将步骤(2)的混合液进行微波处理,微波功率为40~680W,处理时间为1~4 min,自然冷却;
(4)将步骤(3)微波处理后的混合液离心弃上层液,收集下层反应产物,离心洗涤后所得产物60~90℃下真空干燥6~10 h,即得到铜锌锡硫纳米颗粒。
2.根据权利要求1所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,步骤(1)所述铜源为二水氯化铜、硝酸铜水合物、乙酰丙酮铜、氧化铜、无水乙酸铜中的一种或几种任意比例混合,锌源为二水乙酸锌、硝酸锌、硫酸锌、氯化锌、氧化锌中的一种或几种任意比例混合,锡源为二水氯化锡、乙酸锡、四碘化锡、双乙酰丙酮氯化锡、二氧化锡中的一种或几种混合,硫源为硫脲、硫化钠、硫氰酸铵、硫代乙酰胺中的一种或几种任意比例混合。
3.根据权利要求1所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,步骤(1)所述有机溶剂为乙二醇和三乙烯四胺按体积配比(1~3):(4~10)混合的混合物。
4.根据权利要求1所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,步骤(1)所述搅拌为磁力搅拌和超声依次进行。
5.根据权利要求4所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,磁力搅拌速度为500~800 rpm;超声处理频率为40 KHz,超声5~20 min。
6.根据权利要求1所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,步骤(2)所述表面活性剂为聚乙二醇、聚乙烯吡咯烷酮、乙醇胺、十六烷基三甲基溴化铵、十二烷基磺酸钠中的一种或几种任意比例混合。
7.根据权利要求1所述快速制备铜锌锡硫纳米颗粒的方法,其特征在于,步骤(4)所述离心是在转速为10000~12000rpm条件下离心4~10min;所述的离心洗涤是在转速为8000~10000rpm条件下,异丙醇、无水乙醇、去离子水依次分别离心洗涤4~10min,弃上层液。
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CN109148625A (zh) * | 2018-05-17 | 2019-01-04 | 中国科学院物理研究所 | 铜锌锡硫硒薄膜太阳能电池及其制备方法 |
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CN110408391A (zh) * | 2018-04-27 | 2019-11-05 | 中天科技光纤有限公司 | 量子点、量子点/uv胶溶液及量子点掺杂光纤的制备方法 |
CN109148625A (zh) * | 2018-05-17 | 2019-01-04 | 中国科学院物理研究所 | 铜锌锡硫硒薄膜太阳能电池及其制备方法 |
CN112225244A (zh) * | 2020-10-13 | 2021-01-15 | 江曙 | 一种太阳能电池用单分散纳米铜锌锡硫的制备方法 |
CN113979468A (zh) * | 2021-12-09 | 2022-01-28 | 山东中鸿新能源科技有限公司 | 一种太阳能电池组件用CZTS(Se)系纳米粉体的制备方法 |
CN113979468B (zh) * | 2021-12-09 | 2023-05-09 | 山东中鸿新能源科技有限公司 | 一种太阳能电池组件用CZTS(Se)系纳米粉体的制备方法 |
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