CN104993016B - 一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法 - Google Patents
一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法 Download PDFInfo
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- CN104993016B CN104993016B CN201510315108.4A CN201510315108A CN104993016B CN 104993016 B CN104993016 B CN 104993016B CN 201510315108 A CN201510315108 A CN 201510315108A CN 104993016 B CN104993016 B CN 104993016B
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- tin
- noble metal
- zinc
- sulfur
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 60
- 239000002159 nanocrystal Substances 0.000 title abstract description 30
- 238000000034 method Methods 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000004528 spin coating Methods 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 239000010970 precious metal Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 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 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical group NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 239000011135 tin Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- 239000010408 film Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000010931 gold Substances 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 12
- 229940043267 rhodamine b Drugs 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 2
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- -1 octadecylene Chemical group 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- VSKWIQRKBCVBAG-UHFFFAOYSA-N [Cu].[Zn].[Se] Chemical compound [Cu].[Zn].[Se] VSKWIQRKBCVBAG-UHFFFAOYSA-N 0.000 description 1
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法，该方法是先制备贵金属纳米晶颗粒分散液，再制备含铜、锌、锡和硫源的分散液，进一步将两种分散液在稳定剂存在下混合成分散性及稳定性好的前驱体溶液，再结合旋涂、烧结工艺，制备出贵金属纳米晶负载铜锌锡硫薄膜。该制备方法操作简单、反应条件温和、对原料要求低，制备的贵金属纳米晶负载铜锌锡硫薄膜具有优异的催化效果，且贵金属纳米晶的负载量可以任意调控，可广泛应用于不同领域。
Description
技术领域
本发明涉及一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法，属于材料制备领域。
背景技术
贵金属纳米晶是由数量有限的贵金属原子组成的聚合体，它具有贵金属块体所不具备的特殊性质。例如：表面效应，量子尺寸效应，小尺寸效应，宏观量子隧道效应，库伦阻塞与量子隧穿效应和介电限域效应等。正是由于贵金属纳米晶具有以上这些特殊性质，使得其在催化，能源以及生物医学等应用领域展现出优良的性能。近几年，铜锌锡硫作为一种廉价、性能优越的新兴的半导体材料在催化与能源领域也被广泛研究。将贵金属纳米材料与铜锌锡硫复合可以得到一种先进的功能材料，极大地提高其光吸收以及催化性能。香港理工大学研究人员将贵金属纳米晶与铜锌锡硫纳米晶材料复合得到一种以贵金属纳米晶为核，铜锌锡硫为壳结构的纳米材料。将其应用于光催化方面，发现这种复合纳米晶的催化性能优于单纯的铜锌锡硫纳米晶的光催化性能(Advanced Materials，2014年，第26卷，3496-3500页)。西班牙加泰罗尼亚能源研究所的科研人员在铜锌锡硫纳米晶表面生长贵金属纳米晶也得到了一种贵金属负载的铜锌锡硫纳米晶，其表现出优良的催化性能(Journal of the American Chemical society，2014年，第136卷，9236-9239页)。纵观以上研究，其证明了在铜锌锡硫纳米晶中负载贵金属纳米晶对于提升铜锌锡硫纳米晶的光学与催化性能是有帮助的，但是以上两篇论文的负载方法均是在纳米晶尺寸，其制备条件极其苛刻，需要去除掉所有反应原料自带的结晶水以及反应气氛中的水，同时隔绝空气，并且以上方法制备的产物产量极少，因此不利于大规模的工业化生产。若能在铜锌锡硫块体薄膜上进行贵金属负载可以有效解决以上难题。但是如何将贵金属纳米晶负载到铜锌锡硫薄膜中，并应用于铜锌锡硫薄膜领域(例如：铜锌锡硫薄膜光电催化领域)，这方面的研究还未见报道。目前这个方向处于空白是由于常用的铜锌锡硫薄膜制备方法(例如，磁控溅射法，热蒸发法以及电沉积法等)在制备铜锌锡硫薄膜的过程中难以同时实现贵金属纳米晶的负载。
发明内容
针对现有技术中无法实现在块状的铜锌锡硫薄膜上负载贵金属纳米晶的问题，本发明的目的是在于提供一种能将贵金属纳米晶有效负载在铜锌锡硫薄膜上制备出具有高催化活性的贵金属纳米晶负载铜锌锡硫薄膜的方法，通过该方法贵金属纳米晶的负载量可以任意调控，能制备出适应于多种领域需要的催化材料。
为了实现本发明的技术目的，本发明提供了一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法，该方法包括以下步骤：
步骤一：将贵金属盐分散在溶剂I中，再向溶剂I中加入还原剂进行还原反应，得到贵金属纳米晶颗粒，将贵金属纳米晶颗粒分散在溶剂II中，得到溶液A；
步骤二：将铜盐、锌盐、锡盐和硫源分散在溶剂III中，得到溶液B；
步骤三：将溶液A和溶液B混合，在稳定剂存在下搅拌均匀，得到前驱体溶液C；
步骤四：将前驱体溶液C旋涂成膜，在硫蒸汽气氛下烧结，得到贵金属纳米晶负载铜锌锡硫薄膜。
本发明的技术方案在制备的贵金属纳米晶颗粒分散液的基础上，通过稳定剂将贵金属纳米晶颗粒分散液与铜源、锌源、锡源和硫源的混合液形成分散性及稳定性很好的前驱体溶液，再结合旋涂及共烧结工艺，能将贵金属纳米晶颗粒很好地负载的生成的铜锌锡硫薄膜基体中，解决了现有技术中无法实现块体铜锌锡硫薄膜贵金属纳米晶颗粒的缺陷。
本发明的贵金属纳米晶负载铜锌锡硫薄膜的制备方法还包括以下优选方案：
优选的方案中贵金属盐为贵金属的氯化盐、硝酸盐、硫酸盐和氯酸盐中的至少一种。
优选的方案中贵金属为Pt、Au、Ag、Ru、Pd和Ir中的至少一种。
较优选的方案中溶液A中贵金属盐的总摩尔浓度为3～300mM。
优选的方案中所述的还原剂为氢硼化钠、二甲基胺硼烷、三辛基膦和三丁基膦中的至少一种。
优选的方案中还原剂的用量根据贵金属盐中贵金属离子总含量来确定，还原剂的电子转移数为贵金属离子总电子转移数的1～5倍。
优选的方案中稳定剂为二甘醇胺，乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、十八烯、乙二硫醇、1,3-丙硫醇和油胺中的至少一种。
优选的方案中稳定剂的用量为溶液A和溶液B中金属总摩尔量的1～5％。
优选的方案中溶液B中铜盐的浓度为0.2～2.0M，锌盐的浓度为0.1～1.0M，锡盐的浓度为0.1～1.0M，硫源的浓度为0.8～8M。具体浓度根据实际需要的铜锌锡硫材料进行调整。
优选的方案中铜盐、锌盐和锡盐各自独立地选自铜或锌或锡的氯化盐、硝酸盐、硫酸盐、草酸盐、醋酸盐及其它有机盐中的至少一种。
优选的方案中硫源为硫酸铵、乙硫醇、丙硫醇、戊硫醇、硫粉、硫脲、硫化钠和硫化钾中的至少一种。
优选的方案中烧结温度控制在500～700℃。
优选的方案中溶液A和溶液B在30～80℃搅拌反应。
优选的方案中溶剂I、溶剂II和溶剂III各自独立地选自去离子水、甲醇、乙醇、甲醚、乙醚、乙二醇、乙二醇甲醚、N,N-二甲基甲酰胺、1,4-丁内酯、甲苯、异丙醇、正丁烷和丙酮中的至少一种。
优选的方案中贵金属纳米晶负载铜锌锡硫薄膜中贵金属纳米晶的质量含量为0.1～20％。
本发明的步骤一中的分散过程、步骤二的分散过程及步骤三中的溶液A和溶液B的反应过程都在搅拌条件下进行。溶液A和溶液B的反应过程先在低速(100～1000rpm)搅拌5～60s，再在高速(1000～5000rpm)搅拌5～60s。
本发明的制备贵金属纳米晶负载铜锌锡硫薄膜的方法包括以下具体步骤：
第一步：配制含有贵金属纳米晶的溶液A
将贵金属盐分散于溶剂I中，配制成3～300mM的溶液，随后向其溶液中加入还原剂进行还原反应，得到纳米晶颗粒，随后将纳米晶颗粒离心分散于溶剂II中配制成3～300mM的溶液A；
第二步：配制含有铜锌锡硫元素的溶液B
将铜盐(浓度为0.2～2.0M)，锌盐(浓度为0.1～1.0M)，锡源(浓度为0.1～1.0M)和硫源(0.8～8M)按照铜锌锡硫的原子计量比分散于溶剂III中，在30～60℃下搅拌，得到溶液B；
第三步：配制前驱体溶液
根据所需要配制的贵金属负载比例，将溶液A和溶液B混合，同时加入稳定剂，在30～60℃搅拌，配制分散性和稳定性良好的含有贵金属纳米晶的铜锌硒硫前驱体溶液C；
第四步：烧结成型
将前驱体溶液C旋涂成膜，在硫蒸汽条件下烧结，得到贵金属负载的铜锌锡硫薄膜。
相对现有技术，本发明的有益效果：
1、本发明首次在温和条件下成功合成贵金属纳米晶负载的铜锌锡硫薄膜，相对现有的工艺(一般需要真空和惰性气体保护等苛刻条件)，本发明在非真空液相环境下制备，方法简单节能，利于大规模、工业化生产。
2、本发明的技术方案对原料要求不高，分析纯原料即可。现有的磁控溅射法，热蒸发法以及电沉积法等都需要高纯度的原料，成本较高。
3、本发明的方法可以有效地控制贵金属纳米晶在铜锌锡硫薄膜中的负载量，可以针对所需贵金属的量精确调节负载比例，满足实际情况的需求。
4、本发明可以同时实现多种贵金属在铜锌锡硫薄膜中同时负载，进一步加强铜锌锡硫薄膜光电以及催化方面的性能。
5、本发明制备的贵金属纳米晶负载铜锌锡硫薄膜相对铜锌锡硫薄膜具有更好的催化效果。
具体实施方案
以下实施例旨在进一步说明本发明内容，而不是限制本发明权利要求的保护范围。
实施例1
未负载贵金属纳米晶铜锌锡硫薄膜的制备
1.将16mmol氯化锡、30mmol氯化铜、20mmol氯化锌和130mmol硫脲加入到60mL乙二醇甲醚中，40℃搅拌半小时完成铜锌锡硫前驱体的配制
2.将配好的铜锌锡硫前驱体溶液滴在基片表面，200rpm低速旋涂10s，然后以2000rpm的高速旋涂10s完成铜锌锡硫薄膜的旋涂。
3.将2中制备的预制层薄膜置于管式炉中硫化退火，退火温度为500摄氏度，完成未负载贵金属纳米晶铜锌锡硫薄膜的制备。
将制备的铜锌锡硫薄膜应用于罗丹明B水溶液的催化降解(罗丹明B水溶液的浓度10mg/l，液体体积20mL，铜锌锡硫薄膜面积9cm2，氙灯光源150W)，催化降解反应5h后，罗丹明B的降解率为41％。
实施例2
0.5％Pt纳米晶负载铜锌锡硫薄膜的制备
1.将0.18mmol氯铂酸加入到50mL去离子水中配制成氯铂酸的水溶液，将6mmol氢硼化钠加入到50mL去离子水中配制成氢硼化钠的水溶液，将1mL氢硼化钠的水溶液滴加到5mL的氯铂酸的水溶液中室温下反应10分钟，将沉淀产物离心分散于甲苯中，完成3mM铂纳米晶溶液的制备。
2.将16mmol硫酸锡、30mmol硫酸铜、20mmol硫酸锌和130mmol硫化钠加入到40mL N,N-二甲基甲酰胺中，60℃搅拌2小时完成铜锌锡硫前驱体溶液的配制。
3.将1中制备的3mM铂纳米晶的溶液5mL加入到2中所配的375mM铜锌锡硫前驱体溶液8mL中，同时加入1％的稳定剂三乙醇胺，40℃搅拌半小时混合完成0.5％铂纳米晶负载铜锌锡硫前驱体溶液的配制。
4.将配好的含有铂纳米晶的铜锌锡硫前驱体溶液滴在基片表面，500rpm低速旋涂20s，然后以3000rpm的高速旋涂35s完成铜锌锡硫薄膜的旋涂。
5.将4中制备的预制层薄膜置于管式炉中硫化退火，退火温度600摄氏度，完成铂纳米晶负载铜锌锡硫薄膜的制备。
将制备的铂纳米晶负载的铜锌锡硫薄膜应用于罗丹明B水溶液的催化降解(罗丹明B水溶液的浓度10mg/l，液体体积20mL，铜锌锡硫薄膜面积9cm2，氙灯光源150W)，催化降解反应5h后，罗丹明B的降解率为63％。
实施例3
20％Au纳米晶负载铜锌锡硫薄膜的制备
1.将18mmol氯化金加入到50mL乙二醇中配制成氯铂金的溶液，将100mmol三辛基膦加入到50mL乙二醇中配制成三辛基膦的溶液，将15mL三辛基膦的溶液滴加到50mL的氯化金的溶液中室温下反应10分钟，将沉淀产物离心分散于异丙醇中，完成300mM金纳米晶溶液的制备。
2.将16mmol硝酸锡、30mmol硝酸铜、20mmol硝酸锌和130mmol戊硫醇加入到20mL甲醇中，60℃搅拌2小时完成铜锌锡硫前驱体溶液的配制。
3.将1中制备的300mM铂纳米晶的溶液10mL加入到2中所配的750mM铜锌锡硫前驱体溶液20mL中，同时加入5％的稳定剂乙醇胺，40℃搅拌半小时混合完成20％金纳米晶负载铜锌锡硫前驱体溶液的配制。
4.将配好的含有金纳米晶的铜锌锡硫前驱体溶液滴在基片表面，800rpm低速旋涂50s，然后以4500rpm的高速旋涂50s完成铜锌锡硫薄膜的旋涂。
5.将4中制备的预制层薄膜置于管式炉中硫化退火，退火温度650摄氏度，完成铂纳米晶负载铜锌锡硫薄膜的制备。
将制备的金纳米晶负载的铜锌锡硫薄膜应用于罗丹明B水溶液的催化降解(罗丹明B水溶液的浓度10mg/l，液体体积20mL，铜锌锡硫薄膜面积9cm2，氙灯光源150W)，催化降解反应5h后，罗丹明B的降解率为89％。
实施例4
0.1％Pt和1％Au纳米晶共同负载铜锌锡硫薄膜的制备
1.将6mmol氯铂酸加入到50mL正丁烷中配制成氯铂酸的溶液，将25mmol三丁基膦加入到25mL正丁烷中配制成三丁基膦的溶液，将1mL三丁基膦的溶液滴加到5mL的氯铂酸的溶液中室温下反应10分钟，将沉淀产物离心分散于甲醚中，完成100mM铂纳米晶溶液的制备。
2.将6mmol氯化金加入到50mL正丁烷中配制成氯铂金的溶液，将25mmol三丁基膦加入到25mL正丁烷中配制成三丁基膦的溶液，将1mL三丁基膦的溶液滴加到5mL的氯化金的溶液中室温下反应10分钟，将沉淀产物离心分散于甲醚中，完成100mM金纳米晶溶液的制备。
3.将32mmol硝酸锡、60mmol硫酸铜、40mmol氯化锌和260mmol乙硫醇加入到60mL 1,4-丁内酯中，同时加入2％的二乙醇胺作为稳定剂，80℃搅拌半小时完成铜锌锡硫前驱体溶液的配制。
3.将1中制备的100mM铂纳米晶的溶液0.1mL以及2中制备的100mM金纳米晶的溶液1mL一齐加入到2中所配的1000mM铜锌锡硫前驱体溶液10mL中，80℃搅拌1小时混合完成0.1％铂纳米晶和1％金纳米晶共同负载的铜锌锡硫前驱体溶液的配制。
4.将配好的含有铂和金纳米晶的铜锌锡硫前驱体溶液滴在基片表面，1000rpm低速旋涂60s，然后以5000rpm的高速旋涂60s完成铂和金纳米晶共同负载的铜锌锡硫薄膜的旋涂。
5.将4中制备的预制层薄膜置于管式炉中硫化退火，退火温度700摄氏度，完成铂和金纳米晶共同负载的铜锌锡硫薄膜的制备。
将制备的0.1％铂和1％金纳米晶共同负载的铜锌锡硫薄膜应用于罗丹明B水溶液的催化降解(罗丹明B水溶液的浓度10mg/l，液体体积20mL，0.5％铂和0.1％金纳米晶共同负载的铜锌锡硫薄膜面积9cm2，氙灯光源150W)，催化降解反应5h后，罗丹明B的降解率为74％。
Claims (9)
1.一种贵金属纳米晶负载铜锌锡硫薄膜的制备方法，包括以下步骤：
步骤一：将贵金属盐分散在溶剂I中，再向溶剂I中加入还原剂进行还原反应，得到贵金属纳米晶颗粒，将贵金属纳米晶颗粒分散在溶剂II中，得到溶液A；
步骤二：将铜盐、锌盐、锡盐和硫源分散在溶剂III中，得到溶液B；
步骤三：将溶液A和溶液B混合，在稳定剂存在下搅拌均匀，得到前驱体溶液C；
步骤四：将前驱体溶液C旋涂成膜，在硫蒸汽气氛下烧结，得到贵金属纳米晶负载铜锌锡硫薄膜；
所述的溶剂I、溶剂II和溶剂III各自独立地选自去离子水、甲醇、乙醇、甲醚、乙醚、乙二醇、乙二醇甲醚、N,N-二甲基甲酰胺、1,4-丁内酯、甲苯、异丙醇、正丁烷和丙酮中的至少一种。
2.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的贵金属盐为贵金属的氯化盐、硝酸盐、硫酸盐和氯酸盐中的至少一种；所述的贵金属为Pt、Au、Ag、Ru、Pd和Ir中的至少一种。
3.根据权利要求1或2所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的溶液A中贵金属盐的总摩尔浓度为3～300mM。
4.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的还原剂为氢硼化钠、二甲基胺硼烷、三辛基膦和三丁基膦中的至少一种，还原剂的用量根据贵金属盐中贵金属离子总含量来确定，还原剂的电子转移数为贵金属离子总电子转移数的1～5倍；
所述的稳定剂为二甘醇胺，乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、十八烯、乙二硫醇、1,3-丙硫醇和油胺中的至少一种，稳定剂的用量为溶液A和溶液B中金属总摩尔量的1～5％。
5.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的溶液B中铜盐的浓度为0.2～2.0M，锌盐的浓度为0.1～1.0M，锡盐的浓度为0.1～1.0M，硫源的浓度为0.8～8M。
6.根据权利要求1或5所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的铜盐、锌盐和锡盐各自独立地选自铜或锌或锡的氯化盐、硝酸盐、硫酸盐、草酸盐、醋酸盐及其它有机盐中的至少一种；所述的硫源为硫酸铵、乙硫醇、丙硫醇、戊硫醇、硫粉、硫脲、硫化钠和硫化钾中的至少一种。
7.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，所述的烧结温度控制在500～700℃。
8.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，溶液A和溶液B在30～80℃搅拌反应。
9.根据权利要求1所述的贵金属纳米晶负载铜锌锡硫薄膜的制备方法，其特征在于，贵金属纳米晶负载铜锌锡硫薄膜中贵金属纳米晶的摩尔含量为0.1～20％。
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