CN115385582B - 一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法 - Google Patents
一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法 Download PDFInfo
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- CN115385582B CN115385582B CN202210990212.3A CN202210990212A CN115385582B CN 115385582 B CN115385582 B CN 115385582B CN 202210990212 A CN202210990212 A CN 202210990212A CN 115385582 B CN115385582 B CN 115385582B
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- metal oxide
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 35
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 35
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 229910052751 metal Chemical class 0.000 claims abstract description 49
- 239000002184 metal Chemical class 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 amine salt Chemical class 0.000 claims abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 107
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 9
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 238000007641 inkjet printing Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- 229910004647 CaMoO4 Inorganic materials 0.000 claims description 4
- 229910009372 YVO4 Inorganic materials 0.000 claims description 4
- 150000004652 butanoic acids Chemical class 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 239000012702 metal oxide precursor Substances 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000001243 acetic acids Chemical class 0.000 claims 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 73
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000010949 copper Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 238000010790 dilution Methods 0.000 description 11
- 239000012895 dilution Substances 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 230000003746 surface roughness Effects 0.000 description 9
- 150000001242 acetic acid derivatives Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000004666 short chain fatty acids Chemical class 0.000 description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229940100684 pentylamine Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate 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
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 235000021391 short chain fatty acids Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/253—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/217—FeOx, CoOx, NiOx
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/218—V2O5, Nb2O5, Ta2O5
-
- C—CHEMISTRY; METALLURGY
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Abstract
一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，包括以下步骤：(1)配制脂肪酸/脂肪胺盐离子液体；(2)利用脂肪酸/脂肪胺盐离子液体溶解金属氧化物、金属氢氧化物或金属盐原料，然后用水或醇稀释，或加入硫脲和硒脲分别获得金属氧化物、金属硫化物和金属硒化物前体溶液；(3)通过溶液成膜的方法制备金属前体预制膜，经过退火工艺形成金属氧化物、金属硫化物和金属硒化物薄膜。采用本发明能够在低温分解时缓慢释放薄膜形成时的应力，有效地避免针孔和裂缝的产生，制备出高质量的金属氧化物、硫化物和硒化物薄膜。
Description
技术领域
本发明涉及金属氧化物、金属硫化物和金属硒化物薄膜制备技术领域，具体是一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法。
背景技术
金属氧化物、金属硫化物、金属硒化物半导体薄膜，例如Sn掺杂In2O3(ITO)、Al掺杂ZnO(AZO)、F掺杂SnO2(FTO)、ZnO、TiO2、NiO、In2O3、MoO3、WO3、V2O5、CuO、CaMoO4、YVO4、ZnS、CdS、In2S3、CuS、ZnSe、Ag(SbxBi1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu(InxGa1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu2ZnSn(SySe4-y)4(0≤y≤4)等薄膜，在透明导电电极、薄膜晶体管、光电探测器、电致发光二极管、薄膜太阳能电池等领域具有非常广泛的应用前景。这些金属氧化物、硫化物和硒化物薄膜可以采用物理真空沉积的方法制备也可以采用溶液成膜的方法制备。真空沉积的方法包括真空蒸发、磁控溅射、原子层沉积等方法，这些物理方法需要昂贵的真空设备，同时受真空腔室尺寸的限制难以实现大面积、快速、低成本的制备薄膜。此外，通过溶液的方法也可以制备上述提到的金属氧化物、硫化物和硒化物薄膜，常用的溶液成膜方法包括化学水浴法、旋涂法、垂直提拉法、丝网印刷法、刮涂法、喷涂法和喷墨打印等方法。溶液成膜的方法不需要真空，很容易实现大面积、快速、低成本的制备金属氧化物、硫化物和硒化物薄膜。溶液成膜的方法需要经过配置金属前体溶液、制备金属前体预制膜以及高温退火三个步骤。因此，前体溶液的粘度以及前体溶液与基底的浸润性和铺展性对于最终制备的金属氧化物、硫化物和硒化物薄膜有着巨大的影响。其次，在金属前体预制膜退火形成金属氧化物、硫化物和硒化物薄膜的过程中，薄膜的体积会剧烈收缩同时形成结晶，进而产生应力，所制备的薄膜通常伴随着针孔和裂缝的产生。如果要消除这些由于应力产生的针孔和裂缝，通常需要在金属前体溶液中加入有机表面活性剂，通过表面活性剂的热分解进而可以释放薄膜形成时产生的应力，从而避免针孔和裂缝的产生。通常采用的表面活性剂包括聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酸和曲拉通100等，这些常用的有机表面活性剂在高温分解的时候或多或少会造成碳残留，从而严重影响半导体薄膜的电学和光学性能。
发明内容
本发明要解决现有真空制备技术中金属氧化物、硫化物和硒化物半导体薄膜制备成本高且难以大面积快速制备的技术难题，同时解决常规溶液方法中金属前体溶液粘度难以调节且薄膜的制备容易形成针孔和裂缝的难题，提供一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，能够显著地提高金属氧化物、硫化物和硒化物薄膜的成膜质量，有效地消除针孔和裂缝的产生。
为了解决上述技术问题，本发明的技术方案具体如下：一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，包括以下步骤：
(1)配置脂肪酸/脂肪胺盐离子液体；
(2)利用脂肪酸/脂肪胺盐离子液体溶解金属前体原料；
(3)加入水或醇溶剂稀释调节前体溶液的粘度获得金属氧化物前体溶液，或加入硫脲和硒脲制备金属硫化物和金属硒化物前体溶液；
(4)通过溶液成膜的方法沉积制备金属前体预制膜，经过高温退火原位形成金属氧化物、金属硫化物和金属硒化物薄膜。
步骤(1)所述的脂肪酸和脂肪胺盐离子液体至少包含以下脂肪酸和脂肪胺两类物质中一种或多种，脂肪酸和脂肪胺碳链的长度从1个碳到10个碳，所述的脂肪酸为甲酸、乙酸、丙酸、丙烯酸、丁酸、戊酸、己酸、庚酸、辛酸、异辛酸、癸酸中的一种或多种；所述的脂肪胺为甲胺、乙胺、丙胺、丁胺、叔丁胺、戊胺、己胺、庚胺、辛胺、异辛胺、癸胺中的一种或多种。
步骤(2)所述的配置金属原料包括金属氧化物、金属氢氧化物、金属硝酸盐、金属氯化物、金属乙酰丙酮盐、金属甲酸盐、金属乙酸盐、金属丙酸盐、金属丁酸盐中的一种或多种。
步骤(3)所述的稀释溶剂为水、甲醇、乙醇、异丙醇、乙二醇或乙二醇甲醚中的一种或多种。
步骤(4)所述的溶液成膜方法包括旋涂法、垂直提拉法、刮涂法、喷墨打印法、丝网印刷法和喷涂法。
步骤(4)所述的高温退火温度为100℃到700℃。
步骤(4)所述的形成金属氧化物、硫化物和硒化物薄膜包括ZnO、SnO2、TiO2、NiO、In2O3、MoO3、WO3、V2O5、CuO、CaMoO4、YVO4、ZnS、CdS、In2S3、CuS、ZnSe、Ag(SbxBi1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu(InxGa1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu2ZnSn(SySe4-y)4(0≤y≤4)薄膜。
除另有说明外，本发明所述的百分比均为质量百分比，各组分含量百分数之和为100％。
技术原理
本发明提出一种小分子脂肪酸/脂肪胺离子液体辅助的溶液方法来制备金属氧化物、金属硫化物和金属硒化物薄膜。小分子短链的脂肪酸和脂肪胺在室温下会自发反应生成粘稠的液态脂肪酸/脂肪胺盐离子液体。脂肪酸/脂肪胺盐离子液体由于与金属离子具有较强的配位络合作用，因此在室温下它可以溶解多种金属氧化物、金属氢氧化物、金属脂肪酸盐和金属硝酸盐等前体原料，然后通过加入水或醇作为溶剂稀释，制备出空气稳定且透明均相的金属氧化物前体溶液，通过加入硫脲和硒脲，分别可以获得金属硫化物和金属硒化物前体溶液。把这些金属氧化物、金属硫化物和金属硒化物前体溶液通过溶液成膜的方法制备金属前体预制膜，然后经过高温退火原位分解形成金属氧化物、金属硫化物和金属硒化物薄膜。脂肪酸/脂肪胺盐离子液体除了可以溶解金属原料制备金属前体溶液以及调节金属前体溶液的粘度以外，这些短链的脂肪酸/脂肪胺盐离子液体的分解温度通常在200度以下，并且分解的时候不会沸腾，通过其缓慢热分解可以有效地消除金属氧化物、金属硫化物和金属硒化物薄膜形成时产生的应力，进而可以制备出无针孔、无裂缝且表面光滑平整的金属氧化物、硫化物和硒化物薄膜。
本发明的突出优点在于：
1、采用短链的脂肪酸/脂肪胺盐离子液体作为表面活性剂，它不仅可以溶解多种金属氧化物、金属氢氧化物、金属乙酸盐、金属乙酰丙酮盐、金属丙酸盐、金属丁酸盐、金属硝酸盐、金属氯化物和金属硫酸盐原料，而且短链的脂肪酸/脂肪胺盐离子液体室温的粘度高达150cp，通过改变它的浓度可以在1-150cp大范围内调节金属前体溶液的粘度和表面张力，显著提高金属前体溶液在基底上面的接触角、浸润性和铺展性，从而提高薄膜的质量。
2、短链的脂肪酸/脂肪胺盐离子液体具有低温100％分解的性质，最后没有碳残留，不会影响薄膜的质量，而且在低温分解过程中不沸腾，其缓慢分解的性质可以有效释放薄膜形成时产生的应力，进而可以消除薄膜的针孔和裂缝，制备出光滑平整的金属氧化物、硫化物和硒化物薄膜。
3、脂肪酸/脂肪胺盐离子液体辅助制备的金属氧化物、硫化物和硒化物前体溶液可以采用水或醇作为溶剂，绿色环保。
4、脂肪酸/脂肪胺盐辅助溶液方法可以采用多种溶液成膜方法制备金属前体预制膜，包括旋涂法、垂直提拉法、丝网印刷法、刮涂法、喷墨打印法和喷涂法。
5、脂肪酸/脂肪胺盐辅助溶液方法可以制备多种金属氧化物、硫化物和硒化物半导体薄膜，包括ZnO、SnO2、TiO2、NiO、In2O3、MoO3、WO3、V2O5、CuO、CaMoO4、YVO4、ZnS、CdS、In2S3、CuS、ZnSe、Ag(SbxBi1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu(InxGa1-x)(SySe2-y)2(0≤x≤1；0≤y≤2)、Cu2ZnSn(SySe4-y)4(0≤y≤4)薄膜，是一种普适性的方法。
具体实施方式
下面结合实施例对本发明的技术方案作进一步详细说明。
实施例1
丁酸/丁胺盐离子液体辅助溶液法制备ZnO薄膜：
首先将10mmol氧化锌或乙酸锌或乙酰丙酮锌加入到100毫升烧杯中，加入5毫升丁酸和5毫升丁胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升乙醇稀释，获得ZnO前体溶液。将玻璃基片放置在旋涂仪上面，采用旋涂法制备ZnO前体预制膜，然后把预制膜放到300度的加热板上面退火30分钟，获得透明的ZnO薄膜，其可见光透过率高达95％，表面粗超度3.2纳米。
实施例2
乙酸/丁胺盐离子液体辅助溶液法制备NiO薄膜：
首先将10mmol乙酸镍或乙酰丙酮镍加入到100毫升烧杯中，加入5毫升乙酸和10毫升丁胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升水稀释，获得NiO前体溶液。把NiO前体溶液灌入喷墨打印机的墨盒中，利用爱普生L805喷墨打印机在玻璃基板上面打印获得NiO前体预制膜，然后把NiO预制膜放到275度的加热板上面退火60分钟，获得浅黄色的NiO薄膜，薄膜的可见光透过率为85％，表面粗糙度4.7纳米。
实施例3
乙酸/叔丁胺盐离子液体辅助溶液法制备ITO透明导电薄膜：
首先将9mmol乙酸铟或氢氧化铟以及1mmol四氯化锡或氯化亚锡加入到100毫升烧杯中，加入5毫升乙酸和5毫升叔丁胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升异丙醇稀释，获得透明澄清的ITO前体溶液。利用刮涂法把ITO前体溶液在玻璃基板上面制备ITO预制膜，然后把预制膜放到400度的加热板上面退火45分钟，获得透明导电的ITO薄膜，ITO的薄膜厚度180nm，可见光透过率87％，方块电阻120欧姆。
实施例4
乙酸/丙胺盐离子液体辅助溶液法制备MoO3薄膜：
首先将5mmol三氧化钼粉末加入到100毫升烧杯中，加入5毫升乙酸和5毫升丙胺，加热到140度，磁力搅拌2小时后获得均相澄清的溶液，然后加入100毫升甲醇稀释，获得浅黄色澄清的MoO3前体溶液。利用丝网印刷的方法把MoO3前体溶液在玻璃基板上面印刷制备MoO3前体预制膜，然后把预制膜放到200度的加热板上面退火10分钟，获得淡蓝色的MoO3薄膜，薄膜厚度15纳米，可见光透过率86％，表面粗超度2.3纳米。
实施例5
甲酸/甲胺盐离子液体辅助溶液法制备V2O5薄膜：
首先将2.5mmol五氧化二钒粉末加入到100毫升烧杯中，加入5毫升甲酸和5毫升甲胺，加热到100度，磁力搅拌1小时后获得均相澄清的溶液，然后加入100毫升乙二醇稀释，获得浅黄色澄清的V2O5前体溶液。利用喷墨打印的方法把V2O5前体溶液在玻璃基板上面打印制备V2O5前体预制膜，然后把预制膜放到250度的加热板上面退火100分钟，获得无色透明的V2O5薄膜，其厚度12.0纳米，表面粗超度2.6纳米。
实施例6
丁酸/己胺盐离子液体辅助溶液法制备10％Eu3+离子掺杂YVO4薄膜：
首先将5mmol五氧化二钒粉末加入到100毫升烧杯中，加入10毫升丁酸和10毫升己胺，加热到120度，磁力搅拌1小时后获得均相澄清的溶液，然后加入9mmol乙酸钇、1mmol乙酸铕和50毫升乙醇稀释，获得浅黄色澄清的10％Eu3+离子掺杂YVO4前体溶液。利用旋涂的方法把10％Eu3+离子掺杂YVO4前体溶液在玻璃基板上面旋涂制备10％Eu3+离子掺杂YVO4前体预制膜，然后把预制膜放到350度的加热板上面退火45分钟，获得10％Eu3+离子掺杂YVO4薄膜，在紫外灯的照射下薄膜发出明亮的红光，荧光量子产率52％。
实施例7
丙酸/甲胺盐离子液体辅助溶液法制备CdS薄膜：
首先将10mmol乙酸镉或氢氧化镉加入到100毫升烧杯中，加入5毫升丙酸和5毫升甲胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升乙二醇甲醚稀释，加入15mmol硫脲溶解，获得透明澄清的CdS前体溶液。利用垂直提拉法把CdS前体溶液在玻璃基板上面制备CdS前体预制膜，然后把预制膜放到150度的加热板上面退火20分钟，获得黄色光亮的CdS薄膜，薄膜厚度170纳米，表面粗糙度3.6纳米。
实施例8
乙酸/辛胺盐离子液体辅助溶液法制备ZnSe薄膜：
首先将10mmol乙酸锌或氧化锌加入到100毫升烧杯中，加入5毫升乙酸和10毫升辛胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升甲醇稀释，加入12mmol硒脲溶解，获得透明澄清的ZnSe前体溶液。利用喷枪采用喷涂法把ZnSe前体溶液在玻璃基板上面喷涂制备ZnSe前体预制膜，然后把预制膜放到220度的加热板上面退火10分钟，获得黄色光亮的ZnSe薄膜，薄膜厚度85纳米，表面粗超度6.5纳米。
实施例9
乙酸/丁胺盐离子液体辅助溶液法制备AgSb(SSe)2薄膜：
首先将5mmol乙酸锑或三氯化锑以及5mmol乙酸银或2.5mmol Ag2O加入到100毫升烧杯中，加入5毫升乙酸和5毫升丁胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升乙醇稀释，加入5mmol硒脲和5mmol硫脲溶解，获得黑色澄清的AgSb(SSe)2前体溶液。利用喷墨打印机把AgSb(SSe)2前体溶液在玻璃基板上面打印制备AgSb(SSe)2前体预制膜，然后把预制膜放到280度的加热板上面退火10分钟，获得黑色光亮的AgSb(SSe)2薄膜，薄膜厚度110纳米，表面粗超度7.2纳米。
实施例10
乙酸/丁胺盐离子液体辅助溶液法制备Ag(Bi0.5Sb0.5)S2薄膜：
首先将2.5mmol乙酸锑或三氯化锑和2.5mmol氢氧化铋或乙酸铋以及2.5mmol乙酸银或1.25mmol Ag2O加入到100毫升烧杯中，加入5毫升乙酸和5毫升丁胺，磁力搅拌获得均相澄清的溶液，然后加入50毫升乙醇稀释，加入12mmol硫脲溶解，获得黑色澄清的Ag(Bi0.5Sb0.5)S2前体溶液。利用喷墨打印机把Ag(Bi0.5Sb0.5)S2前体溶液在玻璃基板上面打印制备Ag(Bi0.5Sb0.5)S2前体预制膜，然后把预制膜放到350度的加热板上面退火10分钟，获得黑色光亮的Ag(Bi0.5Sb0.5)S2薄膜，薄膜厚度120纳米，表面粗超度9.7纳米。
实施例11
甲酸/戊胺盐离子液体辅助方法制备Cu0.9In0.7Ga0.3S2薄膜：
首先将1.8mmol乙酸铜、1.4mmol氢氧化铟、0.6mmol硝酸镓加入到50毫升烧杯中，加入5毫升甲酸和5毫升戊胺，磁力搅拌获得均相澄清的溶液，然后加入10毫升乙醇稀释，加入12mmol硫脲溶解，获得透明澄清的Cu0.9In0.7Ga0.3S2前体溶液。利用喷墨打印的方法把前体溶液在玻璃基板上面打印制备Cu0.9In0.7Ga0.3S2前体预制膜，然后把预制膜放到500度的加热板上面退火10分钟，获得黑色光亮的Cu0.9In0.7Ga0.3S2薄膜，薄膜厚度210纳米，表面粗超度6.5纳米。
实施例12
乙酸/乙胺盐离子液体辅助方法制备Cu1.8Zn1.2Sn1.0S4薄膜：
首先将3.6mmol氧化铜、2.4mmol硝酸锌、2.0mmol氯化亚锡加入到50毫升烧杯中，加入10毫升乙酸和10毫升乙胺，磁力搅拌获得均相澄清的溶液，然后加入20毫升甲醇稀释，加入10mmol硫脲溶解，获得透明澄清的Cu1.8Zn1.2Sn1.0S4前体溶液。利用喷墨打印的方法把前体溶液在玻璃基板上面打印制备Cu1.8Zn1.2Sn1.0S4前体预制膜，然后把预制膜放到480度的加热板上面退火20分钟，获得黑色光亮的Cu1.8Zn1.2Sn1.0S4薄膜，薄膜厚度260纳米，表面粗超度7.2纳米。
以上实施例只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (5)
1.一种离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，其特征在于，包括以下步骤：
（1）配置脂肪酸/脂肪胺盐离子液体，所述脂肪酸/脂肪胺盐离子液体为丁酸/丁胺盐离子液体、乙酸/丁胺盐离子液体、乙酸/叔丁胺盐离子液体、乙酸/丙胺盐离子液体、丁酸/己胺盐离子液体、丙酸/甲胺盐离子液体、乙酸/辛胺盐离子液体、甲酸/戊胺盐离子液、乙酸/乙胺盐离子液体中的一种；
（2）利用脂肪酸/脂肪胺盐离子液体溶解金属前体原料；
（3）用稀释溶剂调节前体溶液的粘度获得金属氧化物前体溶液，或加入硫脲和硒脲制备金属硫化物和金属硒化物前体溶液；
（4）通过溶液成膜的方法沉积制备金属前体预制膜，经过高温退火原位形成金属氧化物、金属硫化物和金属硒化物薄膜；
步骤（2）所述的金属前体原料包括金属氧化物、金属氢氧化物、金属硝酸盐、金属氯化物、金属乙酰丙酮盐、金属甲酸盐、金属乙酸盐、金属丙酸盐、金属丁酸盐中的一种或多种。
2.根据权利要求1所述的离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，其特征在于，步骤（3）所述的稀释溶剂为水、甲醇、乙醇、异丙醇、乙二醇或乙二醇甲醚中的一种或多种。
3.根据权利要求1所述离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，其特征在于，步骤（4）所述的溶液成膜方法包括旋涂法、垂直提拉法、刮涂法、喷墨打印法、丝网印刷法和喷涂法。
4.根据权利要求1所述的离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，其特征在于，步骤（4）所述的高温退火温度为100℃到700℃。
5.根据权利要求1所述的离子液体辅助制备金属氧化物、硫化物和硒化物薄膜的方法，其特征在于，步骤（4）所述的形成金属氧化物、硫化物和硒化物薄膜包括ZnO、SnO2、TiO2、NiO、In2O3、MoO3、WO3、V2O5、CuO、CaMoO4、YVO4、ZnS、CdS、In2S3、CuS、ZnSe、Ag(SbxBi1-x)(SySe2-y)2 、Cu(InxGa1-x)(SySe2-y)2 、Cu2ZnSn(SySe4-y)4薄膜；其中Ag(SbxBi1-x)(SySe2-y)2 中的0≤x≤1，0≤y≤2；Cu(InxGa1-x)(SySe2-y)2 中的0≤x≤1，0≤y≤2；Cu2ZnSn(SySe4-y)4 中的0≤y≤4。
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