CN101760735A - Vanadium dioxide precursor liquid and method for preparing thin-film material by using the same - Google Patents
Vanadium dioxide precursor liquid and method for preparing thin-film material by using the same Download PDFInfo
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- CN101760735A CN101760735A CN 200910266532 CN200910266532A CN101760735A CN 101760735 A CN101760735 A CN 101760735A CN 200910266532 CN200910266532 CN 200910266532 CN 200910266532 A CN200910266532 A CN 200910266532A CN 101760735 A CN101760735 A CN 101760735A
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- Prior art keywords
- vanadium dioxide
- vanadium
- film
- precursor liquid
- dioxide precursor
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 107
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002243 precursor Substances 0.000 title claims abstract description 98
- 239000007788 liquid Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 15
- 239000010409 thin film Substances 0.000 title abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 239000008204 material by function Substances 0.000 claims abstract description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 108010025899 gelatin film Proteins 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 11
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000005499 meniscus Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 85
- 238000007669 thermal treatment Methods 0.000 abstract description 27
- 239000011521 glass Substances 0.000 abstract description 19
- 230000001105 regulatory effect Effects 0.000 abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000012071 phase Substances 0.000 abstract description 12
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 230000006903 response to temperature Effects 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- 150000003681 vanadium Chemical class 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000005265 energy consumption Methods 0.000 description 11
- 230000009466 transformation Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000003352 sequestering agent Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000004320 controlled atmosphere Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- NQGWALHZCVFGRE-UHFFFAOYSA-N [Ta].[N+](=O)(O)[O-] Chemical compound [Ta].[N+](=O)(O)[O-] NQGWALHZCVFGRE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
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- 239000005329 float glass Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000005344 low-emissivity glass Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
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- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of material chemistry, in particular relates to a vanadium dioxide precursor liquid and a method for preparing a thin-film material by using the same. The vanadium dioxide precursor liquid of the invention comprises a soluble vanadium salt, a film forming accelerator and a solvent. The invention further provides a method for preparing a vanadium dioxide thin film by using the vanadium dioxide precursor liquid. The invention overcomes the shortages of the prior preparation technique of liquid-phase vanadium dioxide, reduces the cost of raw materials, and can previously reduce or oxidize the vanadium raw material in the raw materials to quadrivalence so that vanadium element is not necessarily subjected to an oxidation-reduction reaction in the process of thermal treatment. The vanadium dioxide thin film prepared by the invention has uniform phase, good purity and intelligent response to temperature. The vanadium dioxide thin film prepared on a glass substrate has a light transmittance peak value up to 70% at most in a visual light region and an infrared light regulating performance up to 60% at most, and has wide application prospect in the fields of optical functional materials and electric functional materials.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of vanadium dioxide precursor liquid and prepare the method for thin-film material.
Background technology
China is an energy starved country, but present China unit floor area of building energy consumption but is 2 to 3 times of developed country, and the total amount of China's building energy consumption just is being ascendant trend year by year.China's building energy consumption in energy aggregate consumption shared ratio from last century late nineteen seventies 10%, risen to 2007 about 30%.At present, China is in industrialization and urbanization Rapid development stage, and the floor space that builds up every year surpasses all developed countries and builds up the summation of floor area of building year, and be the high energy consumption building more than 95% up to 1,600,000,000 to 2,000,000,000 square metres.These buildings all will constantly consume a large amount of energy in the duration of service of the supreme a century of the following decades.For example, because of highly energy-consuming building ratio is big, 1,800 ten thousand tons of the annual just many consumption standard coals of single northern area, direct economic loss reaches 7,000,000,000 yuan, arranges 520,000 tons of carbonic acid gas more.Science and technology department of nation-building portion studies show that China's architectural energy consumption ratio rises to about 35% the most at last.Huge proportion like this, building energy consumption has become the heavy burden of Chinese society sustainable economic development.
If can reduce half to the building energy consumption that increases day by day by power-saving technology; and then progressively reach the energy consumption level of developed country; just can reduce the construction scale of colliery, power station equal energy source facility greatly; and caused pollution of corresponding energy consumption and waste, this is one of effective ways that solve energy dilemma and problem of environmental pollution.
Glass port is as building and extraneous principal passage of carrying out energy exchange, to the building energy conservation decisive role.And by glass between the building and the external world in the energy exchange carried out, thermal radiation has occupied integral part (58%), thereby the main task of energy-saving glass is to change its heat-radiating properties.In the energy-saving glass design, main implementation is low radiation (Low-E) glass at present, but low emissivity glass can only play the effect that reduces heat radiation, can not effectively utilize near-infrared band light to heat indoor in the winter time.Scientists has proposed new energy-saving glass notion for this reason, and their implementation has: electrochromism (electricity quick), gas-discoloration (air-sensitive) and photochromic (photosensitive).By exciting of ambient conditions, above energy-saving glass all can be realized the adjusting to the sunlight light transmission, but all has in various degree defective (be referring to number of patent application 200510121424.4 Chinese patent described in).
Vanadium dioxide is a kind of typical temperature induced color changing material, and the intrinsic transformation temperature is 68 ℃.After temperature was elevated to transformation temperature, material mutually changed cubic phase by monocline at the utmost point in the short period of time.Follow phase transformation, the physicals of vanadium dioxide is undergone mutation.For example, vanadium dioxide film is guaranteeing under the constant substantially prerequisite of visible light light transmission that can realize that the near infrared light light transmission sees through the transformation that sees through to low by height, the resistivity of film also can descend 10 simultaneously
2～10
5The order of magnitude.And the phase transformation of completely reversibility can take place in vanadium dioxide when temperature reduces, and makes the performance of film become initial low-temperature condition, so just can circulate to realize above transition process.The phase transformation of vanadium dioxide can also be by optical radiation simultaneously, and alternate manners such as voltage excite, thereby makes it can be integrated on the existing and following electric elements, in fields such as optics, electricity, magnetics very wide application prospect is arranged.For example, vanadium dioxide film has very high temperature coefficient of resistance when phase transformation, it is the ideal material (be CN1392286 Chinese patent described in) of non-refrigerated infrared detector thermistor referring to patent publication No., and the optical property sudden change of following phase transformation can realize the near infrared light that causes heat effect is regulated under the prerequisite that guarantees visible light daylighting fully intelligently, and then can prepare energy-saving glass (be referring to application number CN200510121424.4 Chinese patent described in).Simultaneously, the transformation temperature of vanadium dioxide can be regulated by doping or technology controlling and process, control in different temperature points realization phase transformation (referring to T.D.Manning and I.P.Parkin, Atmospheric pressure chemical vapor deposition of tungsten dopedvanadium (IV) oxide from VOCl
3, water and WCl
6.Journal of Materials Chemistry 2004,14, (16), 2554-2559. and S.H.Chen; H.Ma; J.Dai and X.J.Yi, Nanostructured vanadium dioxide thinfilms with low phase transition temperature.Applied Physics Letters 2007,90, (10) .).
In fact the research of vanadium dioxide as functional materials has been launched very early, but the vanadium atom valence state is a lot, vanadium-oxygen system is too complicated, and only thermodynamically stable phase just has more than 15 kinds.And the vanadium dioxide of using as intelligent material only in very narrow stoichiometric ratio scope stable existence (referring to J.Nag and R.F.Haglund, Synthesis of vanadium dioxide thinfilms and nanoparticles.Journal of Physics-Condensed Matter, 2008,20,264016. and R.Balu and P.V.Ashrit, Applied Physics Letters, 2008,92,021904.), caused the difficulty of pure phase vanadium dioxide material preparation.
Most widely used vanadium dioxide film preparation method is a vapor phase process at present, comprise sputtering method (Sputtering Deposition), pulsed laser deposition (Pulsed Laser Deposition, PLD), ion implantation (Ion Implantation) and chemical Vapor deposition process (Chemical Vapor Deposition, CVD) etc.Vapor phase process can be controlled the oxygen partial pressure in the preparation process well, so the vanadium dioxide film performance that obtains is fine.But vapor phase process equipment used costliness, parameter control is complicated, and production efficiency is low, transforms to suitability for industrialized production also to have a lot of difficult problems.Corresponding therewith, present existing liquid phase method prepares route and mainly contains following several: 1, quick hardening after the Vanadium Pentoxide in FLAKES high temperature melting, plated film behind the formation pentavalent vanadium colloidal sol, thermal treatment under reductibility or vacuum atmosphere; 2, vanadium alkoxide hydrolysis in organic solvent, aggregate into plated film behind the colloidal sol, thermal treatment under reductibility or vacuum atmosphere; 3, vanadium metal is dissolved in the hydrogen peroxide and forms plated film behind the colloidal sol, thermal treatment under reductibility or vacuum atmosphere.Method 1 energy consumption height wherein, high-temperature operation is dangerous and be easy to cause pollution of vanadium; Method 2 used vanadium alkoxides are very expensive, and the control of hydrolysis of alkoxide is difficult, and process controllability is poor; The vanadium metal price is higher and treating processes is longer in the method 3, all is unfavorable for large-scale production.
Summary of the invention
One of purpose of the present invention is to overcome the defective of prior art, and a kind of vanadium dioxide precursor liquid and preparation method thereof is provided.
A kind of vanadium dioxide precursor liquid comprises following component: the solubility vanadic salts, and film forming accelerating and solvent, wherein the weight ratio of each component is (wherein the solubility vanadic salts is the vanadium metal element to wait mole number conversion):
V element: film forming accelerating: solvent=(0.022-3): (0.01-8): 20.
Preferable, described solubility vanadic salts is selected from: vanadylic sulfate (VOSO
4), dichloro vanadyl (VOCl
2) or be the tetravalent vanadium ion solution of the inorganic vanadic salts redox of other valence states gained.
Preferably, the inorganic vanadic salts of described other valence states is selected from: Vanadium Pentoxide in FLAKES (V
2O
5), sodium metavanadate (NaVO
3), dichloro vanadyl (VOCl
2) or vanadium oxalate (C
10O
20V
2), the vanadium ion in the inorganic vanadic salts of described other valence states can preoxidation in solution, be reduced to tetravalence, also can be when thermal treatment controlled atmosphere to obtain the quaternary vanadium dioxide.
The implication of term " controlled atmosphere during thermal treatment " is: heat-treat in inertia or weak reducing atmosphere.
Preferably, described film forming accelerating is selected from: polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA) or tert-polyoxyethylene octylphenol ether (Triton X) etc. improve a kind of in the soluble high-molecular reagent of precursor liquid viscosity.
Further preferred, described film forming accelerating is that mass percent is 10% polyvinyl alcohol water solution.
In the precursor liquid of vanadium dioxide described in the present invention in the component, the weight ratio of film forming accelerating is meant the weight ratio of pure substance in the film forming accelerating, for example: when described film forming accelerating is a mass percent when being 10% polyvinyl alcohol water solution, the weight ratio of each component is in the described vanadium dioxide precursor liquid: v element: polyvinyl alcohol in the film forming accelerating: solvent=(0.022-3): (0.01-8): 20.
Preferable, comprise doped element in the described vanadium dioxide precursor liquid, described doped element is selected from one or more in tungsten, molybdenum, niobium, fluorine, chromium, titanium, aluminium, tantalum or the manganese element, described element adopts the form of soluble salt to add, the doping molar weight of described element is the 0.05-20% of v element molar weight, preferred 0.05-10%, further preferred 0.05-5%.
Preferably, the soluble salt of described W elements is ammonium tungstate ((NH
4)
6H
2W
12O
40XH
2O).
Preferably, the soluble salt of described molybdenum element is an ammonium molybdate.
Preferably, the soluble salt of described niobium element is niobic acid ammonium or nitric acid niobium.
Preferably, the soluble salt of described fluorine element is Sodium Fluoride or Potassium monofluoride.
Preferably, the soluble salt of described chromium element is chromium nitrate or chromium chloride.
Preferably, the soluble salt of described titanium elements is Titanium Nitrate or titanium chloride.
Preferably, the soluble salt of described aluminium element is an aluminum nitrate.
Preferably, the soluble salt of described tantalum element is the nitric acid tantalum.
Preferably, the soluble salt of described manganese element is a manganous nitrate.
When selecting two kinds of elements for use, two kinds of doped elements can be any proportioning, and preferred element is: tungsten, molybdenum, niobium.
Described solvent is selected from one or more the mixture in methyl alcohol, ethanol, water, acetone, ammoniacal liquor, hydrochloric acid and the ethylene glycol.
The preparation method of vanadium dioxide precursor liquid of the present invention comprises the steps:
1) solubility vanadic salts raw material is scattered in the solvent, regulator solution pH value to pH greater than 8, be preferably greater than 9, further be preferably greater than and equal 9.5 and quicken the vanadic salts dissolving, it is translucent or transparent to be stirred to solution, get final product vanadium ion solution;
2) add film forming accelerating in the vanadium ion solution that in step 1), makes, treat fully can make the vanadium dioxide precursor liquid after the dissolving.
Preferably, before described step 1), also carry out one or more element dopings (as elements such as tungsten, molybdenum, niobium, fluorine, chromium, titanium, aluminium, tantalum, manganese), thereby realize the doping of film and the regulation and control of transformation temperature, concrete adulterating method is: directly add soluble salt and get final product.
Preferable, in the described step 1), in the described vanadium ion solution, the solubility vanadic salts is that the molecular volume concentration of vanadium metal element is 0.01～3mol/L to wait mole number conversion.
Preferable, in the described step 1), make after the vanadium ion solution, also need in vanadium ion solution, add sequestrant and carry out metal ion-chelant, and the adding molar weight of described sequestrant is 0.5～2 times of the vanadium ion molar weight.
Preferably, described sequestrant is solvable type or can be total to molten type sequestrant, more preferably ethylenediamine tetraacetic acid (EDTA) (EDAT) or citric acid (Citric Acid) with membrane-forming agent.
Preferably, described step 2) in the vanadium dioxide precursor liquid in, the mass percent of film forming accelerating is 0.25～10wt%.
Preferable, described step 2) in, after finishing, the preparation of vanadium dioxide precursor liquid also needs to heat-treat other ion, film forming accelerating and sequestrant except that removing vanadium.
Described film forming accelerating can be removed through thermal treatment process, or residual but do not influence the performance (as carbon, resistatess such as sulphur) of vanadium dioxide film substantially.
Other ion of described solubility vanadic salts can be removed through thermal treatment or purification (as the precipitator method, ion exchange method) technology, or residual but do not influence the performance (as carbon, resistatess such as sulphur) of vanadium dioxide film substantially.
Described sequestrant can be removed through thermal treatment process, or residual but do not influence the performance (as carbon, resistatess such as sulphur) of vanadium dioxide film substantially.
Preferably, described heat treated temperature is 350～500 ℃, and heat treatment time is 2～5 hours.
Two of purpose of the present invention is the method that is prepared the vanadium dioxide film material by above-mentioned vanadium dioxide precursor liquid is provided, and this preparation method comprises the steps:
1) described vanadium dioxide precursor liquid is formed uniform precursor film with method of spin coating (Spin Coating), dip coated method (Dip Coating), casting method (Tape Casting), meniscus method (Meniscus Coating) or ultrasonic atomizatio method (UltrasonicNebulization) etc. on metal substrate or nonmetal substrate surface, precursor film drying gets gel-film;
2) with the gel-film that makes in the step 1) in vacuum oven or atmosphere furnace, at inertia or weak reducing atmosphere, can make vanadium dioxide film being higher than to heat-treat under 350 ℃ inertia, vacuum or the weak reducing atmosphere.
Preferable, the metal substrate in the described step 1) is common metal blocks and films thereof such as steel, aluminium, nickel, iron, titanium.
Preferable, nonmetal substrate in the described step 1) is common inorganic materials and films thereof such as glass (as vagcor, high lead glass, silica glass, coated glass, devitrified glass, float glass etc.), silicon chip, mica, spinel, aluminum oxide, silicon oxide, zirconium white, stannic oxide, described nonmetal polytetrafluoroethylene (PTFE), polyimide common polymer materials and the films thereof such as (PI) of also can be.
Preferable, metal substrate in the described step 1) or nonmetal substrate surface can deposit one deck inertia transition layer earlier (as SiO
2, Al
2O
3, TiO
2, SnO
2) react when the thermal treatment to prevent alkali metal in the substrate or alkali earth metal and vanadium dioxide gel film.
Preferable, the thickness of the gel-film that makes in the described step 1) is more than or equal to 10nm, more preferably 10～200nm.
Method of spin coating in the described step 1), dip coated method, casting method, meniscus method or ultrasonic atomizatio method can be selected according to prior art by those skilled in the art.
Preferably, the concrete operations step of described method of spin coating is: the cleaning substrate on, with the vanadium dioxide precursor liquid with 1500 rev/mins, 30 seconds plated films.
Preferably, the concrete operations step of described dip coated method is: on the substrate of cleaning, the vanadium dioxide precursor liquid is lifted plated film with the speed of 5cm/min, 250 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times.
Preferable, described step 2) thermal treatment temp in is 350～500 ℃; Heat treatment time is 2～5 hours.
Described step 2) vanadium dioxide film that makes in is because the thermal treatment process difference can have stoichiometric ratio (VO
2) or nonstoichiometry ratio, i.e. VO
2-x(0.3＜x＜0.6), wherein, the pass between thermal treatment process and the stoichiometric ratio is: the too high or overlong time of thermal treatment temp may cause composition
Described step 2) thermal treatment in is meant: the vanadium dioxide precursor liquid is before carrying out film forming, during film forming or after the film forming, be higher than thermal treatment under 350 ℃ inertia, vacuum or the weak reducing atmosphere, its objective is to be deposited on substrate again after making vanadium dioxide have temperature induced color changing performance (thermochromic properties), to prevent the infringement of thermal treatment to substrate.
Preferably, described rare gas element is nitrogen, argon gas etc., and described weakly reducing atmosphere is the mixed gas of nitrogen and hydrogen, and wherein, in the mixed gas of described nitrogen and hydrogen, the mixed volume of hydrogen ratio is preferably 1～5%.
The described vanadium dioxide film surface that makes can be added with other transparent film and improve vanadium dioxide film visible light light transmission as anti-reflection film, or improves the regulation and control performance of vanadium dioxide film to infrared light as optics regulation and control film.
The vanadium dioxide film that makes among the present invention can be used as optical functional materials be applied to energy-conservation, temperature control, optical storage, the infrared laser protection, fields such as optical communication perhaps are applied to infrared imaging as the electrical functions material, thermorelay, temperature-sensitive control, fields such as Novel MOS transistor.
Characteristics of the present invention and significantly innovate part and be:
1) the present invention has overcome the shortcoming (alkoxide raw material costliness, vapor phase process equipment complexity, easily pollute at melt pulling method energy consumption height) of existing liquid phase vanadium dioxide technology of preparing, and the vanadic salts that uses scale operation has reduced raw materials cost as raw material; Developed a kind of simple and effective liquid phase vanadium dioxide precursor liquid preparation method;
2) in the vanadium dioxide precursor liquid, add the film-forming properties that film forming accelerating has been improved precursor liquid, improve the quality of gained film.This step has been simplified the process for preparation of precursor liquid, has reduced precursor liquid blending process difficulty, has improved the stability of precursor liquid.And can add sequestrant and vanadium ion effect, thereby improve the stability of plated film;
3) can introduce the tetravalence vanadium raw materials or in precursor liquid vanadium ion prereduction or be oxidized to tetravalence, make that v element does not need to carry out redox reaction in the heat treatment process, but direct crystallization becomes vanadium dioxide.Thermal treatment process is simplified, and parameter control is convenient, has increased the operability and the repeatability of technology;
The vanadium dioxide crystallization phases purity that method of the present invention makes is good, mixes to be easy to reality Film Optics excellent property, the vanadium dioxide film that is made by vapor phase process under the same thickness condition at transmission of visible light under the identical infrared light adjusting function.
Description of drawings
Fig. 1 is the Raman spectrum that utilizes the prepared vanadium dioxide film of the present invention.
Fig. 2 is vanadium dioxide film Ols and the V that utilizes the present invention prepared
2p3/2XPS spectrum figure (substrate silica glass).
Fig. 3 utilizes prepared pure vanadium dioxide film of the present invention and W doped vanadium dioxide film V
3pAnd W
4fXPS spectrum figure (substrate silica glass).
Fig. 4 is the transmittance-wavelength relationship curve that utilizes the prepared high-transparency vanadium dioxide film energy-saving glass of the present invention.
Fig. 5 is the transmittance-wavelength relationship curve that utilizes the prepared low type vanadium dioxide film energy-saving glass of the present invention.
Fig. 6 utilizes the prepared high-transparency doped vanadium dioxide film energy-saving glass of the present invention at 2000nm wavelength place transmittance-temperature relation curve.
Embodiment
Be several typical specific embodiments in the content of the present invention below, but protection domain of the present invention is not limited only to following examples, everyly belongs to the technical scheme that content of the present invention is equal to, all belong to the protection domain of this patent.
Embodiment 1 is a feedstock production vanadium dioxide precursor liquid with the Vanadium Pentoxide in FLAKES
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 15ml deionized water, add strong aqua with pH value be transferred to 9.5 or more than, stir also maintenance pH value, Vanadium Pentoxide in FLAKES dissolves fully.
2, get precursor liquid to wherein adding 5ml massfraction 10% polyvinyl alcohol (molecular weight 50000) aqueous solution.
Embodiment 2 is a feedstock production quaternary vanadium dioxide precursor liquid with the Vanadium Pentoxide in FLAKES
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, alternately dripping hydrochloric acid and hydrazine hydrate remain on about 1.0 system pH, and the system of being stirred to becomes transparent blue solution.
2, in 1 gained solution, add 0.6g polyoxyethylene glycol (molecular weight 3000), fully dissolve precursor liquid.
Embodiment 3 is the vanadium dioxide precursor liquid that feedstock production is mixed with W elements with the Vanadium Pentoxide in FLAKES
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, the back with ammoniacal liquor with pH value be transferred to 9.5 or more than, stir also maintenance pH value, Vanadium Pentoxide in FLAKES dissolves fully.
2, for keeping solution-stabilized, add the 0.15g citric acid therein.
3, under brute force stirs, add the ammonium tungstate ((NH of 0.1ml tungsten ion concentration 1.0mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.
3, after regulating viscosity, 5ml ethylene glycol gets precursor liquid to wherein adding.
Embodiment 4 is the vanadium dioxide precursor liquid that feedstock production is mixed with tungsten, molybdenum element with the Vanadium Pentoxide in FLAKES
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, the back with ammoniacal liquor with pH value be transferred to 9.5 or more than, stir also maintenance pH value, Vanadium Pentoxide in FLAKES dissolves fully.
2, for keeping solution-stabilized, add the 0.15g citric acid therein.
3, under brute force stirs, the ammonium tungstate ((NH of 0.1ml tungsten ion concentration 0.5mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.The ammonium molybdate ((NH that adds 0.1ml molybdenum ion concentration 0.5mol/L again
4)
2Mo
4O
132H
2O) aqueous solution.
4, after regulating viscosity, the 2ml ethylene glycol and 3ml massfraction 10% polyvinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 5 is a feedstock production quaternary vanadium dioxide precursor liquid with the dichloro vanadyl
1,0.276g dichloro vanadyl is joined in the 20ml deionized water, the system of being stirred to becomes transparent blue solution.
2, for keeping solution-stabilized, add the 0.1g citric acid therein.
3, after regulating viscosity, 5ml 10% polyvinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 6 is that feedstock production is mixed with molybdenum element quaternary vanadium dioxide precursor liquid with the dichloro vanadyl
1,0.276g dichloro vanadyl is joined in the 20ml deionized water, the system of being stirred to becomes transparent blue solution.
2, under brute force stirs, in gained solution, add the ammonium molybdate ((NH of 0.1ml molybdenum ion concentration 1.0mol/L
4)
2Mo
4O
132H
2O) aqueous solution.
3, after regulating viscosity, 5ml 10% polyvinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 7 is the feedstock production vanadium dioxide film with the Vanadium Pentoxide in FLAKES
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with precursor liquid among the embodiment 1.
3, precursor liquid is lifted plated film with dip coating 5cm/min on the quartz glass plate of cleaning, 250 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times, the back is following 600 ℃ of nitrogen, hydrogen mixed airflow (hydrogen molar percentage 5%), naturally cool to room temperature after the 3h thermal treatment, both can get vanadium dioxide film.
Embodiment 8 is a feedstock production doped vanadium dioxide film with the Vanadium Pentoxide in FLAKES
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with precursor liquid among the embodiment 3,4.
3, precursor liquid is lifted plated film with dip coating 5cm/min on the quartz glass plate of cleaning, 250 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times, the back is following 600 ℃ of nitrogen, hydrogen mixed airflow (hydrogen molar percentage 5%), naturally cool to room temperature after the 3h thermal treatment, both can get vanadium dioxide film.
Embodiment 9 is the feedstock production vanadium dioxide film with the dichloro vanadyl
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with precursor liquid among the embodiment 5.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film, 100 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times, back under nitrogen gas stream 600 ℃ naturally cools to room temperature after the 5h thermal treatment, both can get vanadium dioxide film.
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with precursor liquid among the embodiment 6.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film, 100 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times, back under nitrogen gas stream 600 ℃ naturally cools to room temperature after the 5h thermal treatment, both can get vanadium dioxide film.
Embodiment 11 is the vanadium dioxide film that feedstock production is added with antireflection layer with the Vanadium Pentoxide in FLAKES
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with arbitrary precursor liquid among the embodiment 1,3,4.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film, 100 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times.
4, with the volume ratio tetraethoxy: ethanol: water: hydrochloric acid=15: 40: 5: 0.07 preparation SiO
2Precursor liquid, back with 1200rpm/min, 20s rotary coating anti-reflection film, 150 ℃ of dry 10min get gel-film with the gained precursor thin-film, repeat to be coated with 2 times.
5, following 600 ℃ of nitrogen, hydrogen mixed airflow (hydrogen molar percentage 5%), naturally cool to room temperature after the 3h thermal treatment.
Embodiment 12 is the vanadium dioxide film that feedstock production is added with antireflection layer with quaternary vanadium dioxide precursor liquid
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, be raw material with arbitrary precursor liquid among the embodiment 2,5,6.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film, 100 ℃ of dry 30min get gel-film with the gained precursor thin-film, repeat to be coated with 3 times.
4, with the volume ratio tetraethoxy: ethanol: water: hydrochloric acid=15: 40: 5: 0.07 preparation SiO
2Precursor liquid, back with 1200rpm/min, 20s rotary coating anti-reflection film, 150 ℃ of dry 10min get gel-film with the gained precursor thin-film, repeat to be coated with 2 times.
5, under nitrogen gas stream 600 ℃, naturally cool to room temperature after the 5h thermal treatment.
Embodiment 13 is with sodium metavanadate (NaVO
3) be mixed with the vanadium dioxide precursor liquid of W elements for feedstock production
1, the 0.122g sodium metavanadate is joined in the 100ml deionized water, the back with ammoniacal liquor with pH value be transferred to 9.5 or more than, stir also maintenance pH value, sodium metavanadate dissolves fully.
2, for keeping solution-stabilized, add 0.15g EDAT therein.
3, under brute force stirs, add the ammonium tungstate ((NH of 0.005ml tungsten ion concentration 0.01mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.
3, get precursor liquid to wherein adding after polyvinyl alcohol is regulated viscosity, the mass percent of the polyvinyl alcohol of adding in the silicon-dioxide precursor liquid is 0.25wt%.
Embodiment 14 is with vanadium oxalate (C
10O
20V
2) be mixed with the vanadium dioxide precursor liquid of W elements for feedstock production
1, the 1.626g vanadium oxalate is joined in the 1ml deionized water, the back with ammoniacal liquor with pH value be transferred to 9.5 or more than, stir also maintenance pH value, vanadium oxalate dissolves fully.
2, for keeping solution-stabilized, add 0.15g EDAT therein.
3, under brute force stirs, add the ammonium tungstate ((NH of 6ml tungsten ion concentration 0.1mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.
3, get precursor liquid to wherein adding after the tert-polyoxyethylene octylphenol ether is regulated viscosity, the mass percent of tert-polyoxyethylene octylphenol ether in the silicon-dioxide precursor liquid of adding is 10wt%.
Embodiment 15 is with vanadium oxalate (C
10O
20V
2) be mixed with the vanadium dioxide precursor liquid of W elements for feedstock production
1, the 1.626g vanadium oxalate is joined in the 1ml deionized water, the back with ammoniacal liquor with pH value be transferred to 9.5 or more than, the stirring make vanadium oxalate dissolve fully.
2, for keeping solution-stabilized, add 0.15g EDAT therein.
3, under brute force stirs, add the ammonium tungstate ((NH of 6ml tungsten ion concentration 0.1mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.
3, get precursor liquid to wherein adding after the tert-polyoxyethylene octylphenol ether is regulated viscosity, the mass percent of tert-polyoxyethylene octylphenol ether in the silicon-dioxide precursor liquid of adding is 10wt%.
Embodiment 16 is with vanadylic sulfate (VOSO
4) be feedstock production quaternary vanadium dioxide precursor liquid
1, the 0.276g vanadylic sulfate is joined in the mixing solutions of 20ml methyl alcohol and acetone, the system of being stirred to becomes transparent blue solution.
2, for keeping solution-stabilized, add the 0.1g citric acid therein.
3, after regulating viscosity, 5ml 10% vinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 17 is with vanadylic sulfate (VOSO
4) be feedstock production quaternary vanadium dioxide precursor liquid
1, the 0.276g vanadylic sulfate is joined in the 20ml ammoniacal liquor, the system of being stirred to becomes transparent blue solution.
2, for keeping solution-stabilized, add the 0.1g citric acid therein.
3, after regulating viscosity, 5ml 10% vinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 18 is with vanadylic sulfate (VOSO
4) be feedstock production quaternary vanadium dioxide precursor liquid
1, with the 0.163g vanadylic sulfate (with etc. mole number to be converted to the vanadium metal element be 0.051g) join in the mixing solutions of 46.4g ethanol and ethylene glycol, the system of being stirred to becomes transparent blue solution.
2, for keeping solution-stabilized, add the 0.1g citric acid therein.
3, after regulating viscosity, 18.5g polyvinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Embodiment 19 is with vanadylic sulfate (VOSO
4) be feedstock production quaternary vanadium dioxide precursor liquid
1, with the 0.163g vanadylic sulfate (with etc. mole number to be converted to the vanadium metal element be 0.051g) join in the 0.34g hydrochloric acid, the system of being stirred to becomes transparent blue solution.
2, for keeping solution-stabilized, add the 0.1g citric acid therein.
3, after regulating viscosity, 0.136g vinyl alcohol (molecular weight 50000) aqueous solution gets precursor liquid to wherein adding.
Single-layer membrane structure vanadium dioxide film intelligent glass
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone;
2,1.2g VOSO
4(99.4% is pure, 32% weight loss on drying) is dissolved in 30ml water, and gained solution is transferred to 6～7 with strong aqua with the pH value, and the centrifugation muddy precipitates, and precipitation is scattered in the 80ml acetic acid solvent, stirs down and arrives-0.15 with the salt acid for adjusting pH value, gets clear solution.
3, in 2 gained solution, add 2.4mg PEG (molecular weight 30000), fully dissolving.The gained coating liquid with method of spin coating the cleaning quartz glass plate on 1500 rev/mins, 30 seconds plated films.With 60 ℃ of dryings of gained precursor thin-film 10 minutes gel-film, repeat to be coated with back under nitrogen atmosphere 500 ℃, the straight room temperature of naturally cooling after the 1h thermal treatment 5 times.
Embodiment 21
The structure of composite membrane vanadium dioxide film intelligent glass that composition gradient changes
1, step 1 is identical with specific embodiment 20, does not repeat them here; Other step is as follows:
2,1.2g VOSO
4(99.4% is pure, 32% weight loss on drying) is dissolved in 30ml water, and gained solution is transferred to 6～7 with strong aqua with the pH value, and centrifugation muddy precipitation is scattered in precipitation in the 80ml deionized water solvent, stirs and uses salt acid for adjusting pH value to 1.5 down, gets clear solution.In solution, add the finely dispersed SiO of various dose
2Colloidal sol (particle diameter is less than 20nm) is mixed with different solution.
3, in 2 gained solution, add 2.4mg PEG (molecular weight 30000), fully dissolving.The gained coating liquid according to V/Si than descending rotary coating successively (1500 rev/mins, 30 seconds plated films).60 ℃ of dryings of each coating back gained precursor thin-film 10 minutes gel-film, back under nitrogen atmosphere 500 ℃, the straight room temperature of naturally cooling after the 1h thermal treatment.
Embodiment 22
The single-layer membrane structure vanadium dioxide film intelligent glass of Doped Tungsten element
Step 1 is identical with specific embodiment 20 with 3, does not repeat them here; Step 2 adopts embodiment 1, only needs before regulating the pH value, with VOSO
4Be dissolved in 20ml water and in formed solution, add fast the sodium wolframate (Na of 0.1ml concentration 1.0mol/L
2WO
42H
2O) aqueous solution.Technology is as follows:
1.2g VOSO
4(99.4% is pure, 32% weight loss on drying) is dissolved in 20ml water, adds the sodium wolframate (Na of 0.1ml concentration 0.5mol/L in gained solution fast
2WO
42H
2O) aqueous solution.With strong aqua above-mentioned pH value of solution value is transferred to 6～7, the centrifugation muddy precipitates, and precipitation is scattered in the 80ml acetic acid solvent, stirs down and arrives-0.15 with the salt acid for adjusting pH value, gets clear solution.
Embodiment 23 is added with SiO
2Two tunic structure vanadium dioxide film intelligent glass of antireflection layer
Step 1 is identical with specific embodiment 20 with 2, does not repeat them here; Step 3 adopts embodiment one, only needs rotary coating one deck SiO on gel-film that forms or the vanadium dioxide film that burns till
2Antireflection layer, preparation technology is as follows:
In 2 gained solution, add 2.4mg PEG (molecular weight 30000), fully dissolving.The gained coating liquid with method of spin coating the cleaning quartz glass plate on 1500 rev/mins, 30 seconds plated films.60 ℃ of dryings of gained precursor thin-film were got gel-film in 10 minutes, repeat to be coated with 5 times.
With the volume ratio tetraethoxy: ethanol: water: hydrochloric acid=15: 40: 5: 0.07 preparation SiO
2Coating liquid, back be with 1200 rev/mins, 20 seconds rotary coating anti-reflection films, with 60 ℃ of dryings of gained precursor thin-film 10 minutes gel-film, repeat to be coated with 2 times after under nitrogen atmosphere 500 ℃, the straight room temperature of naturally cooling after the 1h thermal treatment.
Claims (10)
1. vanadium dioxide precursor liquid comprises following component: the solubility vanadic salts, and film forming accelerating and solvent, wherein the weight ratio of each component is:
V element: film forming accelerating: solvent=(0.022-3): (0.01-8): 20.
2. the vanadium dioxide precursor liquid described in claim 1 is characterized in that, described solubility vanadic salts is selected from: vanadylic sulfate, dichloro vanadyl or be the tetravalent vanadium ion solution of the inorganic vanadic salts redox of other valence states gained.
3. the vanadium dioxide precursor liquid described in claim 2 is characterized in that, the inorganic vanadic salts of described other valence states is selected from Vanadium Pentoxide in FLAKES, sodium metavanadate, dichloro vanadyl or vanadium oxalate.
4. the vanadium dioxide precursor liquid described in claim 1 is characterized in that, comprises doped element in the described vanadium dioxide precursor liquid, and described doped element is selected from one or more in tungsten, molybdenum, niobium, fluorine, chromium, titanium, aluminium, tantalum or the manganese element.
5. the vanadium dioxide precursor liquid described in claim 1 is characterized in that, described solvent is one or more the mixing in methyl alcohol, ethanol, water, acetone, ammoniacal liquor, hydrochloric acid or the ethylene glycol.
6. the vanadium dioxide precursor liquid described in claim 1 is characterized in that, described film forming accelerating is selected from: polyoxyethylene glycol, polyvinyl alcohol or tert-polyoxyethylene octylphenol ether.
7. the described vanadium dioxide precursor liquid of arbitrary claim is used to prepare vanadium dioxide film among the claim 1-6.
8. the preparation method of a vanadium dioxide film comprises the steps:
1) the described vanadium dioxide precursor liquid of arbitrary claim among the claim 1-6 is formed uniform precursor film with method of spin coating, dip coated method, casting method, meniscus method or ultrasonic atomizatio method on metal substrate or nonmetal substrate surface, precursor film drying gets gel-film;
2) with the gel-film that makes in the step 1) in vacuum oven or atmosphere furnace, at inertia or weak reducing atmosphere and be higher than to heat-treat under 350 ℃ the temperature condition of heat treatment and promptly get vanadium dioxide film.
9. a vanadium dioxide film is made by the described method of claim 8.
10. the vanadium dioxide film described in the claim 9 is as optical functional materials or electrical functions material.
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