CN101760735B - 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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- CN101760735B CN101760735B CN 200910266532 CN200910266532A CN101760735B CN 101760735 B CN101760735 B CN 101760735B CN 200910266532 CN200910266532 CN 200910266532 CN 200910266532 A CN200910266532 A CN 200910266532A CN 101760735 B CN101760735 B CN 101760735B
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- vanadium dioxide
- vanadium
- film
- precursor liquid
- dioxide precursor
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 103
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002243 precursor Substances 0.000 title claims abstract description 96
- 239000007788 liquid Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000010409 thin film Substances 0.000 title abstract description 22
- 239000000463 material Substances 0.000 title abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 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
- 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
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000004528 spin coating Methods 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
- 239000003352 sequestering agent Substances 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
- 239000002994 raw material Substances 0.000 abstract description 33
- 238000007669 thermal treatment Methods 0.000 abstract description 27
- 239000011521 glass Substances 0.000 abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 13
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- 238000006479 redox reaction Methods 0.000 abstract description 2
- 230000006903 response to temperature Effects 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 36
- 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
- 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
- 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
- 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
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
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- 206010013786 Dry skin Diseases 0.000 description 4
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- 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
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- 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
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 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
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
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- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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 year by year ascendant trend.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 mass energy within the duration of service of the supreme a century of the following decades.For example, because highly energy-consuming building ratio is large, 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 Minstry of Housing and Urban-Rural Development of People Republic of China (MOHURD) 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 day by day increases by power-saving technology; and then progressively reach the energy consumption level of developed country; just can greatly reduce the construction scale of colliery, power station equal energy source facility; and the 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 plays conclusive effect as building and extraneous principal passage of carrying out energy exchange to building energy conservation.And by glass between 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 in the winter time near-infrared band light to heat indoor.Scientists has proposed new energy-saving glass concept 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 thermochromic material, and the intrinsic transformation temperature is 68 ℃.After temperature was elevated to transformation temperature, material changed Tetragonal by monoclinic phase 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 guaranteeing under the substantially constant prerequisite of visible light light transmission, can realize the near infrared light light transmission by high transmission to the low transformation that sees through, the resistivity of film also can descend 10 simultaneously
2～10
5The order of magnitude.And the phase transformation of completely reversibility can occur 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 the 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.), the difficulty that has caused pure phase vanadium dioxide material to prepare.
Most widely used vanadium dioxide film preparation method is 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 the vapor phase process equipment used is expensive, and 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 preparation methods route 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 in the Water in Organic Solvents solution, aggregate into colloidal sol after plated film, 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.Wherein method 1 energy consumption is high, and 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 to wait the mole number conversion as the vanadium metal element):
V element: film forming accelerating: solvent=(0.022-3): (0.01-8): 20.
Better, 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 vanadium dioxide of tetravalence.
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 refers to the weight ratio of pure substance in the film forming accelerating, for example: when described film forming accelerating is 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.
Better, 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 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 aluminum nitrate.
Preferably, the soluble salt of described tantalum element is the nitric acid tantalum.
Preferably, the soluble salt of described manganese element is manganous nitrate.
When selecting two kinds of elements, 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 accelerate the vanadic salts dissolving, it is translucent or transparent to be stirred to solution, gets final product to get vanadium ion solution;
2) to step 1) in add film forming accelerating in the vanadium ion solution that makes, until fully making the vanadium dioxide precursor liquid after the dissolving.
Preferably, in described step 1) before, also carry out one or more element dopings (such 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.
Better, described step 1) in, in the described vanadium ion solution, the molecular volume concentration of solubility vanadic salts take conversion such as mole number such as grade as the vanadium metal element is as 0.01～3mol/L.
Better, described step 1) in, 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%.
Better, 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 removing vanadium.
Described film forming accelerating can be removed through thermal treatment process, or residual but substantially do not affect the performance (such as carbon, resistatess such as sulphur) of vanadium dioxide film.
Other ion of described solubility vanadic salts can be removed through thermal treatment or purification (such as the precipitator method, ion exchange method) technique, or residual but substantially do not affect the performance (such as carbon, resistatess such as sulphur) of vanadium dioxide film.
Described sequestrant can be removed through thermal treatment process, or residual but substantially do not affect the performance (such as carbon, resistatess such as sulphur) of vanadium dioxide film.
Preferably, described heat treated temperature is 350～500 ℃, and heat treatment time is 2～5 hours.
Two of purpose of the present invention is to provide the method that is prepared the vanadium dioxide film material by above-mentioned vanadium dioxide precursor liquid, 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. in metal substrate or nonmetal substrate surface, precursor film drying gets gel-film;
2) with step 1) in the gel-film that makes 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.
Better, described step 1) metal substrate in is common metal blocks and the films thereof such as steel, aluminium, nickel, iron, titanium.
Better, described step 1) the nonmetal substrate in is common inorganic materials and the films thereof such as glass (such 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 Common Polymers material and the films thereof such as tetrafluoroethylene (PTFE), polyimide (PI) of also can be.
Better, described step 1) metal substrate or nonmetal substrate surface in can deposit first one deck inertia transition layer (such 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.
The thickness of the gel-film that makes better, described step 1) is more than or equal to 10nm, more preferably 10～200nm.
Described step 1) method of spin coating in, 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 operation 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 operation 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 of gained precursor thin-film are got gel-film, repeat to be coated with 3 times.
Better, 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 refers to: 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 again substrate after making vanadium dioxide have temperature induced color changing performance (thermochromic properties), to prevent that thermal treatment is to the infringement of 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 vanadium dioxide film to the performance of control of 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, the fields such as optical communication perhaps are applied to infrared imaging as the electrical functions material, thermorelay, temperature-sensitive control, the fields such as Novel MOS transistor.
Characteristics of the present invention and remarkable innovation thereof are:
1) the present invention has overcome the shortcoming (alkoxide raw material is expensive, and vapor phase process equipment is complicated, the melt pulling method energy consumption is high, easily pollute) of existing liquid phase vanadium dioxide technology of preparing, uses the vanadic salts of scale operation as raw material, has reduced raw materials cost; 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 operability and the repeatability of technique;
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 the 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 that utilizes the prepared high-transparency vanadium dioxide film energy-saving glass of the present invention-wavelength relationship curve.
Fig. 5 is the transmittance that utilizes the prepared low type vanadium dioxide film energy-saving glass of the present invention-wavelength relationship curve.
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
The below is several typical specific embodiments in the content of the present invention, 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, and all belongs to the protection domain of this patent.
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.
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, alternately drip hydrochloric acid and hydrazine hydrate, system pH is remained on about 1.0, 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 to get precursor liquid.
Embodiment 3 prepares the vanadium dioxide precursor liquid that is mixed with W elements take Vanadium Pentoxide in FLAKES as raw material
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, rear with ammoniacal liquor with the pH value be transferred to 9.5 or more than, stir and also to keep the pH value, Vanadium Pentoxide in FLAKES dissolves fully.
2, for keeping solution-stabilized, add therein the 0.15g citric acid.
3, under strong stirring, add the ammonium tungstate ((NH of 0.1ml tungsten ion concentration 1.0mol/L
4)
6H
2W
12O
40XH
2O) aqueous solution.
3, after wherein adding 5ml ethylene glycol adjusting viscosity, get precursor liquid.
Embodiment 4 prepares the vanadium dioxide precursor liquid that is mixed with tungsten, molybdenum element take Vanadium Pentoxide in FLAKES as raw material
1, the 0.182g Vanadium Pentoxide in FLAKES is joined in the 20ml deionized water, rear with ammoniacal liquor with the pH value be transferred to 9.5 or more than, stir and also to keep the pH value, Vanadium Pentoxide in FLAKES dissolves fully.
2, for keeping solution-stabilized, add therein the 0.15g citric acid.
3, under strong stirring, 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 again 0.1ml molybdenum ion concentration 0.5mol/L
4)
2Mo
4O
132H
2O) aqueous solution.
4, after wherein adding 2ml ethylene glycol and 3ml massfraction 10% polyvinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 5 prepares the vanadium dioxide precursor liquid of tetravalence take the dichloro vanadyl as raw material
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 therein the 0.1g citric acid.
3, after wherein adding 5ml 10% polyvinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 6 prepares the vanadium dioxide precursor liquid that is mixed with the molybdenum element tetravalence take the dichloro vanadyl as raw material
1,0.276g dichloro vanadyl is joined in the 20ml deionized water, the system of being stirred to becomes transparent blue solution.
2, under strong stirring, add the ammonium molybdate ((NH of 0.1ml molybdenum ion concentration 1.0mol/L in the gained solution
4)
2Mo
4O
132H
2O) aqueous solution.
3, after wherein adding 5ml 10% polyvinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 7 prepares vanadium dioxide film take Vanadium Pentoxide in FLAKES as raw material
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, in the embodiment 1 precursor liquid as raw material.
3, precursor liquid is lifted plated film with dip coating 5cm/min on the quartz glass plate of cleaning, 250 ℃ of dry 30min of gained precursor thin-film are got gel-film, repeat to be coated with 3 times, afterwards lower 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 prepares the doped vanadium dioxide film take Vanadium Pentoxide in FLAKES as raw material
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, in the embodiment 3,4 precursor liquid as raw material.
3, precursor liquid is lifted plated film with dip coating 5cm/min on the quartz glass plate of cleaning, 250 ℃ of dry 30min of gained precursor thin-film are got gel-film, repeat to be coated with 3 times, afterwards lower 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 prepares vanadium dioxide film take the dichloro vanadyl as raw material
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, in the embodiment 5 precursor liquid as raw material.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film gets gel-film with 100 ℃ of dry 30min of gained precursor thin-film, repeat to be coated with 3 times, under nitrogen gas stream 600 ℃ afterwards, naturally cool 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, in the embodiment 6 precursor liquid as raw material.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film gets gel-film with 100 ℃ of dry 30min of gained precursor thin-film, repeat to be coated with 3 times, under nitrogen gas stream 600 ℃ afterwards, naturally cool to room temperature after the 5h thermal treatment, both can get vanadium dioxide film.
Embodiment 11 prepares the vanadium dioxide film that is added with antireflection layer take Vanadium Pentoxide in FLAKES as raw material
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, in the embodiment 1,3,4 arbitrary precursor liquid as raw material.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film gets gel-film with 100 ℃ of dry 30min of gained precursor thin-film, repeats 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, afterwards with 1200rpm/min, 20s rotary coating anti-reflection film gets gel-film with 150 ℃ of dry 10min of gained precursor thin-film, repeats to be coated with 2 times.
5, lower 600 ℃ of nitrogen, hydrogen mixed airflow (hydrogen molar percentage 5%), naturally cool to room temperature after the 3h thermal treatment.
Embodiment 12 is added with the vanadium dioxide film of antireflection layer as the raw material preparation take the vanadium dioxide precursor liquid of tetravalence
1, adopting quartz glass is made substrate, and substrate is distinguished ultrasonic cleaning 5 minutes, drying for standby in deionized water, ethanol, acetone.
2, in the embodiment 2,5,6 arbitrary precursor liquid as raw material.
3, with precursor liquid method of spin coating 1500rpm/min on quartz glass plate, the 30s plated film gets gel-film with 100 ℃ of dry 30min of gained precursor thin-film, repeats 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, afterwards with 1200rpm/min, 20s rotary coating anti-reflection film gets gel-film with 150 ℃ of dry 10min of gained precursor thin-film, repeats 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 raw material preparation
1, the 0.122g sodium metavanadate is joined in the 100ml deionized water, rear with ammoniacal liquor with the pH value be transferred to 9.5 or more than, stir and also to keep the pH value, sodium metavanadate dissolves fully.
2, for keeping solution-stabilized, add therein 0.15g EDAT.
3, under strong stirring, 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 after wherein adding the polyvinyl alcohol adjusting 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 raw material preparation
1, the 1.626g vanadium oxalate is joined in the 1ml deionized water, rear with ammoniacal liquor with the pH value be transferred to 9.5 or more than, stir and also to keep the pH value, vanadium oxalate dissolves fully.
2, for keeping solution-stabilized, add therein 0.15g EDAT.
3, under strong stirring, 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 after wherein adding tert-polyoxyethylene octylphenol ether adjusting 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 raw material preparation
1, the 1.626g vanadium oxalate is joined in the 1ml deionized water, rear with ammoniacal liquor with the pH value be transferred to 9.5 or more than, stir so that vanadium oxalate dissolves fully.
2, for keeping solution-stabilized, add therein 0.15g EDAT.
3, under strong stirring, 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 after wherein adding tert-polyoxyethylene octylphenol ether adjusting 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) prepare the vanadium dioxide precursor liquid of tetravalence for raw material
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 therein the 0.1g citric acid.
3, after wherein adding 5ml 10% vinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 17 is with vanadylic sulfate (VOSO
4) prepare the vanadium dioxide precursor liquid of tetravalence for raw material
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 therein the 0.1g citric acid.
3, after wherein adding 5ml 10% vinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 18 is with vanadylic sulfate (VOSO
4) prepare the vanadium dioxide precursor liquid of tetravalence for raw material
1, with the 0.163g vanadylic sulfate (take etc. mole number be converted to the vanadium metal element as 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 therein the 0.1g citric acid.
3, after wherein adding 18.5g polyvinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
Embodiment 19 is with vanadylic sulfate (VOSO
4) prepare the vanadium dioxide precursor liquid of tetravalence for raw material
1, with the 0.163g vanadylic sulfate (take etc. mole number be converted to the vanadium metal element as 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 therein the 0.1g citric acid.
3, after wherein adding 0.136g vinyl alcohol (molecular weight 50000) aqueous solution adjusting viscosity, get precursor liquid.
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 centrifugation muddy precipitation is scattered in precipitation in the 80ml acetic acid solvent, stirs the lower salt acid for adjusting pH value of using to-0.15, 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 5 times, under nitrogen atmosphere 500 ℃ afterwards, the straight room temperature of naturally cooling after the 1h thermal treatment.
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 the lower salt acid for adjusting pH value to 1.5 of using, and 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 successively rotary coating (1500 rev/mins, 30 seconds plated films).After each coating 60 ℃ of dryings of gained precursor thin-film 10 minutes gel-film, under nitrogen atmosphere 500 ℃ afterwards, 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
1.2g VOSO
4(99.4% is pure, 32% weight loss on drying) is dissolved in 20ml water, adds fast the sodium wolframate (Na of 0.1ml concentration 0.5mol/L in gained solution
2WO
42H
2O) aqueous solution.With strong aqua mentioned solution pH value is transferred to 6～7, centrifugation muddy precipitation is scattered in precipitation in the 80ml acetic acid solvent, stirs the lower salt acid for adjusting pH value of using to-0.15, gets clear solution.
Embodiment 23 is added with SiO
2Two tunic structure vanadium dioxide film intelligent glass of antireflection layer
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, afterwards 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 (5)
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;
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;
Described film forming accelerating is selected from: polyoxyethylene glycol, polyvinyl alcohol or tert-polyoxyethylene octylphenol ether;
Described solvent is one or more the mixing in methyl alcohol, ethanol, water, acetone, ammoniacal liquor, hydrochloric acid or the ethylene glycol;
Also comprise the adding sequestrant in the described vanadium dioxide precursor liquid, the adding molar weight of described sequestrant is 0.5～2 times of vanadium ion molar weight.
2. vanadium dioxide precursor liquid as described in claim 1 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.
3. vanadium dioxide precursor liquid as described in claim 1 is characterized in that 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.
Among the claim 1-3 the described vanadium dioxide precursor liquid of arbitrary claim for the preparation of vanadium dioxide film.
5. the preparation method of a vanadium dioxide film comprises the steps:
1) the described vanadium dioxide precursor liquid of arbitrary claim among the claim 1-3 is formed uniform precursor film with method of spin coating, dip coated method, casting method, meniscus method or ultrasonic atomizatio method in metal substrate or nonmetal substrate surface, precursor film drying gets gel-film;
2) with step 1) in the gel-film that makes 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 namely get vanadium dioxide film.
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