CN103695874A - Preparation method of intelligent temperature control color changing vanadium oxide film - Google Patents
Preparation method of intelligent temperature control color changing vanadium oxide film Download PDFInfo
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Abstract
The invention relates to a preparation method of an intelligent temperature control color changing vanadium oxide film, which is characterized by comprising the following steps: (1) preparing tungstenic sol; (2) preparing sol comprising vanadium ions; (3) preparing tungsten-doped vanadium oxide sol, i.e. adding the tungstenic sol obtained in the step (1) into the sol comprising vanadium ions, which is obtained in the step (2), so as to obtain the tungsten-doped vanadium oxide sol; and (4) preparing a tungsten-doped vanadium oxide film, i.e. plating the tungsten-doped vanadium oxide sol obtained in the step (3) on the surface of a washed substrate and then carrying out annealing processing in the inert atmosphere or under the vacuum condition so as to obtain the tungsten-doped vanadium oxide film with an intelligent temperature control color changing function. The method disclosed by the invention has low energy consumption, adopts a simple preparation process, has high safety and has wide application prospect in the field of photoelectronic functional materials.
Description
Technical field
The invention belongs to material chemistry technical field, particularly a kind of preparation method who mixes tungsten vanadium oxide film.
Background technology
Along with socioeconomic development, modern architecture is more and more higher to printing opacity and energy-conservation requirement, and the function of window glass, except daylighting, wind sheltering, screening rain, also will have insulation and control and utilize the functions such as sunlight.Buildings or indoor energy-conservation aspect, day by day perfect due to materials for wall, the heat transfer coefficient of suitable thickness body of wall is only 1.4W/ (M
2and the heat transfer coefficient of the thick common building glass of 3mm reaches 5.8W/ (M K),
2k).Therefore, window glass is one of key factor affecting building energy conservation effect, and 50% of building energy consumption causes because building glass energy-saving effect is poor.In addition, there is very large area and calendar variation in China, therefore researches and develops high performance Energy-saving Building Glass building energy conservation is reduced discharging and even the development of global low-carbon economy is had very important significance.
Vanadium oxide (VO
2) there is semi-conductor-Metal Phase Transition (MIT) characteristic, be a kind of intelligent thermochromic material, in the time of 68 ℃, vanadium oxide changes high temperature four directions metallographic phase into mutually by low temperature monocline semi-conductor, be accompanied by semi-conductor-Metal Phase Transition, its electricity, optics, magnetic property all occurs larger reversible change.By controlling film before and after phase transformation, for the transmitance of infrared band, can reach energy-saving effect, so vanadium oxide all has very important using value in various fields such as automobile, infrared acquisition, photoswitch, optical memories.
Monocrystalline vanadium oxide occurs repeatedly can to break or become fragment afterwards in phase transformation, still can stable existence after phase transformation circulation occurs repeatedly and make thin-film material, and this has benefited from its polycrystalline phase structure.The preparation method of vanadium oxide film has three kinds of main approach up to now, sol-gel (Sol-gel) method, physical vaporous deposition (PVD) and chemical Vapor deposition process (CVD).In all these methods, CVD applies lessly owing to being difficult to control exactly stoichiometric ratio, and PVD method is usually used to carry out the basic research of film performance.And sol-gel method is because its preparation technology is simple, low to equipment and operational requirement, be easy to the preparation that the advantages such as doping are widely used in vanadium oxide film.
Vanadium oxide film, in the practical application of smart window, need to be down to its transformation temperature near room temperature (25 ℃) from 68 ℃.It is reported, the metal ion of high valence state is as tungsten (VI), and niobium (V) etc. can reduce MIT temperature while being incorporated in vanadium oxide.Wherein, W elements is considered to the most effective doped source, valency as the tungsten atom of doped element is 6 valencys, higher than 4 valency vanadium ions in vanadium oxide, during doping, in d track, can introduce excess electron, the division of d interband is reduced, cause vanadium oxide to reduce from semi-conductor state time of changing metallic state into institute's energy requirement, thereby reach the object of effective reduction vanadium oxide transformation temperature.The tungsten doping of 2% atomic percent just can make transformation temperature be reduced to room temperature.
Presoma that tungsten vanadium oxide film uses according to it is mixed in sol-gel method preparation
Difference is divided into two large classes, and a class is inorganic sol-gel method; Another kind is organosol-gel method.When tungsten vanadium oxide film is mixed in sol-gel method preparation at present, reported that the Doped Tungsten source as doping agent mainly exists three problems: the one, Doped Tungsten source is difficult to form and mix uniformly tungsten coating liquid with coexisting containing vanadium Stability of Sols; The 2nd, in active lower Doped Tungsten source, W atom is difficult to enter vanadium oxide lattice and replaces V atom, but is present in vanadium oxide film with the form of tungsten compound, is therefore difficult to reach the object of Effective Doping; The 3rd, some Doped Tungsten sources (as WCl6, ammonium tungstate, sodium wolframate etc.) contain other impurity elements (as N, Cl, Na etc.), when mixing W, can introduce other impurity (N, Cl, Na etc.) element, this all has disadvantageous effect to improving film infrared adjusting function and reducing thin film phase change temperature.
(Jeong-Ho Cho, Young-Jun Byun, the Jin-Ho Kim et al..Thermochromic characteristics of WO such as Jeong-Ho Cho
3-doped vanadium dioxide thin films prepared by sol – gel method.Ceramics International, Ceramics International, 2012,38:589 – 593) adopt inorganic water quenching, with WO
3for the preparation of tungsten source, mix tungsten vanadium oxide film, while often mixing tungsten 1%, thin film phase change temperature only reduces by 15.5 ℃.
Patent CN1436606A discloses a kind of methyl ethyl diketone vanadyl (VO (acac) that utilizes
2) as the presoma of vanadium, be dissolved in methyl alcohol and make organosol, finally by anneal, generate the method for the vanadium oxide film of crystal form.When the method is mixed tungsten vanadium oxide film in preparation, there is VO (acac)
2colloidal sol and Doped Tungsten source are difficult to the problem such as molten, poor stability, preparation process complexity altogether.Utilize the method with WCl
6doping vanadium oxide film thin film phase change temperature when mixing tungsten 12.02% of preparing for Doped Tungsten source only reduces by 10 ℃, transformation temperature is not reduced (Yuankai Liu effectively, Haizheng Tao, Xinhong Chu et al.Effects of addition of tungsten chloride on optical properties of VO
2-based thermochromic films prepared by sol – gel method[J] .Non-Crystalline Solids, 2014,383 (1): 116-120).
Patent CN102757764A discloses a kind of method that acid tungsten colloidal sol mixes tungsten vanadium oxide film as Doped Tungsten source preparation of usining.Prepared by the method mixes tungsten vanadium oxide film transformation temperature when mixing tungsten 2% and can be down to 35 ℃, but transformation temperature lowers efficiency far below 23 ℃/at.%W.In addition, can only be at stable existence under acidic conditions as the tungsten colloidal sol in Doped Tungsten source, this has limited its use range.And prepare tungsten colloidal sol tungsten compound ammonium tungstate used, can introduce impurity N element, regulate tungsten collosol PH value hydrochloric acid used can introduce impurity Cl element, the introducing of these impurity elements all has disadvantageous effect to improving film infrared adjusting function and reducing thin film phase change temperature.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provide a kind of intelligent temperature control look to become the preparation method of vanadium oxide film, technique is relatively simple, and the intelligent temperature control look of preparation becomes vanadium oxide film transformation temperature can be adjustable continuously within the scope of 25-60 ℃, is suitable for industrial production.
The technical scheme that solution the technology of the present invention problem adopts is that the preparation method of this intelligent temperature control look change vanadium oxide film comprises the following steps:
(1) preparation of tungstenic colloidal sol: tungsten or Tungstenic compound are dissolved in the mixing solutions of excessive hydrogen peroxide and organic solvent, stir at 0-60 ℃, centrifuging obtains transparent tungstenic colloidal sol until completely dissolved;
(2) contain the preparation of the colloidal sol of vanadium ion: under room temperature, solubility vanadic salts is dissolved in solvent, then adds dispersion agent to be uniformly dispersed, obtain the colloidal sol containing vanadium ion;
(3) mix the preparation of tungsten vanadium oxide colloidal sol: step (1) gained tungstenic colloidal sol is joined to step (2) gained containing in the colloidal sol of vanadium ion, obtain mixing tungsten vanadium oxide colloidal sol;
(4) mix the preparation of tungsten vanadium oxide film: step (3) gained is mixed to tungsten vanadium oxide colloidal sol and be sputtered at the substrate surface through clean, then under inert atmosphere or vacuum condition, carry out anneal, obtain having that intelligent temperature control look becomes function mixes tungsten vanadium oxide film.
Preferably, the described Tungstenic compound of step (1) comprises a kind of in wolframic acid or Tungsten oxide 99.999; The described organic solvent of step (1) comprises one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, ether, methyl ethyl diketone or toluene.
In the mixing solutions of the described hydrogen peroxide of above-mentioned steps (1) and organic solvent, the volume ratio of hydrogen peroxide and organic solvent is 1:10-10:1.Preferably, in the mixing solutions of the described hydrogen peroxide of step (1) and organic solvent, the volume ratio of hydrogen peroxide and organic solvent is 1:1, and the time of stirring is 18-24h.
In the described tungstenic colloidal sol of step (1), the volumetric molar concentration of tungsten is 0.1-1mol/L.Preferably, in the described tungstenic colloidal sol of step (1), the volumetric molar concentration of tungsten is 0.2-0.3mol/L.Further preferably, in the described tungstenic colloidal sol of step (1), the volumetric molar concentration of tungsten is 0.3mol/L.
Room temperature of the present invention refers to 10-30 ℃.
Preferably, the described solubility vanadic salts of step (2) comprises one or more in methyl ethyl diketone vanadyl, vanadylic sulfate, dichloro vanadyl or oxalic acid vanadyl; The described solvent of step (2) comprises one or more the mixing in methyl alcohol, ethanol, water, n-propyl alcohol, Virahol, acetone, ethylene glycol, methyl ethyl diketone, ammoniacal liquor or hydrochloric acid.
Preferably, the described dispersion agent of step (2) comprises a kind of in polyvinylpyrrolidone (PVP) or polyoxyethylene glycol, the 0.5-5% that the add-on of dispersion agent is solvent quality.Further preferably, the add-on of dispersion agent is solvent quality 1.5%.
The described volumetric molar concentration containing vanadium ion in the colloidal sol of vanadium ion of step (2) is 0.1-1.0mol/L.
Preferably, the described volumetric molar concentration containing vanadium ion in the colloidal sol of vanadium ion of step (2) is 0.1-0.3mol/L.
Further preferably, the described volumetric molar concentration containing vanadium ion in the colloidal sol of vanadium ion of step (2) is 0.125mol/L.
Preferably, described in step (3), mixing the mol ratio of tungsten and vanadium ion in tungsten vanadium oxide colloidal sol is 0.5:100-10:100.
Preferably, the described substrate of step (4) comprises soda-lime-silica glass, silica glass, sheet mica or sapphire.The film-forming process that step (4) adopts comprises the processing methodes such as spin-coating method, crystal pulling method, spraying method.
Preferably, the described clean of step (4) is for adopting successively deionized water, acetone and ethanol supersound washing, and each supersound washing time is 10-20 minute.
Preferably, the described inert atmosphere of step (4) is nitrogen or argon gas; Described vacuum condition is that low oxygen partial pressure vacuum tightness is 8 * 10
2-1 * 10
3the vacuum atmosphere of Pa.
Preferably, the described annealing treating process of step (4) is that temperature rise rate is 3-10 ℃/min, and annealing temperature is 500-600 ℃, and annealing time is 30-240min.
In tungstenic colloidal sol as vanadium oxide Doped Tungsten source provided by the invention, tungsten or Tungstenic compound react generated peroxide wolframic acid chemistry of complex activity far above the vanadium oxide Doped Tungsten source of having reported with hydrogen peroxide and small molecule solvent, make tungsten atom be easier to enter vanadium oxide lattice and replace vanadium atom, thereby reaching the object of effective reduction vanadium oxide transformation temperature.
In addition, reported that with other Doped Tungsten source (tungsten chloride, ammonium tungstate, sodium wolframate etc.) compares, tungstenic colloidal sol provided by the invention can not be introduced other impurity elements when implementing tungsten doping, when reducing thin film phase change temperature, do not affect film infrared adjusting function, contribute to the raising of vanadium oxide film over-all properties; This tungstenic collosol stability is good, can long-term stability exist and not produce precipitation, and good with the precursor sol mutual solubility containing vanadium ion, be applicable to the multiple sol systems such as traditional inorganic shrend sol-gel method and organosol gel method.
The present invention also provides the intelligent temperature control look of preparing according to aforesaid method to become vanadium oxide film, described vanadium oxide film transformation temperature is adjustable continuously within the scope of 25-60 ℃, and film has height preferred orientation, before and after phase transformation, for ir radiation, has excellent regulating power
In addition, the present invention also comprises that above-mentioned intelligent temperature control look becomes vanadium oxide film as the purposes of intelligent temperature control window glass.
The invention has the beneficial effects as follows: effectively solved in prior art tungsten doping intelligent temperature control look and become vanadium oxide film complicated process of preparation, easily introduce impurity, affect the problem of the infrared adjusting function of vanadium oxide film, the vanadium oxide film of preparation has height preferred orientation, before and after phase transformation, for red radiation, have excellent regulating power, transformation temperature can be adjustable continuously within the scope of 25-60 ℃.In addition, the inventive method power consumption is few, and preparation technology is simple, and security is good, in photoelectric functional material field, has broad application prospects.
Accompanying drawing explanation
Fig. 1 does not adulterate in prior art with respect to air, the transmitance of ultraviolet-visible-infrared light to be changed to the heat stagnation loop line at 2000nm place before and after the phase transformation of vanadium oxide film sample;
Fig. 2 is the XRD figure spectrum of the prepared vanadium oxide film of mixing tungsten 1% of the embodiment of the present invention one;
Fig. 3 changes the heat stagnation loop line at 2000nm with respect to air to the transmitance of ultraviolet-visible-infrared light before and after the prepared vanadium oxide film phase transformation of mixing tungsten 1% of the embodiment of the present invention one.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment mono-
Take 1.25g wolframic acid powder and be placed in beaker, the hydrogen peroxide that is 30wt% by 10mL concentration and 10mL methyl alcohol join in the beaker that fills wolframic acid powder simultaneously, at 45 ℃, heating in water bath stirs 24h and dissolves completely to pressed powder, through centrifuging, can obtain the transparent tungstenic colloidal sol that tungsten ion concentration is 0.3mol/L.
0.663g methyl ethyl diketone vanadyl is joined in 25mL methyl alcohol, stirring at room, when methyl alcohol evaporates into 20mL, centrifuging obtains the blackish green colloidal sol containing vanadium ion.To adding its mass percent in above-mentioned colloidal sol, be 1.5% polyvinylpyrrolidone (PVP), then in above-mentioned colloidal sol, add the tungstenic colloidal sol of the above-mentioned preparation of 0.08mL, after stirring at room 18h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 1:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 10 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: under argon gas atmosphere, 10 ℃/min of temperature rise rate, is warming up to 550 ℃ of insulation 0.5h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 1%, recording this thin film phase change temperature is 35 ℃, and heat stagnation loop line width is 9 ℃.Be illustrated in figure 3 the prepared vanadium oxide film sample of the present embodiment at the heat stagnation loop line of 2000nm.When solid line is heating, film is at 2000nm place transmitance change curve, and when dotted line is cooling, film is at 2000nm place transmitance change curve.Before and after Figure 1 shows that the vanadium oxide film sample phase transformation of not adulterating in prior art, with respect to air, the transmitance of ultraviolet-visible-infrared light is changed to the heat stagnation loop line at 2000nm place.Compare with the vanadium oxide film sample that do not adulterate in prior art, the vanadium oxide film sample transformation temperature of mixing tungsten 1% has reduced by 25 ℃, and heat stagnation loop line width has reduced 25 ℃.Illustrate that tungsten doping vanadium oxide film of the present invention can reduce transformation temperature and the heat stagnation loop line width thereof of vanadium oxide film effectively.Fig. 2 is the XRD figure spectrum of the prepared vanadium oxide film sample of the present embodiment, in XRD figure spectrum, only contain the diffraction peak of monocline vanadium oxide phase (011), (022) crystal face and silica glass at the 10-40 ° of steamed bun peak of locating, vanadium oxide (72-0514, P21/c that film is (011) preferred orientation are described.a=0.5743nm,b=0.4517nm,c=0.5375,β=122.61°）。
Embodiment bis-
Adopt the method identical with embodiment mono-to prepare tungstenic colloidal sol.
0.663g methyl ethyl diketone vanadyl is joined in 25mL methyl alcohol, stirring at room, when methyl alcohol evaporates into 20mL, centrifuging obtains the blackish green colloidal sol containing vanadium ion.To adding its mass percent in above-mentioned colloidal sol, be 1.5% PVP, then in above-mentioned colloidal sol, add 0.16mL tungstenic colloidal sol, after stirring at room 20h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 2:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 15 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: vacuum tightness is 1 * 10
3under the vacuum atmosphere of Pa, 3 ℃/min of temperature rise rate, is warming up to 530 ℃ of insulation 4h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 2%, recording this thin film phase change temperature is 33 ℃, and heat stagnation loop line width is 11 ℃.
Embodiment tri-
Adopt the method identical with embodiment mono-to prepare tungstenic colloidal sol.
0.663g methyl ethyl diketone vanadyl is joined in 25mL methyl alcohol, stirring at room, when methyl alcohol evaporates into 20mL, centrifuging obtains the blackish green colloidal sol containing vanadium ion.To adding its mass percent in above-mentioned colloidal sol, be 1.5% PVP, then in above-mentioned colloidal sol, add 0.4mL tungstenic colloidal sol, after stirring at room 24h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 5:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 20 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: vacuum tightness is 8 * 10
2under the vacuum atmosphere of Pa, 10 ℃/min of temperature rise rate, is warming up to 550 ℃ of insulation 0.5h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 5%, recording this thin film phase change temperature is 25 ℃, and heat stagnation loop line width is 12 ℃.
Embodiment tetra-
Adopt the method identical with embodiment mono-to prepare tungstenic colloidal sol.
0.978g vanadylic sulfate is joined in the mixing solutions of 25mL methyl alcohol and acetone, stirring at room, until solvent evaporates during to 20mL centrifuging obtain transparent blueness containing the colloidal sol of vanadium ion.To adding its mass percent in above-mentioned colloidal sol, be 0.5% PVP, then in above-mentioned colloidal sol, add 0.2mL tungstenic colloidal sol, after stirring at room 18h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 1:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 20 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: under nitrogen atmosphere, 10 ℃/min of temperature rise rate, is warming up to 500 ℃ of insulation 0.5h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 1%, recording this thin film phase change temperature is 42 ℃, and heat stagnation loop line width is 12 ℃.
Embodiment five
Take 1.25g Tungsten oxide 99.999 powder and be placed in 50mL beaker, the hydrogen peroxide that is 30% by 10mL mass concentration and 10mL ethanol join in the beaker that fills Tungsten oxide 99.999 powder simultaneously, at 60 ℃, heating in water bath stirs 24h and dissolves completely to pressed powder, through centrifuging, can obtain the transparent tungstenic colloidal sol that tungsten ion concentration is 0.25mol/L.
0.276g dichloro vanadyl is joined in 20mL deionized water, and stirring at room to system becomes transparent blue solution.To adding its mass percent in above-mentioned solution, be 5% PVP, then in above-mentioned colloidal sol, add the tungstenic colloidal sol of the above-mentioned preparation of 0.04mL, after stirring at room 18h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 0.5:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 20 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: under nitrogen atmosphere, 5 ℃/min of temperature rise rate, is warming up to 600 ℃ of insulation 4h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 0.5%, recording this thin film phase change temperature is 48 ℃, and heat stagnation loop line width is 16 ℃.
Embodiment six
Take 1.25g metal tungsten powder and be placed in 50mL beaker, the hydrogen peroxide that is 30% by 10mL mass concentration and 10mL ethanol slowly join in the beaker that fills metal tungsten powder simultaneously, at 0-6 ℃, ice bath stirs 24h and dissolves completely to pressed powder, through centrifuging, can obtain the transparent tungstenic colloidal sol that tungsten ion concentration is 0.2mol/L.
1.355g oxalic acid vanadyl is joined in 20mL deionized water, and stirring at room to system becomes transparent blue solution.To adding its mass percent in above-mentioned solution, be 1.5% polyoxyethylene glycol, then in above-mentioned colloidal sol, add the tungstenic colloidal sol of the above-mentioned preparation of 2.75mL, after stirring at room 18h, obtain the stable tungsten coating liquid of mixing.In coating liquid, the mol ratio of tungsten and vanadium is 10:100.
By silica glass, successively through deionized water, acetone and ethanol supersound washing, the supersound washing time is 20 minutes, and clean quartz glass plate is placed in alcohol and preserves stand-by.Adopt spin-coating method plated film, after every thin film has been coated with, at 80 ℃, toast 10min to remove the residual unnecessary solvent of film surface.
Coated film is placed in to tubular annealing stove anneals.Annealing conditions is: under nitrogen atmosphere, 5 ℃/min of temperature rise rate, is warming up to 600 ℃ of insulation 1h.After having annealed, with stove naturally cooling, can obtain vanadium oxide film.
By the measurement to above-mentioned see through-temperature relation of the vanadium oxide film of mixing tungsten 10%, recording this thin film phase change temperature is 32 ℃, and heat stagnation loop line width is 6 ℃.
Comparative example: do not adulterate in prior art before and after the phase transformation of vanadium oxide film sample and with respect to air, the transmitance of ultraviolet-visible-infrared light to be changed at the heat stagnation loop line at 2000nm place as shown in Figure 1, when solid line is heating, vanadium oxide film is at 2000nm place transmitance change curve, when dotted line is cooling, vanadium oxide film is at 2000nm place transmitance change curve, and its transformation temperature is 60 ℃.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves ordinary method preparation and mix tungsten vanadium oxide film complex process, difficult situation that cost is high, the tungsten vanadium oxide film phase transformation front and back of mixing of preparation simultaneously have excellent regulating power for ir radiation, transformation temperature can be adjustable continuously, of many uses within the scope of 25-60 ℃.
Be understandable that, above embodiment is only used to principle of the present invention is described and the illustrative embodiments that adopts, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. intelligent temperature control look becomes a preparation method for vanadium oxide film, it is characterized in that comprising the following steps:
(1) preparation of tungstenic colloidal sol: tungsten or Tungstenic compound are dissolved in the mixing solutions of excessive hydrogen peroxide and organic solvent, stir at 0-60 ℃, centrifuging obtains transparent tungstenic colloidal sol until completely dissolved;
(2) contain the preparation of the colloidal sol of vanadium ion: under room temperature, solubility vanadic salts is dissolved in solvent, then adds dispersion agent to be uniformly dispersed, obtain the colloidal sol containing vanadium ion;
(3) mix the preparation of tungsten vanadium oxide colloidal sol: step (1) gained tungstenic colloidal sol is joined to step (2) gained containing in the colloidal sol of vanadium ion, obtain mixing tungsten vanadium oxide colloidal sol;
(4) mix the preparation of tungsten vanadium oxide film: step (3) gained is mixed to tungsten vanadium oxide colloidal sol and be sputtered at the substrate surface through clean, then under inert atmosphere or vacuum condition, carry out anneal, obtain having that intelligent temperature control look becomes function mixes tungsten vanadium oxide film.
2. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the described Tungstenic compound of step (1) comprises a kind of in wolframic acid or Tungsten oxide 99.999; The described organic solvent of step (1) comprises one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, ether, methyl ethyl diketone or toluene; In the mixing solutions of the described hydrogen peroxide of step (1) and organic solvent, the volume ratio of hydrogen peroxide and organic solvent is 1:1, and the time of stirring is 18-24h.
3. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the volumetric molar concentration of tungsten in the described tungstenic colloidal sol of step (1) is 0.2-0.3mol/L.
4. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the described solubility vanadic salts of step (2) comprises one or more in methyl ethyl diketone vanadyl, vanadylic sulfate, dichloro vanadyl or oxalic acid vanadyl; The described solvent of step (2) comprises one or more the mixing in methyl alcohol, ethanol, water, n-propyl alcohol, Virahol, acetone, ethylene glycol, methyl ethyl diketone, ammoniacal liquor or hydrochloric acid; The described dispersion agent of step (2) is a kind of in polyvinylpyrrolidone or polyoxyethylene glycol, the 0.5-5% that the add-on of dispersion agent is solvent quality.
5. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the described volumetric molar concentration containing vanadium ion in the colloidal sol of vanadium ion of step (2) is 0.1-0.3mol/L.
6. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, and it is characterized in that mixing described in step (3) mol ratio of tungsten and vanadium ion in tungsten vanadium oxide colloidal sol is 0.5:100-10:100.
7. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the described substrate of step (4) comprises soda-lime-silica glass, silica glass, sheet mica or sapphire; The described clean of step (4) is for adopting successively deionized water, acetone and ethanol supersound washing, and each supersound washing time is 10-20 minute; The described inert atmosphere of step (4) is nitrogen or argon gas; Described vacuum condition is that low oxygen partial pressure vacuum tightness is 8 * 10
2-1 * 10
3the vacuum atmosphere of Pa.
8. intelligent temperature control look according to claim 1 becomes the preparation method of vanadium oxide film, it is characterized in that the described annealing treating process of step (4) is that temperature rise rate is 3-10 ℃/min, and annealing temperature is 500-600 ℃, and annealing time is 30-240min.
9. the intelligent temperature control look of preparing according to method described in claim 1-8 becomes a vanadium oxide film, it is characterized in that described vanadium oxide film transformation temperature is adjustable continuously within the scope of 25-60 ℃.
One kind according to claim 9 intelligent temperature control look become vanadium oxide film as the purposes of intelligent temperature control window glass.
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| CN104032278A (en) * | 2014-06-12 | 2014-09-10 | 中国科学院上海技术物理研究所 | Method for preparing vanadium dioxide film |
| CN104445990A (en) * | 2014-11-21 | 2015-03-25 | 武汉理工大学 | Method for reducing phase change temperature of vanadium dioxide film |
| CN105088198A (en) * | 2014-05-23 | 2015-11-25 | 武汉理工大学 | Method for preparing vanadium dioxide thermochromic thin film |
| CN105543810A (en) * | 2015-12-30 | 2016-05-04 | 湖北大学 | Nano VO2 film with superhydrophilic self-cleaning function and intelligent temperature control function and preparation method of nano VO2 film |
| CN106517325A (en) * | 2016-11-15 | 2017-03-22 | 北京理工大学 | W-and-Eu-codoped vanadium dioxide film and preparation method thereof |
| CN109384265A (en) * | 2017-08-02 | 2019-02-26 | Tcl集团股份有限公司 | The preparation method and applications of nano-metal-oxide film |
| CN109722653A (en) * | 2019-01-02 | 2019-05-07 | 华南理工大学 | A kind of method that solwution method prepares witch culture tin oxide transparent conductive film |
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| CN106517325B (en) * | 2016-11-15 | 2019-08-23 | 北京理工大学 | A kind of vanadium dioxide film and preparation method thereof of W and Eu codope |
| CN109384265A (en) * | 2017-08-02 | 2019-02-26 | Tcl集团股份有限公司 | The preparation method and applications of nano-metal-oxide film |
| CN109722653A (en) * | 2019-01-02 | 2019-05-07 | 华南理工大学 | A kind of method that solwution method prepares witch culture tin oxide transparent conductive film |
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