CN108585539A - Long-life alternative regulates and controls electrochomeric films and preparation method of the light with heat - Google Patents

Long-life alternative regulates and controls electrochomeric films and preparation method of the light with heat Download PDF

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CN108585539A
CN108585539A CN201810344704.9A CN201810344704A CN108585539A CN 108585539 A CN108585539 A CN 108585539A CN 201810344704 A CN201810344704 A CN 201810344704A CN 108585539 A CN108585539 A CN 108585539A
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fto
film
battle array
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amorphous
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CN108585539B (en
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任洋
周晓歌
赵高扬
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Xian University of Technology
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Xian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials

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  • Life Sciences & Earth Sciences (AREA)
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  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
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Abstract

The invention discloses a kind of long-life alternative regulation and control light and the electrochomeric films of heat, and FTO nano-pore battle arrays film, amorphous WO have been sequentially prepared on substrate using transparent conductive coated glass as substrate3Film, to form the amorphous WO with FTO nano-array embedded types3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film fills FTO nano-pores battle array film circular hole and the depth higher than FTO nano-pore battle array film circular holes.Preparation method is：It combines photosensitive sol-gel technique to prepare FTO nano-pore battle arrays using laser interference, then fills amorphous WO on the Kong Zhen using sol-gel technique3Matrix, to form composite membrane.The laminated film is because of chemical stability superpower FTO, it can still be kept after 100,000 electrochromism cycle preferably to light and heat selection modulation effect, moreover, the preparation method of the film has the characteristics that technique is controllable, easy large area film forming, it is suitable for industrial mass production.

Description

Long-life alternative regulates and controls electrochomeric films and preparation method of the light with heat
Technical field
The invention belongs to photoelectric function thin films technical fields, and in particular to a kind of long-life alternative regulation and control light and heat Electrochomeric films；The invention further relates to the preparation methods of long-life alternative regulation and control light and the electrochomeric films of heat.
Background technology
Electrochomeric films refer under alternate height or positive and negative External Electrical Field, can low transmission rate coloured state and A kind of novel intelligent material that reversible change occurs between the colour fading state of high-transmission rate, is the core of energy saving smart window.Mesh The electrochomeric films of preceding commercialization, can by regulation and control film in the transmissivity of near infrared band based on amorphous oxide W film Control penetrates the heat of the film, reaches energy-efficient purpose.But this film, can while obtaining relatively low nearinfrared transmittance Light-exposed transmissivity also drastically reduces, and affects the daylighting ability of coated glass window, moreover, because the unstability of non crystalline structure, Tungsten oxide film after repeatedly recycling, chemical property change dramatically, electrochromic property fade away, thus recycle the longevity Life is not high.
In view of the above-mentioned problems, at present it has been reported that settling mode be design and prepare with conductive oxide nano-particle Tungsten oxide electrochomeric films (the denomination of invention of embedded type：The nanocrystalline enhancing tungsten oxide electrochomeric films of one kind and its preparation Method, application No. is：201510358853.7 Publication No.：105036564 A of CN, publication date：2015.11.11), utilize Conductive oxide nano-particle regulating near-infrared transmitted light regulates and controls visible light using tungsten oxide, reaches to light (visible light) and heat The purpose of (near infrared light) selective regulation.Exist moreover, oxide nano-particles preferably electric conductivity can effectively facilitate electronics Being injected and extracted from tungsten oxide, the laminated film after the cycle that repeatedly changes colour, tungsten oxide still keep preferable chemical stabilization Property.However, the service life of this kind of composite material is not only influenced by tungsten oxide, it is also steady by conductive oxide nano particle chemistry It qualitatively restricts, the conductive oxide nano-particle chemistry state after multiple electrochemical discoloration cycle changes so that multiple It closes film to disappear to light and heat selective modulating action, is equally difficult to meet the minimum requirement in 25 years of service life.Therefore, to Realize large scale application of this novel electrochromic film in building energy saving field, it is necessary to film layer structure is redesigned, And study the technology of preparing of corresponding film layer.
Invention content
The object of the present invention is to provide a kind of electrochomeric films of long-life alternative regulation and control light and heat, which can Effectively to solve the problems, such as commercial tungsten oxide film short life and lack to regulate and control light and heat selective.
It is a further object to provide a kind of long-life alternative regulation and control light and the electrochomeric films of heat Preparation method, this method can large area film, be suitable for industrialization volume production.
The technical solution adopted in the present invention is：Long-life alternative regulates and controls the electrochomeric films of light and heat, with saturating Bright conductive coated glass is substrate, and FTO nano-pore battle arrays film, amorphous WO have been sequentially prepared on substrate3Film has to be formed The amorphous WO of FTO nano-array embedded types3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film fills FTO Nano-pore battle array film circular hole and the depth for being higher than FTO nano-pore battle array film circular holes.
The features of the present invention also characterized in that
Hole battle array depth is 30~60nm, the hole battle array period be 200nm, FTO nano-pore battle array Circularhole diameter is 100nm.
Amorphous WO3The thickness of film is 200~300nm.
Another technical solution of the present invention is：Long-life alternative regulates and controls the electrochomeric films of light and heat Preparation method, be as follows：
Step 1：Benzoyl acetone is mixed with absolute ethyl alcohol, is stirred at room temperature to its dissolving, obtains solution A；By two positive fourths Base tin oxide is mixed with solution A, is stirred 2 hours in 60 DEG C under dry nitrogen atmosphere, is obtained faint yellow sol B；To sol B In be mixed into a certain amount of polyethylene glycol 400 and trifluoroacetic acid, and stir 1 hour under 45 DEG C of dry nitrogen atmospheres to get yellowish The photosensitive colloidal sol C of color FTO；
Step 2：Using spin-coating method, colloidal sol C is coated on transparent conductive coated glass substrate, and in a vacuum furnace in 80 DEG C Lower drying 10 minutes, forms the photosensitive gel moulds of FTO；
Step 3：The photosensitive gel plastic substrates of FTO are placed in four beam laser interference systems and expose 20min, wherein exposure Wavelength 325nm, laser power 20mW, 108 ° of angle between coherent beam；
Step 4：The photosensitive gel plastic substrates of FTO after exposure are placed in dissolve and wash away in agent and are dissolved and washed away, unexposed portion is dissolved and washed away It removes, obtains the FTO gel moulds with nano-pore battle array, the hole battle array period is 200nm；
Step 5：By the FTO gel plastic substrates with nano-pore battle array, annealing 1 is small at 500 DEG C in oxygen atmosphere When, obtain FTO nano-pore battle array films；
Step 6：By WCl6It is mixed 1 hour in dry nitrogen atmosphere with absolute ethyl alcohol, obtains yellow WO3Colloidal sol D；
Step 7：Colloidal sol D is filled in FTO nano-pore battle arrays using spin-coating method, is made annealing treatment 0.5 hour through 300 DEG C, you can Obtain required electrochomeric films.
The features of the present invention also characterized in that
In step 1, di-nbutyltin oxide, benzoyl acetone, trifluoroacetic acid, polyethylene glycol 400, absolute ethyl alcohol mole Than being 1：0.5：0.167：0.02：20.
In step 2, the spin coating proceeding taken is：It is 2500~3000 revs/min, rotational time to control turntable rotary speed It is 30~50 seconds.
Described to dissolve and wash away the mixed solution that agent is methanol and n-butanol in step 4, the volume ratio of wherein methanol and n-butanol is 1:4, it is 20~50 seconds to dissolve and wash away the time.
In step 7, the spin coating proceeding taken is：Turntable rotary speed is 800~1500 revs/min, rotational time 60 ~80 seconds.
The preparation-obtained electrochomeric films of step 7 are using transparent conductive coated glass as substrate, on substrate successively Preparation has FTO nano-pore battle arrays film, amorphous WO3Film, to form the amorphous WO with FTO nano-array embedded types3THIN COMPOSITE Film, wherein array are regularly arranged Kong Zhen, and hole battle array depth is 30~60nm, the hole battle array period is 200nm, FTO nano-pore battle array circle Bore dia is 100nm, amorphous WO3Film fills FTO nano-pores battle array film circular hole and the depth higher than FTO nano-pore battle array film circular holes Degree, thickness are 200~300nm.
The beneficial effects of the invention are as follows：
(1) the stronger chemical stabilities of FTO is utilized to improve repeatedly cycle discoloration rear film to near-infrared electrochromic property Holding capacity, using the Modulatory character optimization laminated film of nano array structure to the electrochromism ability of near infrared light (often Conductive oxide nano-particle is disordered structure, is difficult to the electrochromic property of near infrared light), and then obtain The electrochomeric films that long-life, high-performance, multiband are selectively modulated.The film can effectively solve commercial tungsten oxide film The problem of short life and shortage regulate and control light and heat selective；
(2) FTO selected and tungsten oxide (WO3) combination, in combination with both electrochromism wave band, realize laminated film pair The selective regulation of light and heat.What is more important, FTO have stronger chemical stability, place it in electro-chemical systems, It is recycled through 100,000 discolorations, FTO chemical property is still stablized, and it is compound with amorphous oxide tungsten, also enhances oxidation The service life cycle of tungsten can effectively solve commercial tungsten oxide electrochomeric films and be difficult to meet service life to be more than to want for 25 years It asks；
(3) the preparation method is that laser interference exposure technology is combined with ultraviolet photosensitive sol-gel technique, The higher FTO nano-pores battle array of resolution ratio can be prepared, compared with corresponding lattice structure, the local surface plasma of hole battle array structure Resonance body coupling effect is more notable, and the near-infrared electrochromism ability thus brought is stronger.It is adopted moreover, whether preparing Kong Zhen Laser interference combines photosensitive sol-gal process, still prepares the sol-gal process of amorphous oxide tungsten use, is used equally for big Prepared by area thin film, technique is controllable, to realize that industrialization volume production is laid a good foundation.
Description of the drawings
Fig. 1 is the negative and positive extreme current for the electrochomeric films being prepared using the method for the present invention with discoloration cycle-index Change curve；
Fig. 2 is the transmittance curve figure of the electrochomeric films that are prepared using the method for the present invention under different voltages.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The present invention provides a kind of electrochomeric films of long-life alternative regulation and control light and heat, with transparent conductive coatings Glass is substrate, and Fluorin doped stannic oxide (abbreviation FTO) nano-pore battle array film, amorphous WO have been sequentially prepared on substrate3Film, To form the amorphous WO with FTO nano-array embedded types3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3 Film fills FTO nano-pores battle array film circular hole and the depth higher than FTO nano-pore battle array film circular holes；
Wherein, battle array depth in the holes FTO is 30~60nm, the hole battle array period is 200nm, Circularhole diameter 100nm；Amorphous WO3It is thin Film thickness is 200~300nm.
The present invention also provides a kind of preparation method of long-life alternative regulation and control light and the electrochomeric films of heat, tools Steps are as follows for body：
Step 1：Benzoyl acetone is mixed with absolute ethyl alcohol, is stirred at room temperature to its dissolving, obtains solution A；By two positive fourths Base tin oxide is mixed with solution A, is stirred 2 hours in 60 DEG C under dry nitrogen atmosphere, is obtained faint yellow sol B；To sol B In be mixed into a certain amount of polyethylene glycol 400 and trifluoroacetic acid, and stir 1 hour under 45 DEG C of dry nitrogen atmospheres to get yellowish The photosensitive colloidal sol C of color FTO；
In step 1, di-nbutyltin oxide, benzoyl acetone, trifluoroacetic acid, polyethylene glycol 400, absolute ethyl alcohol mole Than being 1：0.5：0.167：0.02：20；
Step 2：Using spin-coating method, colloidal sol C is coated on transparent conductive coated glass substrate, and in a vacuum furnace in 80 DEG C Lower drying 10 minutes, forms the photosensitive gel moulds of FTO in homogeneous thickness；
In step 2, the spin coating proceeding taken is：It it is 2500~3000 revs/min by controlling turntable rotary speed, rotation Time is 30~50 seconds；
Step 3：The photosensitive gel plastic substrates of FTO are placed in four beam laser interference systems and are exposed 20 minutes, wherein exposure Wavelength 325nm, laser power 20mW, 108 ° of angle between coherent beam；
Step 4：The photosensitive gel plastic substrates of FTO after exposure are placed in dissolve and wash away in agent and are dissolved and washed away, it, will not due to dissolubility difference Exposed portion dissolves and washes away removal, obtains the FTO gel moulds with nano-pore battle array, and the hole battle array period is 200nm；
In step 4, the mixed solution that agent is methanol and n-butanol is dissolved and washed away, the wherein volume ratio of methanol and n-butanol is 1:4, It is 20~50 seconds to dissolve and wash away the time；
Step 5：By the FTO gel plastic substrates with nano-pore battle array, annealing 1 is small at 500 DEG C in oxygen atmosphere When, obtain FTO nano-pore battle array films；
Step 6：By WCl6It is mixed 1 hour in dry nitrogen atmosphere with absolute ethyl alcohol, obtains yellow WO3Colloidal sol D；
Step 7：Colloidal sol D is filled in FTO nano-pore battle arrays using spin-coating method, is made annealing treatment 0.5 hour through 300 DEG C, you can Obtain required electrochomeric films；
In step 7, the spin coating proceeding taken is：Turntable rotary speed is 800~1500 revs/min, rotational time 60 ~80 seconds；
The preparation-obtained electrochomeric films of step 7 are to be sequentially prepared FTO on transparent conductive coated glass substrate Nano-pore battle array film, amorphous WO3Film, to form the amorphous WO with FTO nano-array embedded types3Laminated film, wherein array For regularly arranged Kong Zhen, hole battle array depth is 30~60nm, the hole battle array period is 200nm, Circularhole diameter 100nm, amorphous WO3It is thin Film fills FTO nano-pores battle array film circular hole and the depth higher than FTO nano-pore battle array film circular holes, amorphous WO3The thickness of film is 200~300nm.
Fig. 1 is the negative and positive extreme current for the electrochomeric films being prepared using the method for the present invention with discoloration cycle-index Change curve, for characterizing the service life cycle of the film, from figure 1 it appears that through 100,000 times discoloration cycle after, The anode and cathode extreme current of film still keeps higher numerical value.
Fig. 2 is the transmittance curve figure of the electrochomeric films that are prepared using the method for the present invention under different voltages, For characterizing electrochromic property of the film to light and heat selective modulation, from figure 2 it can be seen that when applying 1.5V voltages When, laminated film all has higher transmissivity in visible (400~800nm) and near-infrared region (800~2500nm)；When applying When adding -0.3V voltages, laminated film is significantly reduced near infrared region transmissivity, but is still kept not in the transmissivity of visible region Become, realizes the independence regulation and control to transmission of near infra red light rate；When application -1.5V voltages, laminated film is in visible and near-infrared Light area transmissivity declines, and thus illustrates that the selective regulation to light and heat may be implemented in the laminated film.
Embodiment 1
A kind of electrochomeric films of long-life alternative regulation and control light and heat, have FTO nano-array embedded types Amorphous WO3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film is filled FTO nano-pore battle array circular holes and is higher than Its circular hole depth.The holes FTO battle array depth is 60nm, period 200nm, Circularhole diameter 100nm, amorphous WO3Film thickness is 300nm。
Preparation method of composite film with the above structural parameters, is as follows：
The benzoyl acetone of 0.81g is mixed with the absolute ethyl alcohol of 9.22g, is stirred at room temperature to its dissolving, then by its turn Enter in the three-necked flask configured with drying nitrogen device, the di-nbutyltin oxide of 2.49g is added into the flask, adds at 60 DEG C Thermal agitation 2 hours, is naturally cooled to 45 DEG C, and the polyethylene glycol 400 of the trifluoroacetic acid and 0.08g of 0.19g is added thereto, Continue stirring 1 hour, obtains the photosensitive colloidal sols of flaxen FTO.
The photosensitive colloidal sols of FTO are coated on transparent conductive coated glass substrate using spin coating proceeding, wherein turntable rotary speed It it is 2500 revs/min, rotational time is 50 seconds, to form the uniform FTO gel moulds of surface thickness.Then FTO senses are coated with The gel plastic substrate of light colloidal sol is placed in drying box, is toasted 10 minutes in 80 DEG C, is taken out, is cooled to room temperature, and be positioned over four light Beam laser interference system is exposed, wherein angle is 108 ° between coherent beam, laser power 20mW, and exposure wavelength is The substrate is put into organic solvent (mixed solution of methanol and n-butanol, volume ratio 1 by 325nm after exposure in 20 minutes:4) In dissolve and wash away 50 seconds, take out simultaneously dried up with drying nitrogen, finally put it into the vacuum drying oven for being connected with high purity oxygen gas, at 500 DEG C Annealing 1 hour, obtain FTO nano-pore battle array films, wherein Circularhole diameter 100nm, circular hole depth be 60nm, hole battle array the period be 200nm。
And then, by the WCl of 5g6It is dissolved in the absolute ethyl alcohol of 30ml, is stirred at room temperature 1 hour and obtains yellow WO3Colloidal sol.It is logical It crosses spin coating proceeding and the colloidal sol is coated on FTO nano-pore battle arrays surface, turntable rotary speed is 800 revs/min, rotational time 80 Second, to form the uniform WO of surface thickness3Gel mould.Finally by the gel plastic substrate be placed in the oxygen atmosphere in 300 DEG C into Row heat treatment 0.5 hour obtains the amorphous oxide tungsten laminated film for having FTO nano-arrays embedded type and film thickness is 300nm.
By the film after 100,000 discoloration cycles, negative and positive extreme current only declines 10% (attached drawing 1), illustrates that the film has There are good cyclical stability, service life longer；In addition, it is 40% in the optical modulation value of 632.5nm wave bands, 2000nm wave band optics modulation values are 45%, and with the selection modulation capability (attached drawing 2) preferably to light and heat.
Embodiment 2
A kind of electrochomeric films of long-life alternative regulation and control light and heat, have FTO nano-array embedded types Amorphous WO3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film is filled FTO nano-pore battle array circular holes and is higher than Its circular hole depth.The holes FTO battle array depth is 30nm, period 200nm, Circularhole diameter 100nm, and noncrystal membrane thickness is 200nm.
Preparation method of composite film with the above structural parameters, is as follows：
The benzoyl acetone of 0.81g is mixed with the absolute ethyl alcohol of 9.22g, is stirred at room temperature to its dissolving, then by its turn Enter in the three-necked flask configured with drying nitrogen device, the di-nbutyltin oxide of 2.49g is added into the flask, adds at 60 DEG C Thermal agitation 2 hours, is naturally cooled to 45 DEG C, and the polyethylene glycol 400 of the trifluoroacetic acid and 0.08g of 0.19g is added thereto, Continue stirring 1 hour, obtains the photosensitive colloidal sols of flaxen FTO.
The photosensitive colloidal sols of FTO are coated on transparent conductive coated glass substrate using spin coating proceeding, wherein turntable rotary speed It it is 3000 revs/min, rotational time is 30 seconds, to form the uniform FTO gel moulds of surface thickness.Then FTO senses are coated with The gel plastic substrate of light colloidal sol is placed in drying box, is toasted 10 minutes in 80 DEG C, is taken out, is cooled to room temperature, and be positioned over four light Beam laser interference system is exposed, wherein angle is 108 ° between coherent beam, laser power 20mW, and exposure wavelength is The substrate is put into organic solvent (mixed solution of methanol and n-butanol, volume ratio 1 by 325nm after exposure in 20 minutes:4) In dissolve and wash away 20 seconds, take out simultaneously dried up with drying nitrogen, finally put it into the vacuum drying oven for being connected with high purity oxygen gas, at 500 DEG C Annealing 1 hour, obtain FTO nano-pore battle array films, wherein Circularhole diameter 100nm, circular hole depth be 30nm, hole battle array the period be 200nm。
And then, by the WCl of 5g6It is dissolved in the absolute ethyl alcohol of 30ml, is stirred at room temperature 1 hour and obtains yellow WO3Colloidal sol.It is logical It crosses spin coating proceeding and the colloidal sol is coated on FTO nano-pore battle arrays surface, turntable rotary speed is 1500 revs/min, and rotational time is 60 seconds, to form the uniform WO of surface thickness3Gel mould.Finally the gel plastic substrate is placed in the oxygen atmosphere in 300 DEG C Heat treatment 0.5 hour is carried out, the amorphous oxide tungsten laminated film that there is FTO nano-arrays embedded type and film thickness is 200nm is obtained.
By the film after 100,000 discoloration cycles, negative and positive extreme current only declines 5%, and it is good to illustrate that the film has Cyclical stability, service life are longer；In addition, it is 42% in the optical modulation value of 632.5nm wave bands, in 2000nm band of light It is 60% to learn modulation value, and with the selection modulation capability preferably to light and heat.
Embodiment 3
A kind of electrochomeric films of long-life alternative regulation and control light and heat, have FTO nano-array embedded types Amorphous WO3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film is filled FTO nano-pore battle array circular holes and is higher than Its circular hole depth.The holes FTO battle array depth is 45nm, period 200nm, Circularhole diameter 100nm, and noncrystal membrane thickness is 260nm.
Preparation method of composite film with the above structural parameters, is as follows：
The benzoyl acetone of 0.81g is mixed with the absolute ethyl alcohol of 9.22g, is stirred at room temperature to its dissolving, then by its turn Enter in the three-necked flask configured with drying nitrogen device, the di-nbutyltin oxide of 2.49g is added into the flask, adds at 60 DEG C Thermal agitation 2 hours, is naturally cooled to 45 DEG C, and the polyethylene glycol 400 of the trifluoroacetic acid and 0.08g of 0.19g is added thereto, Continue stirring 1 hour, obtains the photosensitive colloidal sols of flaxen FTO.
The photosensitive colloidal sols of FTO are coated on transparent conductive coated glass substrate using spin coating proceeding, wherein turntable rotary speed It it is 2800 revs/min, rotational time is 40 seconds, to form the uniform FTO gel moulds of surface thickness.Then FTO senses are coated with The gel plastic substrate of light colloidal sol is placed in drying box, is toasted 10 minutes in 80 DEG C, is taken out, is cooled to room temperature, and be positioned over four light Beam laser interference system is exposed, wherein angle is 108 ° between coherent beam, laser power 20mW, and exposure wavelength is The substrate is put into organic solvent (mixed solution of methanol and n-butanol, volume ratio 1 by 325nm after exposure in 20 minutes:4) In dissolve and wash away 30 seconds, take out simultaneously dried up with drying nitrogen, finally put it into the vacuum drying oven for being connected with high purity oxygen gas, at 500 DEG C Annealing 1 hour, obtain FTO nano-pore battle array films, wherein Circularhole diameter 100nm, circular hole depth be 45nm, hole battle array the period be 200nm。
And then, by the WCl of 5g6It is dissolved in the absolute ethyl alcohol of 30ml, is stirred at room temperature 1 hour and obtains yellow WO3Colloidal sol.It is logical It crosses spin coating proceeding and the colloidal sol is coated on FTO nano-pore battle arrays surface, turntable rotary speed is 1200 revs/min, and rotational time is 70 seconds, to form the uniform WO of surface thickness3Gel mould.Finally the gel plastic substrate is placed in the oxygen atmosphere in 300 DEG C Heat treatment 0.5 hour is carried out, the amorphous oxide tungsten laminated film that there is FTO nano-arrays embedded type and film thickness is 260nm is obtained.
By the film after 100,000 discoloration cycles, negative and positive extreme current only declines 8%, and it is good to illustrate that the film has Cyclical stability, service life are longer；In addition, it is 41% in the optical modulation value of 632.5nm wave bands, in 2000nm band of light It is 55% to learn modulation value, and with the selection modulation capability preferably to light and heat.
Embodiment 4
A kind of electrochomeric films of long-life alternative regulation and control light and heat, have FTO nano-array embedded types Amorphous WO3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film is filled FTO nano-pore battle array circular holes and is higher than Its circular hole depth.The holes FTO battle array depth is 50nm, period 200nm, Circularhole diameter 100nm, and noncrystal membrane thickness is 280nm.
Preparation method of composite film with the above structural parameters, is as follows：
The benzoyl acetone of 0.81g is mixed with the absolute ethyl alcohol of 9.22g, is stirred at room temperature to its dissolving, then by its turn Enter in the three-necked flask configured with drying nitrogen device, the di-nbutyltin oxide of 2.49g is added into the flask, adds at 60 DEG C Thermal agitation 2 hours, is naturally cooled to 45 DEG C, and the polyethylene glycol 400 of the trifluoroacetic acid and 0.08g of 0.19g is added thereto, Continue stirring 1 hour, obtains the photosensitive colloidal sols of flaxen FTO.
The photosensitive colloidal sols of FTO are coated on transparent conductive coated glass substrate using spin coating proceeding, wherein turntable rotary speed It it is 2600 revs/min, rotational time is 45 seconds, to form the uniform FTO gel moulds of surface thickness.Then FTO senses are coated with The gel plastic substrate of light colloidal sol is placed in drying box, is toasted 10 minutes in 80 DEG C, is taken out, is cooled to room temperature, and be positioned over four light Beam laser interference system is exposed, wherein angle is 108 ° between coherent beam, laser power 20mW, and exposure wavelength is The substrate is put into organic solvent (mixed solution of methanol and n-butanol, volume ratio 1 by 325nm after exposure in 20 minutes:4) In dissolve and wash away 40 seconds, take out simultaneously dried up with drying nitrogen, finally put it into the vacuum drying oven for being connected with high purity oxygen gas, at 500 DEG C Annealing 1 hour, obtain FTO nano-pore battle array films, wherein Circularhole diameter 100nm, circular hole depth be 50nm, hole battle array the period be 200nm。
And then, by the WCl of 5g6It is dissolved in the absolute ethyl alcohol of 30ml, is stirred at room temperature 1 hour and obtains yellow WO3Colloidal sol.It is logical It crosses spin coating proceeding and the colloidal sol is coated on FTO nano-pore battle arrays surface, turntable rotary speed is 1000 revs/min, and rotational time is 75 seconds, to form the uniform WO of surface thickness3Gel mould.Finally the gel plastic substrate is placed in the oxygen atmosphere in 300 DEG C Heat treatment 0.5 hour is carried out, the amorphous oxide tungsten laminated film that there is FTO nano-arrays embedded type and film thickness is 280nm is obtained.
By the film after 100,000 discoloration cycles, negative and positive extreme current only declines 6%, and it is good to illustrate that the film has Cyclical stability, service life are longer；In addition, it is 40% in the optical modulation value of 632.5nm wave bands, in 2000nm band of light It is 50% to learn modulation value, and with the selection modulation capability preferably to light and heat.
Embodiment 5
A kind of electrochomeric films of long-life alternative regulation and control light and heat, have FTO nano-array embedded types Amorphous WO3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film is filled FTO nano-pore battle array circular holes and is higher than Its circular hole depth.The holes FTO battle array depth is 40nm, period 200nm, Circularhole diameter 100nm, and noncrystal membrane thickness is 230nm.
Preparation method of composite film with the above structural parameters, is as follows：
The benzoyl acetone of 0.81g is mixed with the absolute ethyl alcohol of 9.22g, is stirred at room temperature to its dissolving, then by its turn Enter in the three-necked flask configured with drying nitrogen device, the di-nbutyltin oxide of 2.49g is added into the flask, adds at 60 DEG C Thermal agitation 2 hours, is naturally cooled to 45 DEG C, and the polyethylene glycol 400 of the trifluoroacetic acid and 0.08g of 0.19g is added thereto, Continue stirring 1 hour, obtains the photosensitive colloidal sols of flaxen FTO.
The photosensitive colloidal sols of FTO are coated on transparent conductive coated glass substrate using spin coating proceeding, wherein turntable rotary speed It it is 2900 revs/min, rotational time is 35 seconds, to form the uniform FTO gel moulds of surface thickness.Then FTO senses are coated with The gel plastic substrate of light colloidal sol is placed in drying box, is toasted 10 minutes in 80 DEG C, is taken out, is cooled to room temperature, and be positioned over four light Beam laser interference system is exposed, wherein angle is 108 ° between coherent beam, laser power 20mW, and exposure wavelength is The substrate is put into organic solvent (mixed solution of methanol and n-butanol, volume ratio 1 by 325nm after exposure in 20 minutes:4) In dissolve and wash away 25 seconds, take out simultaneously dried up with drying nitrogen, finally put it into the vacuum drying oven for being connected with high purity oxygen gas, at 500 DEG C Annealing 1 hour, obtain FTO nano-pore battle array films, wherein Circularhole diameter 100nm, circular hole depth be 40nm, hole battle array the period be 200nm。
And then, by the WCl of 5g6It is dissolved in the absolute ethyl alcohol of 30ml, is stirred at room temperature 1 hour and obtains yellow WO3Colloidal sol.It is logical It crosses spin coating proceeding and the colloidal sol is coated on FTO nano-pore battle arrays surface, turntable rotary speed is 1300 revs/min, and rotational time is 65 seconds, to form the uniform WO of surface thickness3Gel mould.Finally the gel plastic substrate is placed in the oxygen atmosphere in 300 DEG C Heat treatment 0.5 hour is carried out, the amorphous oxide tungsten laminated film that there is FTO nano-arrays embedded type and film thickness is 230nm is obtained.
By the film after 100,000 discoloration cycles, negative and positive extreme current only declines 5%, and it is good to illustrate that the film has Cyclical stability, service life are longer；In addition, it is 42% in the optical modulation value of 632.5nm wave bands, in 2000nm band of light It is 58% to learn modulation value, and with the selection modulation capability preferably to light and heat.
Advantages of the present invention is that technique is controllable, easily realizes large area industrialization film, and acquisition film impurities are less, simultaneously Due in amorphous WO3FTO nano-arrays are uniform-distribution in matrix, there are a large amount of structural rearrangements around array, by receiving Rice is modified so that fine and close nanometer crystal boundary becomes loose porous originally, these nanovoids constitute Li in electrolyte+Ion passes Defeated channel keeps the electrochromism ability of laminated film stronger.The requirement of commercial application can be met.

Claims (9)

1. long-life alternative regulates and controls the electrochomeric films of light and heat, which is characterized in that be with transparent conductive coated glass Substrate has been sequentially prepared FTO nano-pore battle arrays film, amorphous WO on substrate3Film has the insertion of FTO nano-arrays to be formed The amorphous WO of type3Laminated film, wherein array are regularly arranged Kong Zhen, amorphous WO3Film fills FTO nano-pore battle array films circle Hole and the depth for being higher than FTO nano-pore battle array film circular holes.
2. the electrochomeric films of long-life alternative regulation and control light and heat according to claim 1, which is characterized in that institute State that hole battle array depth is 30~60nm, the hole battle array period be 200nm, FTO nano-pore battle array Circularhole diameter is 100nm.
3. the electrochomeric films of long-life alternative regulation and control light and heat according to claim 1, which is characterized in that non- Brilliant WO3The thickness of film is 200~300nm.
4. long-life alternative regulates and controls the preparation method of light and the electrochomeric films of heat, which is characterized in that specific steps are such as Under：
Step 1：Benzoyl acetone is mixed with absolute ethyl alcohol, is stirred at room temperature to its dissolving, obtains solution A；By di-n-butyl oxygen Change tin to mix with solution A, is stirred 2 hours in 60 DEG C under dry nitrogen atmosphere, obtain faint yellow sol B；It is mixed into sol B Enter a certain amount of polyethylene glycol 400 and trifluoroacetic acid, and 1 hour is stirred to get faint yellow FTO under 45 DEG C of dry nitrogen atmospheres Photosensitive colloidal sol C；
Step 2：Using spin-coating method, colloidal sol C is coated on transparent conductive coated glass substrate, and dried at 80 DEG C in a vacuum furnace It is 10 minutes dry, form the photosensitive gel moulds of FTO；
Step 3：The photosensitive gel plastic substrates of FTO are placed in four beam laser interference systems and expose 20min, wherein exposure wavelength 325nm, laser power 20mW, 108 ° of angle between coherent beam；
Step 4：The photosensitive gel plastic substrates of FTO after exposure are placed in dissolve and wash away in agent and are dissolved and washed away, unexposed portion is dissolved and washed away into removal, is obtained To the FTO gel moulds with nano-pore battle array, the hole battle array period is 200nm；
Step 5：FTO gel plastic substrates with nano-pore battle array are made annealing treatment 1 hour in oxygen atmosphere at 500 DEG C, are obtained To FTO nano-pore battle array films；
Step 6：By WCl6It is mixed 1 hour in dry nitrogen atmosphere with absolute ethyl alcohol, obtains yellow WO3Colloidal sol D；
Step 7：Colloidal sol D is filled in FTO nano-pore battle arrays using spin-coating method, is made annealing treatment 0.5 hour through 300 DEG C, you can obtain Required electrochomeric films.
5. the preparation side of a kind of long-life alternative regulation and control light and the electrochomeric films of heat according to claim 4 Method, which is characterized in that in step 1, di-nbutyltin oxide, benzoyl acetone, trifluoroacetic acid, polyethylene glycol 400, absolute ethyl alcohol Molar ratio be 1：0.5：0.167：0.02：20.
6. the preparation method of long-life alternative regulation and control light and the electrochomeric films of heat according to claim 4, It is characterized in that, in step 2, the spin coating proceeding taken is：Control turntable rotary speed be 2500~3000 revs/min, rotation when Between be 30~50 seconds.
7. the preparation method of long-life alternative regulation and control light and the electrochomeric films of heat according to claim 4, It is characterized in that, it is described to dissolve and wash away the mixed solution that agent is methanol and n-butanol, the wherein volume ratio of methanol and n-butanol in step 4 It is 1:4, it is 20~50 seconds to dissolve and wash away the time.
8. the preparation method of long-life alternative regulation and control light and the electrochomeric films of heat according to claim 4, It is characterized in that, in step 7, the spin coating proceeding taken is：Turntable rotary speed is 800~1500 revs/min, rotational time 60 ~80 seconds.
9. the preparation method of long-life alternative regulation and control light and the electrochomeric films of heat according to claim 4, step Rapid 7 preparation-obtained electrochomeric films are using transparent conductive coated glass as substrate, and on substrate being sequentially prepared FTO receives Metre hole battle array film, amorphous WO3Film, to form the amorphous WO with FTO nano-array embedded types3Laminated film, wherein array are Regularly arranged Kong Zhen, hole battle array depth is 30~60nm, the hole battle array period be 200nm, FTO nano-pore battle array Circularhole diameter is 100nm, Amorphous WO3Film fills FTO nano-pores battle array film circular hole and the depth higher than FTO nano-pore battle array film circular holes, thickness 200 ~300nm.
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