CN101805135A - Photovoltaic glass plated with double-layer antireflection film and preparation method thereof - Google Patents
Photovoltaic glass plated with double-layer antireflection film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses photovoltaic glass plated with a double-layer antireflection film, wherein the double-layer antireflection film comprises a high refraction index oxide layer plated on the surface of the photovoltaic glass and a low refraction index porous silicon oxide layer plated on the high refraction index oxide layer; and high refraction index oxide is selected from one of titanium dioxide, zinc oxide and zirconium oxide. The photovoltaic glass plated with the double-layer antireflection film has higher transmissivity to visible light wavebands which are good for improving the power of a solar battery, simultaneously has lower transmissivity to far infrared wavebands which are harmful to improving the power of the solar battery and is remarkable in advantages; and meanwhile, the invention also discloses a preparation method of the photovoltaic glass, which has low cost and simple technical routes and is suitable for industrial production.
Description
Technical field
The present invention relates to the photovoltaic glass surface treatment process, relate in particular to photovoltaic glass of a kind of plated with double-layer antireflection film and preparation method thereof.
Background technology
Worldwide energy shortage and environmental protection pressure have greatly promoted research and development and the application of people to the solar cell photovoltaic assembly.Along with people to the continuing to optimize of solar cell photovoltaic assembly, the efficiency of conversion of crystal silicon cell sheet continues to rely on and improves the efficient of battery sheet own and improve the photovoltaic module real output and become very difficult near ultimate value in the solar photovoltaic assembly.At present, the packaged glass that people generally adopt the lower photovoltaic glass of a kind of iron-holder to use as the solar cell photovoltaic assembly, this glass has higher transmittance at visible light wave range.But because refractive index difference between photovoltaic glass and the air, still there is about 8% reflection in photovoltaic glass to visible light.Can improve the transmitance of light effectively by coat one deck antireflective coating at photovoltaic glass surface, thereby improve the output rating of solar cell photovoltaic assembly.
At present, photovoltaic glass is limited by the requirement of cost with antireflective coating, mainly is the antireflective film structure that adopts the individual layer porous silica of chemical corrosion method or Prepared by Sol Gel Method.For example, U.S. Pat 45355026 discloses and deposited one deck SiO earlier on substrate
2Film is realized antireflecting effect thereby adopt chemical etching to form hole then.Publication number be in the Chinese patent application of CN1263354A then by in nano SiO 2 particle cross-linked network or particle network, infiltrating organic additive and silane coupling agent, utilize the soda acid two-step approach to prepare the antireflection coatings of high-strength film-substrate cohesion.Though the individual layer antireflective coating is produced easily, because the requirement of hardness and film-substrate cohesion is arranged, structure is comparatively fine and close with silica-based antireflective coating for photovoltaic, and reflection preventing ability is often lower, and the control measures of its antireflection characteristic are single.Simultaneously, therefore the classical antireflective film structure of common multilayer, is difficult to realize with the method for collosol and gel owing to very responsive to the thickness of every tunic; Though the antireflective film gauge control that magnetron sputtering method is coated with is accurate; easy large-area preparation high-performance multilayer antireflective coating; thereby can regulate and control flexibly also to realize the wide spectrum anti-reflective effect to the optical characteristics of antireflective film; but cost is comparatively expensive comparatively speaking, is difficult to use in the mass-producing of photovoltaic field.So far, find as yet to encapsulate the bibliographical information of using and can utilizing the high-performance double-layer antireflective coating of sol-gel method scale preparation at photovoltaic module specially.
Summary of the invention
The present invention is directed to the photovoltaic glass that is coated with conventional individual layer antireflective coating at present still there is higher reflection in visible light, influence the problem of the raising of solar cell photovoltaic assembly output rating, a kind of photovoltaic glass of plated with double-layer antireflection film is provided.
The present invention is also not high to the control accuracy of thickness at present sol-gel method big area film forming; and can't utilize the sol-gel method scale preparation to be coated with the defective of the photovoltaic glass of common multilayer classical architecture antireflective coating, provide a kind of and can utilize Prepared by Sol Gel Method, be coated with the optical characteristics double-deck SiO not too responsive of film system to the error of individual layer thickness
2/ TiO
2The preparation method of the photovoltaic glass of antireflective coating.
A kind of photovoltaic glass of plated with double-layer antireflection film, described double layer antireflection coating is made up of high refractive index oxide layer that is plated in photovoltaic glass surface and the porous silica layer that is plated on the high refractive index oxide layer;
As preferably:
Described high refractive index oxide is selected from a kind of in the oxide compounds such as titanium oxide, zinc oxide, zirconium white.
The thickness of described high refractive index oxide layer is 5nm～25nm.
The thickness of described porous silica layer is 100nm～150nm.
The simulation calculation of utilizing the optical delivery matrix to carry out shows, double layer antireflection coating according to above-mentioned preferred construction preparation, the useful visible light wave range of solar cell there is being better anti-reflective effect than mono-layer oxidized silicon antireflective coating, and in 400nm～1200nm wavelength region, the average reflectance of solar spectrum weighting is also being had the effect of improvement.
The preparation method of the photovoltaic glass of described plated with double-layer antireflection film comprises step:
(1) with the presoma is raw material, preparation high refractive index oxide Nano sol in the mixing solutions of alcohol, acid and deionized water;
Described presoma is selected from a kind of in tetrabutyl titanate, zinc acetate, the basic zirconium chloride;
(2) the high refractive index oxide Nano sol that obtains in the step (1) is coated on process cleaning and the dried photovoltaic glass surface, makes the photovoltaic glass that is coated with the high refractive index oxide layer through solidification treatment;
(3) be raw material with deionized water, catalyzer, silicon source, silane coupling agent and solvent, prepare silicon colloidal sol; Described silicon source is selected from one or both in methyl silicate, the tetraethoxy;
(4) silicon sol that obtains in the step (3) is coated on the photovoltaic glass that is coated with the high refractive index oxide layer that makes in the step (2), makes the photovoltaic glass of plated with double-layer antireflection film through solidification treatment.
Described pure preferred alcohol.
Preferred acetate of described acid or hydrochloric acid.
Wherein, for the preparation of titanium oxide sol, the preferred tetrabutyl titanate of the presoma of selecting for use, pure preferred alcohol, preferred acetate of acid or hydrochloric acid; For the preparation of zinc oxide colloidal sol, the preferred zinc acetate of the presoma of selecting for use, pure preferred alcohol, the preferred acetate of acid; For the preparation of zirconia sol, the preferred basic zirconium chloride of the presoma of selecting for use, pure preferred alcohol, the preferred hydrochloric acid of acid.
In the step (1), presoma, deionized water, acid is preferably 1: 1 with pure mol ratio～and 5: 0.5～2.5: 45～250.
In the step (3), a kind of in the preferred hydrochloric acid of described catalyzer, the ammoniacal liquor.
In the preferred γ-An Bingjisanyiyangjiguiwan of described silane coupling agent, 13 fluoro octyl triethoxyl silanes, vinyltriethoxysilane or (3-chloropropyl) Trimethoxy silane one or more.
In described solvent particular methanol, ethanol, ethylene glycol or the Virahol one or more.
In the step (3), the mol ratio of silicon source, deionized water, catalyzer, solvent and silane coupling agent is preferably 3: 1～and 5: 1～3: 60～100: 1.5～3.75.
Preferred 200 ℃～550 ℃ of described solidification treatment temperature, the solidification treatment time is preferably 1 minute～and 180 minutes.
Described coating by spin coating, lift, spray or existing coating method such as printing is finished.
Compared with prior art, the invention has the advantages that:
Because the existence of the high refractive index oxide layer of thickness 5nm～25nm is arranged between the low-refraction porous silica layer of photovoltaic glass surface thickness 100nm～150nm and photovoltaic glass substrate, silica-based antireflective coating provides means in the anti-reflection characteristic of visible light wave range and the characteristic of improving at infrared band that sees through on the photovoltaic glass in order to regulate and control flexibly and effectively.
With the high refractive index layer is that titania meterial is an example, optical property to silicon oxide/titanium oxide double layer antireflection coating is carried out theoretical modeling, the result shows, the existence of the titanium oxide layer of thickness 5nm～25nm can significantly improve the reflection preventing ability of antireflective coating at photovoltaic anti-reflection centre wavelength 550nm place, as shown in Figure 2; Simultaneously, the existence of the titanium oxide layer of thickness 5nm～25nm also has the effect of improvement to antireflective coating in 400nm～1200nm wavelength region to the average reflectance of solar spectrum weighting, as shown in Figure 3; In addition, the optical characteristics of whole double layer antireflection coating is insensitive to the error of individual layer antireflective thickness, can not produce serious deterioration even increase reflex action, therefore be fit to the sol-gel technology big area and produce because of the optical property of the fluctuation of individual layer thickness about 10nm to rete.Low whole process cost of the present invention, technological line is simple, is fit to industrial and large-scale application.
The photovoltaic glass of plated with double-layer antireflection film of the present invention is having higher transmitance to improving the useful visible light wave range of solar cell power, and then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
Description of drawings
Fig. 1 is the structural representation of the photovoltaic glass of plated with double-layer antireflection film of the present invention;
Fig. 2 is the theoretical modeling figure of the double layer antireflection coating of different porous silica layer thicknesses and different titanium oxide layer thickness at 550nm wavelength place reflectivity;
Fig. 3 be different porous silica layer thicknesses with different titanium oxide layer thickness double layer antireflection coatings at the theoretical modeling figure of 400nm～1200nm wavelength to the average reflectance of solar spectrum weighting;
Fig. 4 is the photovoltaic glass and the transmitance correlation curve figure that is coated with mono-layer oxidized silicon antireflective coating photovoltaic glass of plated with double-layer silicon oxide/titanium oxide antireflective coating of making of embodiment 1.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
0.1mol water, 0.035mol HCl and 1.5mol ethanol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.0235mol tetrabutyl titanate rapidly and mix stirring 30 hours, obtain the titanium oxide sol of stable transparent, aging 3 days stand-by.
With the photovoltaic glass is matrix, and the titanium oxide sol after aging is carried out plated film with crystal pulling method at photovoltaic glass surface, and pull rate 2mm/s lifts number of times 1 time, lifts the end back and dries the photovoltaic glass that just can obtain being coated with the transparent titanium dioxide gel-film naturally.To the thermal treatment 1 minute in 550 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent titanium dioxide gel-film that makes, just can obtain being coated with the photovoltaic glass sample that thickness is about 20nm, titanium dioxide film that film-substrate cohesion is good.
With 0.25mol water, 0.078mol NH
3H
2O and 4.75mol dehydrated alcohol mix stirring heating, treat that temperature reaches 40 ℃ of design temperatures, add 0.15mol tetraethoxy (TEOS) rapidly, keep temperature-resistant, continue to stir 30 hours, obtain the silicon dioxide gel A of stable transparent; 0.075mol 13 fluoro octyl triethoxyl silanes are slowly added in the 0.25mol dehydrated alcohol, continue to stir 5 minutes, obtain solution B.Solution B is slowly splashed among the silicon dioxide gel A, stirred 5 minutes, obtain silicon sol, aging 3 days stand-by.
Silicon sol after aging is coated on the aforementioned photovoltaic glass sample that is coated with titanium dioxide film with crystal pulling method, and pull rate 2mm/s lifts number of times 1 time, lifts to finish the back and dry the photovoltaic glass that just can obtain being coated with the transparent silicon dioxide gel-film naturally.To the thermal treatment 1 minute in 550 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent silicon dioxide gel-film that makes, obtain the photovoltaic glass that silicon oxide layer thickness is about 100nm and has transmissivity height, earth silicon/titanic oxide double layer antireflection coating that film-substrate cohesion is good.
The transmitance of the photovoltaic glass of the photovoltaic glass of above-mentioned plated with double-layer antireflection film and mono-layer oxidized silicon antireflective coating is compared test, correlation curve figure such as Fig. 4 of transmitance, as known in the figure, compare with mono-layer oxidized silicon antireflective coating, the photovoltaic glass of above-mentioned plated with double-layer silicon oxide/titanium oxide antireflective coating is having higher transmitance to improving the useful visible light wave range of solar cell power, then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
0.1175mol water, 0.01175mol HCl and 1.175mol ethanol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.0235mol tetrabutyl titanate rapidly and mix stirring 30 hours, obtain the titanium oxide sol of stable transparent, aging 3 days stand-by.
With the photovoltaic glass is matrix, and the titanium oxide sol after aging is carried out plated film with crystal pulling method at photovoltaic glass surface, and pull rate 2mm/s lifts number of times 1 time, lifts the end back and dries the photovoltaic glass that just can obtain being coated with the transparent titanium dioxide gel-film naturally.To the thermal treatment 3 hours in 200 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent titanium dioxide gel-film that makes, just can obtain being coated with the photovoltaic glass sample that thickness is about 25nm, titanium dioxide film that film-substrate cohesion is good.
0.05mol water, 0.05mol hydrochloric acid and 3mol dehydrated alcohol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add 0.15mol tetraethoxy (TEOS) and 0.075mol 13 fluoro octyl triethoxyl silanes rapidly, keep temperature-resistant, continue to stir 30 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by.
Silicon sol after aging is coated on the aforementioned photovoltaic glass sample that is coated with titanium dioxide film with crystal pulling method, and pull rate 2mm/s lifts number of times 1 time, lifts to finish the back and dry the photovoltaic glass that just can obtain being coated with the transparent silicon dioxide gel-film naturally.To the thermal treatment 3 hours in 200 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent silicon dioxide gel-film that makes, obtain the photovoltaic glass that silicon oxide layer thickness is about 150nm and has transmissivity height, earth silicon/titanic oxide double layer antireflection coating that film-substrate cohesion is good.
The transmitance of the photovoltaic glass of the photovoltaic glass of above-mentioned plated with double-layer antireflection film and mono-layer oxidized silicon antireflective coating is compared test, find: compare with mono-layer oxidized silicon antireflective coating, the photovoltaic glass of above-mentioned plated with double-layer silicon oxide/titanium oxide antireflective coating is having higher transmitance to improving the useful visible light wave range of solar cell power, then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
Embodiment 3
0.0235mol water, 0.05875mol acetic acid and 5.875mol ethanol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.0235mol tetrabutyl titanate rapidly and mix stirring 30 hours, obtain the titanium oxide sol of stable transparent, aging 3 days stand-by.
With the photovoltaic glass is matrix, and the titanium oxide sol after aging is carried out plated film with crystal pulling method at photovoltaic glass surface, and pull rate 2mm/s lifts number of times 1 time, lifts the end back and dries the photovoltaic glass that just can obtain being coated with the transparent titanium dioxide gel-film naturally.To the thermal treatment 0.5 hour in 300 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent titanium dioxide gel-film that makes, just can obtain being coated with the photovoltaic glass sample that thickness is about 5nm, titanium dioxide film that film-substrate cohesion is good.
0.05mol water, 0.15mol hydrochloric acid and 4.75mol dehydrated alcohol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add 0.15mol tetraethoxy (TEOS) rapidly, keep temperature-resistant, continue to stir 30 hours, obtain the silicon dioxide gel A of stable transparent; 0.1875mol 13 fluoro octyl triethoxyl silanes are slowly added in the 0.25mol dehydrated alcohol, continue to stir 5 minutes, obtain solution B.Solution B is slowly splashed among the silicon dioxide gel A, stirred 5 minutes, obtain silicon sol, aging 3 days stand-by.
Silicon sol after aging is coated on the aforementioned photovoltaic glass sample that is coated with titanium dioxide film with crystal pulling method, and pull rate 2mm/s lifts number of times 1 time, lifts to finish the back and dry the photovoltaic glass that just can obtain being coated with the transparent silicon dioxide gel-film naturally.To the thermal treatment 0.5 hour in 300 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent silicon dioxide gel-film that makes, obtain the photovoltaic glass that silicon oxide layer thickness is about 150nm and has transmissivity height, earth silicon/titanic oxide double layer antireflection coating that film-substrate cohesion is good.
The transmitance of the photovoltaic glass of the photovoltaic glass of above-mentioned plated with double-layer antireflection film and mono-layer oxidized silicon antireflective coating is compared test, find: compare with mono-layer oxidized silicon antireflective coating, the photovoltaic glass of above-mentioned plated with double-layer silicon oxide/titanium oxide antireflective coating is having higher transmitance to improving the useful visible light wave range of solar cell power, then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
Embodiment 4
0.1mol water, 0.05mol acetic acid and 1.95mol ethanol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.03mol zinc acetate rapidly and mix stirring 30 hours, obtain the zinc oxide colloidal sol of stable transparent, aging 3 days stand-by.
With the photovoltaic glass is matrix, and the zinc oxide colloidal sol after aging is carried out plated film with crystal pulling method at photovoltaic glass surface, and pull rate 2mm/s lifts number of times 1 time, lifts the end back and dries the photovoltaic glass that just can obtain being coated with transparent zinc oxide gel-film naturally.To the thermal treatment 0.1 hour in 500 ℃ of air of the above-mentioned photovoltaic glass that is coated with transparent zinc oxide gel-film that makes, just can obtain being coated with the photovoltaic glass sample that thickness is about 15nm, zinc oxide film that film-substrate cohesion is good.
With 0.25mol water, 0.078mol NH
3H
2O and 3.9mol dehydrated alcohol mix stirring heating, treat that temperature reaches 40 ℃ of design temperatures, add 0.15mol tetraethoxy (TEOS) rapidly, keep temperature-resistant, continue to stir 30 hours, obtain the silicon dioxide gel A of stable transparent; 0.075mol 13 fluoro octyl triethoxyl silanes are slowly added in the 0.25mol dehydrated alcohol, continue to stir 5 minutes, obtain solution B.Solution B is slowly splashed among the silicon dioxide gel A, stirred 5 minutes, obtain silicon sol, aging 3 days stand-by.
Silicon sol after aging is coated on the aforementioned photovoltaic glass sample that is coated with the zinc oxide film with crystal pulling method, and pull rate 2mm/s lifts number of times 1 time, lifts to finish the back and dry the photovoltaic glass that just can obtain being coated with the transparent silicon dioxide gel-film naturally.To the thermal treatment 0.5 hour in 300 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent silicon dioxide gel-film that makes, obtain the photovoltaic glass that silicon oxide layer thickness is about 120nm and has transmissivity height, silicon-dioxide/zinc oxide double layer antireflection coating that film-substrate cohesion is good.
The transmitance of the photovoltaic glass of the photovoltaic glass of above-mentioned plated with double-layer antireflection film and mono-layer oxidized silicon antireflective coating is compared test, find: compare with mono-layer oxidized silicon antireflective coating, the photovoltaic glass of above-mentioned plated with double-layer silicon oxide/zinc oxide antireflective coating is having higher transmitance to improving the useful visible light wave range of solar cell power, then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
0.1mol water, 0.05mol hydrochloric acid and 1.45mol ethanol are mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.03mol basic zirconium chloride rapidly and mix stirring 30 hours, obtain the zirconia sol of stable transparent, aging 3 days stand-by.
With the photovoltaic glass is matrix, and the zirconia sol after aging is carried out plated film with crystal pulling method at photovoltaic glass surface, and pull rate 2mm/s lifts number of times 1 time, lifts the end back and dries the photovoltaic glass that just can obtain being coated with transparent zirconium dioxide gel-film naturally.To the thermal treatment 0.1 hour in 400 ℃ of air of the above-mentioned photovoltaic glass that is coated with transparent zirconium dioxide gel-film that makes, just can obtain being coated with the photovoltaic glass sample that thickness is about 20nm, zirconium dioxide film that film-substrate cohesion is good.
0.25mol water, 0.078mol hydrochloric acid and 3.6mol dehydrated alcohol are mixed stirring heating, treat that temperature reaches 40 ℃ of design temperatures, add 0.15mol tetraethoxy (TEOS) rapidly, keep temperature-resistant, continue to stir 30 hours, obtain the silicon dioxide gel A of stable transparent; 0.075mol 13 fluoro octyl triethoxyl silanes are slowly added in the 0.25mol dehydrated alcohol, continue to stir 5 minutes, obtain solution B.Solution B is slowly splashed among the silicon dioxide gel A, stirred 5 minutes, obtain silicon sol, aging 3 days stand-by.
Silicon sol after aging is coated on the aforementioned photovoltaic glass sample that is coated with the zirconium dioxide film with crystal pulling method, and pull rate 2mm/s lifts number of times 1 time, lifts to finish the back and dry the photovoltaic glass that just can obtain being coated with the transparent silicon dioxide gel-film naturally.To the thermal treatment 0.1 hour in 400 ℃ of air of the above-mentioned photovoltaic glass that is coated with the transparent silicon dioxide gel-film that makes, obtain the photovoltaic glass that silicon oxide layer thickness is about 130nm and has transmissivity height, silicon-dioxide/zirconium dioxide double layer antireflection coating that film-substrate cohesion is good.
The transmitance of the photovoltaic glass of the photovoltaic glass of above-mentioned plated with double-layer antireflection film and mono-layer oxidized silicon antireflective coating is compared test, find: compare with mono-layer oxidized silicon antireflective coating, the photovoltaic glass of above-mentioned plated with double-layer silicon oxide/zirconium white antireflective coating is having higher transmitance to improving the useful visible light wave range of solar cell power, then lower to improving the deleterious far infrared band transmitance of solar cell power, advantage is remarkable simultaneously.
Claims (10)
1. the photovoltaic glass of a plated with double-layer antireflection film is characterized in that, described double layer antireflection coating is made up of high refractive index oxide layer that is plated in photovoltaic glass surface and the porous silica layer that is plated on the high refractive index oxide layer;
Described high refractive index oxide is selected from a kind of in titanium oxide, zinc oxide, the zirconium white.
2. photovoltaic glass according to claim 1 is characterized in that, the thickness of described high refractive index oxide layer is 5nm～25nm.
3. photovoltaic glass according to claim 1 and 2 is characterized in that, the thickness of described porous silica layer is 100nm～150nm.
4. according to the preparation method of the photovoltaic glass of each described plated with double-layer antireflection film of claim 1～3, comprise step:
(1) with the presoma is raw material, preparation high refractive index oxide Nano sol in the mixing solutions of alcohol, acid and deionized water;
Described presoma is selected from a kind of in tetrabutyl titanate, zinc acetate, the basic zirconium chloride;
(2) the high refractive index oxide Nano sol that obtains in the step (1) is coated on process cleaning and the dried photovoltaic glass surface, makes the photovoltaic glass that is coated with the high refractive index oxide layer through solidification treatment;
(3) be raw material with deionized water, catalyzer, silicon source, silane coupling agent and solvent, prepare silicon colloidal sol; Described silicon source is selected from one or both in methyl silicate, the tetraethoxy;
(4) silicon sol that obtains in the step (3) is coated on the photovoltaic glass that is coated with the high refractive index oxide layer that makes in the step (2), makes the photovoltaic glass of plated with double-layer antireflection film through solidification treatment.
5. preparation method according to claim 4 is characterized in that, in the step (1), described alcohol is selected ethanol for use;
Perhaps, described acid is selected from acetate or hydrochloric acid.
6. according to claim 4 or 5 described preparation methods, it is characterized in that in the step (1), the mol ratio of presoma, deionized water, acid and alcohol is 1: 1～5: 0.5～2.5: 45～250.
7. preparation method according to claim 4 is characterized in that, in the step (3), described catalyzer is selected from a kind of in hydrochloric acid, the ammoniacal liquor;
Perhaps, described silane coupling agent is selected from one or more in γ-An Bingjisanyiyangjiguiwan, 13 fluoro octyl triethoxyl silanes, vinyltriethoxysilane or (3-chloropropyl) Trimethoxy silane;
Perhaps, described solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol or the Virahol.
8. according to claim 4 or 7 described preparation methods, it is characterized in that in the step (3), the mol ratio of silicon source, deionized water, catalyzer, solvent and silane coupling agent is 3: 1～5: 1～3: 60～100: 1.5～3.75.
9. preparation method according to claim 4 is characterized in that, described solidification treatment temperature is 200 ℃～550 ℃, and the solidification treatment time is 1 minute～180 minutes.
10. preparation method according to claim 4 is characterized in that, described coating by spin coating, lift, spray or print and finish.
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