CN101985390A - Self-cleaning glass and preparation method thereof - Google Patents
Self-cleaning glass and preparation method thereof Download PDFInfo
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- CN101985390A CN101985390A CN2009101090678A CN200910109067A CN101985390A CN 101985390 A CN101985390 A CN 101985390A CN 2009101090678 A CN2009101090678 A CN 2009101090678A CN 200910109067 A CN200910109067 A CN 200910109067A CN 101985390 A CN101985390 A CN 101985390A
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Abstract
The invention provides a self-cleaning glass. The self-cleaning glass comprises a glass base, a nano sliver layer and a titanium dioxide layer in turn, wherein the nano sliver layer is distributed between the glass base and the titanium dioxide layer; and the titanium dioxide layer is a photo-catalyst layer. The invention also provides a preparation method for the self-cleaning glass. Because the nano sliver layer is distributed on the glass and the titanium dioxide layer is distributed on the nano sliver layer, the self-cleaning glass can effectively improve the utilization rate of sunlight and improve the photo-catalysis efficiency of a TiO2 film so that the photo-catalysis efficiency of the self-cleaning glass is improved. In the preparation method for the self-cleaning glass, the nano sliver layer with strong bonding force with glass is formed on the surface of the glass by adopting a magnetron sputtering method, and the titanium dioxide layer which is not easy to fall from the glass is formed on the nano sliver layer by a sol-gel method, so the service life of the glass is long; and meanwhile, the preparation method has simple process and the reaction condition is easy to control.
Description
[technical field]
The present invention relates to technical field of glass materials, particularly a kind of glass with clean and preparation method thereof.
[background technology]
At present glass with clean has two research directions, allows glass surface form super hydrophilic or super-hydrophobic coat, wherein the water droplet contact angle less than 10 ° be super-hydrophilic coating, the water droplet contact angle greater than 110 ° be super-hydrophobic coat.TiO
2Film has Superhydrophilic and photocatalytic degradation, under illumination condition, can also decompose adsorbed organic matter, avoids adhering to of organic pollutant, therefore prepares TiO at glass surface
2Film is widely used.
At present, prepare TiO at glass surface
2The method of film is a lot.CN101255019A discloses a kind of chromatic self-cleaning film-coating glass, comprises glass substrate, titanium deoxid film and noble metal nano particles; Titanium deoxid film is deposited on glass substrate surface, and noble metal nano particles is entrained among the titanium oxide film layer or at the interface, described noble metal nano particles mainly is gold and silver, copper etc.A kind of coated glass that has from clean and low radiation functions is disclosed among the CN101182128A, one side at glass surface is coated with titanium dioxide from clean rete, another side is coated with low-radiation film or reflected infrared rete, or be coated with titanium oxide film layer on the two sides of glass, Yi Mian titanium oxide film layer is coated with low-radiation film or reflected infrared rete outward more therein, and described low-radiation film or reflected infrared rete are oxide semiconductor film or money base multilayer film.
Above-mentioned two kinds of glass are directly at the direct deposition of titanium oxide layer of glass surface, have two problems: 1) TiO
2The exciting light of photocatalyst is at the ultraviolet band of wavelength less than 387.5nm, and it is about 4% that sunlight medium ultraviolet light only accounts for, and this wavelength also can't be utilized effectively less than the light of 387.5nm, causes the photocatalysis efficiency of glass low; 2) TiO that directly forms of glass surface
2The bonding force of film and glass is lower, TiO
2Film easily from glass surface scrape from, will influence work-ing life of glass with clean.
[summary of the invention]
The present invention is low for the photocatalysis efficiency that solves the glass that exists in the prior art, TiO
2The problem that layer is low with the glass bonding force has proposed a kind of glass with clean.
A kind of glass with clean comprises substrate of glass, nano-silver layer and titanium dioxide layer successively, and described nano-silver layer is distributed in the centre of substrate of glass and titanium dioxide layer; Contain nitrogen-doped titanium dioxide in the described titanium dioxide layer; Total amount with titanium dioxide layer is a benchmark, and wherein the mol ratio of nitrogen-atoms and titanium atom is 0.01-0.05.
The present invention is directed to the problem that prior art exists, a kind of preparation method of glass with clean also be provided, may further comprise the steps:
1) glass surface cleaning, drying;
2) form described nano-silver layer at glass surface by magnetron sputtering method through step 1);
3) sol-gel method prepares urea-containing TiO 2 sol, through step 2) glass in described urea-containing TiO 2 sol, lift plated film, form the titanium dioxide layer that contains nitrogen-doped titanium dioxide at glass surface through Overheating Treatment then;
By above-mentioned steps, obtain described glass with clean.
Glass with clean of the present invention, nano-silver layer is distributed on glass, and titanium dioxide layer is distributed on the nano-silver layer, compared with prior art, has the following advantages:
(1) nano-silver layer is distributed in below the titanium dioxide layer, can effectively improve the utilization ratio of sunlight, and titanium dioxide layer contains the adulterated titanium dioxide of nitrogen simultaneously, can effectively improve the photocatalysis efficiency of glass with clean;
(2) among the preparation method of glass with clean provided by the invention, adopt magnetron sputtering method to form nano-silver layer at glass surface, strong with the bonding force of glass, form described titanium dioxide layer in nano-silver layer by sol-gel method again, make that rete on glass is difficult for coming off from glass, bonding force is good.
[embodiment]
Glass with clean provided by the invention comprises substrate of glass, nano-silver layer and titanium dioxide layer successively, and described nano-silver layer is distributed in the centre of substrate of glass and titanium dioxide layer; Contain nitrogen-doped titanium dioxide in the described titanium dioxide layer; Total amount with titanium dioxide layer is a benchmark, and wherein the mol ratio of nitrogen-atoms and titanium atom is 0.01-0.05.
The present inventor finds that the nanometer Ag layer is distributed in the centre of substrate of glass and titanium dioxide layer, can reflect the UV-light of printing opacity titanium dioxide layer, makes UV-light obtain second stage employ; Simultaneously, nanometer silver can make upper strata optically catalytic TiO 2 wavelength produce red shift, be that the photochemical catalysis wavelength region is widened, even reach the visible light part, therefore can effectively improve the utilization ratio of sunlight, thereby improve the photocatalysis efficiency of titanium dioxide layer, improve the photocatalysis efficiency of glass with clean of the present invention.
The present inventor is unexpected to find that when titanium dioxide layer contained the adulterated titanium dioxide of nitrogen, the photocatalysis efficiency of described glass with clean was higher.The part Sauerstoffatom is replaced by nitrogen-atoms in the adulterated titanium dioxide of described nitrogen, and energy level generation hydridization make that being with of titanium dioxide can responding to visible light, so the photocatalytic of titanium dioxide improves.
According to glass with clean provided by the invention, the nano silver particles in the described nano-silver layer exists with the form of silver-colored simple substance, and median size is 0.3-3nm.
Thickness for nano-silver layer and titanium dioxide layer among the present invention is not particularly limited.For improving the photochemical catalysis rate efficient of titanium dioxide layer, under the preferable case, the thickness of described nano-silver layer is 0.2-5nm.The thickness of described titanium dioxide layer is 5-200nm.
The present inventor finds that also when the porosity of described titanium dioxide layer was big more, the specific surface area of titanium dioxide was big more, and the photocatalysis efficiency of corresponding glass with clean and Superhydrophilic are high more.Under the preferable case, the porosity of described titanium dioxide layer is 0.1-0.5.
The present invention also provides a kind of preparation method of glass with clean, may further comprise the steps:
1) glass surface cleaning, drying;
2) form described nano-silver layer at glass surface by magnetron sputtering method through step 1);
3) sol-gel method prepares urea-containing TiO 2 sol, through step 2) glass in described urea-containing TiO 2 sol, lift plated film, form the titanium dioxide layer that contains nitrogen-doped titanium dioxide at glass surface through Overheating Treatment then;
By above-mentioned steps, obtain glass with clean provided by the present invention.
According to preparation method provided by the invention, need earlier to glass surface clean, drying.The whole bag of tricks that described cleaning, exsiccant method are used always for those skilled in the art, the present invention does not have particular determination.For example, can for: earlier with deionized water cleaning glass surface, ultrasonic wave soaking and washing 5-30min in dehydrated alcohol again is with deionized water ultrasonic cleaning 3-5 time repeatedly, 110 ℃ of dryings in baking oven then.Described glass is various glass commonly used, for example white glass, toughened glass, mat glass, figured glass etc.
In the glass with clean that is provided among the present invention, nano-silver layer directly is covered in glass surface.For improving the bonding force of nano-silver layer and glass, among the present invention, described nano-silver layer forms at glass surface by magnetron sputtering method.Described magnetron sputtering method comprises under the argon gas atmosphere, make the target material sputter on the magnetic controlling target and be deposited on described on glass applying power supply on the magnetic controlling target, be plated on described nano-silver layer on glass with formation, described target is the nanometer silver target, can obtain the wave carrier piece that surface coverage has nano-silver layer.The preferred radio frequency reaction magnetron sputtering method that adopts plates nano-silver layer among the present invention on glass surface.The condition of described magnetron sputtering method comprises: the power of power supply is 2000-5000W, and vacuum tightness is 0.5-1Pa, and sputtering time is 1-60s, and bias voltage is 50-200V, and dutycycle is 50-90%.The thickness of the nano-silver layer that magnetron sputtering method is formed under the preferable case, for improving the photocatalysis efficiency of titanium dioxide, reduces cost without limits simultaneously, and the thickness of described nano-silver layer is 0.2-5nm.
Preparation in accordance with the present invention, prepare urea-containing TiO 2 sol by sol-gel method, then surface coverage there is the slide glass of nano-silver layer in this TiO 2 sol, to lift plated film, on slide glass, form the described titanium dioxide layer that contains nitrogen-doped titanium dioxide of one deck again through Overheating Treatment then, can obtain glass with clean of the present invention.Contain nitrogen-doped titanium dioxide in the formed titanium dioxide layer, make that described titanium dioxide layer Superhydrophilic and photocatalytic degradation are stronger, can effectively improve the self-cleaning performance of glass surface.
According to the method for preparing TiO 2 sol that those skilled in the art use always, for example sol-gel method prepares urea-containing TiO 2 sol of the present invention.The TiO 2 sol difference that described urea-containing TiO 2 sol and those skilled in the art use always is that mixing by urea makes that the photocatalytic of titanium dioxide of the present invention is stronger.The described method for preparing TiO 2 sol comprises butyl (tetra) titanate, urea and diethanolamine is dissolved in the ethanol, adds deionized water, mixes, and promptly obtains described urea-containing TiO 2 sol; Wherein, the mol ratio of butyl (tetra) titanate, diethanolamine, ethanol and deionized water is 1: 0.5-1: 20-50: 0.5-1.
Wherein, the alcoholic acid that is dissolved in of butyl (tetra) titanate, urea and diethanolamine is not particularly limited in proper order, under the preferable case, can proportionally earlier urea be dissolved in the ethanol, form urea-ethanolic soln; Then butyl (tetra) titanate and diethanolamine are mixed in proportion, add in above-mentioned urea-ethanolic soln; Drip the mixing solutions of small amount of deionized water and dehydrated alcohol again, stir under the room temperature and make butyl (tetra) titanate generation hydrolysis.
The contriver is surprised to find that, when the preparation TiO 2 sol, adds urea in ethanol, and the photocatalytic degradation of the glass with clean that obtains at last is significantly improved.The contriver thinks: add urea in ethanol, the TiO 2 sol that obtains is in heat treatment process, and the nitrogen-atoms in the urea can be doped in the titanium dioxide crystal lattice, and promptly nitrogen-atoms can replace the position of partial oxygen atom, obtains the adulterated titanium dioxide layer of nitrogen.The adulterated titanium dioxide energy level of described nitrogen hydridization, can be with can responding to visible light, so photocatalytic improves.
As general knowledge known in this field, separate out and control the acidity of colloidal sol for preventing the metatitanic acid colloidal, also need in system, to add appropriate hydrochloric acid, adjustment pH is 5-6, obtains faint yellow colloidal sol transparent, homogeneous at last, is described urea-containing TiO 2 sol.
The described step that lifts plated film comprises: the glass that (a) surface is coated with nano-silver layer places above-mentioned TiO 2 sol, dipping 5-60s, then TiO 2 sol is discharged with the speed of 0.2-5mm/s, promptly the time of lifting is 30-60s/ time, obtains lifting 1 time slide glass; (b) take out cooling after this slide glass being placed 80-300 ℃ of constant temperature roaster baking 10min; (d) the refrigerative slide glass is repeated above-mentioned (a) and (b) step, lift 1-9 time, obtain lifting the slide glass of plated film.
According to preparation method provided by the invention, the slide glass that lifts after plated film is finished is heat-treated, make the surface form titanium dioxide layer, can obtain glass with clean of the present invention.Described heat treated condition comprises: temperature is 400-650 ℃, and the time is 0.5-5 hour.Under the preferable case, described thermal treatment is divided into three phases: the fs rises to design temperature from room temperature, and described design temperature is 400-550 ℃, time is 0.5-2h, subordinate phase is a constant temperature calcining, and the time is 1-5h, and the phase III closes heating and reduces to room temperature from design temperature.The thickness of described titanium dioxide layer is 5-200nm.
Under the preferable case,, in the method for the urea-containing TiO 2 sol of preparation described in the present invention, also be included in the step that adds polyoxyethylene glycol in the ethanol for improving the photocatalysis efficiency of titanium dioxide.The contriver finds, when the preparation TiO 2 sol, adds polyoxyethylene glycol in ethanol, and the photocatalytic degradation performance of last glass with clean is improved.Contain polyoxyethylene glycol in the described TiO 2 sol, in the heat treatment process, ethylene glycol volatilizees, and can improve the porosity of titanium dioxide layer, increases TiO
2Specific surface area, thereby strengthen the Superhydrophilic and the photocatalytic activity of glass with clean.Described polyoxyethylene glycol can adopt in the prior art polyoxyethylene glycol commonly used, and adopting molecular weight under the preferable case is the polyoxyethylene glycol of 2000-6000, for example can adopt a kind of among PEG2000, PEG4000 or the PEG6000.For improving the effective rate of utilization of raw material, more preferably under the situation, the mol ratio of butyl (tetra) titanate and polyoxyethylene glycol is 1: (0.005-0.1).
Glass with clean of the present invention, the adulterated titanium dioxide of nitrogen improves the Superhydrophilic and the photocatalytic degradation of titanium dioxide layer, nano-silver layer, titanium dioxide layer and substrate of glass bonding force are strong simultaneously, in automobile, train, steamer, light fixture and various Penetrating door and window glass art, have widely and use.
The present invention is further illustrated below by embodiment.
Embodiment 1
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
(1) glass surface cleaning: (surface blot of 2cm * 5cm), ultrasonic wave soaking and washing 5min in dehydrated alcohol again is with deionized water ultrasonic cleaning 3 times repeatedly, 110 ℃ of dryings in baking oven then for washed with de-ionized water glass.
(2) magnetron sputtering nanometer Ag layer: utilize magnetron sputtering sputter nano metal Ag film on glass surface, control sputtered film thickness is 0.2nm, obtains the slide glass that there is nano-silver layer on the surface.The magnetron sputtering machine is radio frequency reaction magnetron sputtering machine (northern instrument is innovated vacuum technique limited liability company and produced, model JP-900A), and sputtering target material is pure Ag palladium, and sputtering atmosphere is a pure argon.Power is 2000W during the sputter reaction, and vacuum tightness is 0.8Pa, and sputtering time is 5s, and bias voltage is 100V, and dutycycle is 60%.
(3) TiO 2 sol preparation: 0.36g urea is added in the 40ml dehydrated alcohol, and magnetic agitation is to dissolving fully; Measure 10.42g metatitanic acid fourth fat and 3.14g diethanolamine, mix the back and add in the above-mentioned solution magnetic agitation 1h; 12.64ml dehydrated alcohol, 0.54g deionized water and 0.09g concentrated hydrochloric acid are mixed, add above-mentioned solution, stir 30min; Add 0.3g PEG2000, stir 3h, obtain TiO 2 sol to all dissolvings.
(4) lift plated film: the TiO 2 sol of step (3) is changed in the beaker, and place TiO 2 sol to flood 30s the slide glass of step (2); Colloidal sol is at the uniform velocity discharged beaker with the speed of 1mm/s then, finishes 1 time when colloidal sol has been arranged and lifts; Take out cooling after the slide glass that lifts 1 time placed 200 ℃ of constant temperature roasters baking 10min; Repeat to lift, baking procedure, slide glass is repeated to lift 4 times.
(5) thermal treatment: set the retort furnace heating schedule: the fs rises to 500 ℃ of design temperatures from room temperature, and the time is 1h, and subordinate phase is a constant temperature calcining, and the time is 2h, and the phase III closes heating and reduces to room temperature from design temperature; The slide glass of step (4) packed into put into retort furnace in the enamel pallet, the operation heating schedule; Treat after retort furnace is cooled to room temperature sample to be taken out.
By above-mentioned steps, can obtain the glass with clean of present embodiment, be designated as A1.
Embodiment 2
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (2), controlling sputtered film thickness is 2nm; Sputtering condition comprises: power is 2000W, and vacuum tightness is 0.5Pa, and sputtering time is 20s, and bias voltage is 150V, and dutycycle is 80%.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as A2.
Embodiment 3
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (3), do not add PEG2000.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as A3.
Embodiment 4
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (3), the add-on of diethanolamine is 1.6g.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as A4.
Embodiment 5
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (4), slide glass floods 20s, and colloidal sol is at the uniform velocity discharged with the speed of 0.5mm/s; Slide glass is repeated to lift 2 times.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as A5.
Embodiment 6
Present embodiment is used to illustrate glass with clean of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (5), design temperature is 400 ℃, and time fs is 0.5h, and the subordinate phase time is 4h.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as A6.
Comparative Examples 1
This Comparative Examples is used to illustrate the self-cleaning glass of prior art.
The step of employing and embodiment 1 step (1) cleans glass surface, then glass is placed under the radio frequency reaction magnetron sputtering machine (northern instrument is innovated vacuum technique limited liability company and produced, model JP-900A) TiO
2TiO is adopted in the preparation of film
2Ceramic target (purity 99.5%), power 160W; Metal A g target is adopted in the preparation of nanometer silverskin, and power is 3000W; Sputtering atmosphere is an argon gas, and flow velocity is 30sccm; Adopt TiO
2The mode of target and Ag target co-sputtering is at the glass surface plated film.The time of cosputtering is 5s.
By aforesaid method, obtain the self-cleaning glass of this Comparative Examples, be designated as D1.
Comparative Examples 2
This Comparative Examples is used to illustrate the self-cleaning glass of prior art.
This Comparative Examples is handled glass according to the concrete operations of each step among the embodiment 1, and difference is: wherein the order of step is undertaken by following: carry out step (1) glass surface cleaning earlier; Carry out step (3), (4), (5) more successively, carry out step (2) magnetron sputtering nanometer Ag layer at last.
By aforesaid method, obtain the self-cleaning glass of this Comparative Examples, be designated as D2.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare the glass with clean of present embodiment, difference is: in the step (3), do not add urea.
By aforesaid method, obtain the glass with clean of present embodiment, be designated as D3.
Performance test:
1, titanium dioxide layer thickness measuring: adopt Talysurf5P-120 type surface topographic apparatus fo to test the thickness of glass surface film.The thickness of the titanium dioxide layer of glass sample A1-A7, test result is as shown in table 1.
2, titanium dioxide layer porosity test: (Beijing gold dust spectrum Science and Technology Ltd. produces to adopt specific surface area and porosity meter; Model F-Sorb 3400) porosity of having tested the glass surface film.Glass sample A1-A7 and D1-D2 go up the porosity of titanium dioxide layer, and test result is as shown in table 1.
3, Superhydrophilic test: (model that German Dataphysics company produces is OCA20 with contact angle measurement; The key technical indexes is: the contact angle useful range: 0～180 °, and measuring accuracy: ± 0.1 °) measure the contact angle of water on each glass sample A1-A7 and D1-D2 surface, adopt the mode of promptly dripping i.e. survey to test, test result is as shown in table 1.
4, photocatalytic test: measure the methylene blue solution that 30ml concentration is 20mg/L, put into the quartz surfaces ware; Each glass sample A1-A7 and D1-D2 are immersed in the methylene blue solution, with desk-top ultraviolet germicidal (high temperature composite factory production behind the sky of Haidian, Beijing, the model SJD-1 of 20W; Predominant wavelength is that λ=254nm) (Zibo three brilliant Electrical Appliances Co., Ltd produce model SJG160 with the visible light source lamp; Predominant wavelength is after λ=650nm) shines 4h simultaneously, to take out an amount of solution with dropper, with UV752 ultraviolet-visible pectrophotometer (Shanghai is helped instrument company limited of section and produced), measures the solution absorbency at λ=668nm place.By methylene blue concentration the typical curve of absorbancy is calculated respective concentration, calculates the photocatalytic degradation rate η of methylene blue then as follows:
η＝(C
0-C
i)/C
0×100％＝(A
0-A
i)/A
0×100％；
C wherein
0Be the concentration of dye solution before reacting, C
iFor reacting back dyestuff solution absorbency; A
0Be the concentration of dye solution before reacting, A
iFor reacting back dyestuff solution absorbency.Test result is as shown in table 1.
5, bonding force test
On glass sample A1-A7 and D1-D2, mark the lattice (number 100 of the 1mm of being spaced apart of uniform size with sharp blade; Scratch depth is controlled at film lower substrate glass exposure), the lattice that comes off of statistics film is counted N1, and the scotch tape that width is 24mm is sticked in the lattice zone of drawing on film, and guarantees to combine between adhesive tape and the film that grid is arranged tight.Behind the 5min, adhesive tape is uncovered, and added up the lattice that film comes off once more and count N2 with the power of a vertical face.Binding force of membrane mark Z=(100-N1-N2)/100 * 100%.Test result is as shown in table 1.
Table 1
By last table 1 as can be seen, the Superhydrophilic of glass with clean of the present invention and photocatalytic all are better than the various glass with clean of prior art, and the bonding force of rete on the glass with clean of the present invention and glass is strong, reaches 100%.
More as can be seen, adopt preferred implementation of the present invention from the test result of A3 and other embodiment, promptly in preparation glass with clean process, when adding polyoxyethylene glycol, the TiO on glass with clean surface
2When layer porosity was 0.1-0.5, the photocatalytic degradation rate of glass with clean was high more, and water is more little at the contact angle of glass surface, illustrated that the photocatalysis efficiency of glass with clean and Superhydrophilic are high more.
Claims (13)
1. a glass with clean comprises substrate of glass, nano-silver layer and titanium dioxide layer successively, and described nano-silver layer is distributed in the centre of substrate of glass and titanium dioxide layer; Contain nitrogen-doped titanium dioxide in the described titanium dioxide layer; Total amount with titanium dioxide layer is a benchmark, and wherein the mol ratio of nitrogen-atoms and titanium atom is 0.01-0.05.
2. glass with clean according to claim 1 is characterized in that, the median size of nanometer silver is 0.3-3nm in the described nano-silver layer.
3. glass with clean according to claim 1 is characterized in that, the thickness of described nano-silver layer is 0.2-5nm.
4. glass with clean according to claim 1 is characterized in that, the thickness of described titanium dioxide layer is 5-200nm.
5. glass with clean according to claim 1 is characterized in that, the porosity of described titanium dioxide layer is 0.1-0.5.
6. the preparation method of the described glass with clean of claim 1 may further comprise the steps:
1) glass surface cleaning, drying;
2) form described nano-silver layer at glass surface by magnetron sputtering method through step 1);
3) sol-gel method prepares urea-containing TiO 2 sol, through step 2) glass in described urea-containing TiO 2 sol, lift plated film, form the titanium dioxide layer that contains nitrogen-doped titanium dioxide at glass surface through Overheating Treatment then;
By above-mentioned steps, obtain described glass with clean.
7. method according to claim 6, it is characterized in that, step 2) magnetron sputtering method comprises under the argon gas atmosphere in, make the target material sputter on the magnetic controlling target and be deposited on described on glass applying power supply on the magnetic controlling target, be plated on described nano-silver layer on glass with formation, described target is the nanometer silver target.
8. method according to claim 6 is characterized in that step 2) in the condition of magnetron sputtering method comprise: the power of power supply is 2000-5000W, and vacuum tightness is 0.5-1Pa, and sputtering time is 1-60s, and bias voltage is 50-200V, and dutycycle is 50-90%.
9. method according to claim 6 is characterized in that, the thickness of nano-silver layer is 0.2-5nm.
10. method according to claim 6, it is characterized in that the method for the urea-containing TiO 2 sol of described preparation comprises butyl (tetra) titanate, urea and diethanolamine are dissolved in the ethanol, adds deionized water, mix, promptly obtain described urea-containing TiO 2 sol; Wherein, the mol ratio of butyl (tetra) titanate, urea, diethanolamine and deionized water is 1: (0.1-0.5): (0.5-1): (0.5-1).
11. method according to claim 10 is characterized in that, the method for the urea-containing TiO 2 sol of described preparation also comprises polyoxyethylene glycol is dissolved in step in the ethanol.
12. method according to claim 11 is characterized in that, the mol ratio of butyl (tetra) titanate and polyoxyethylene glycol is 1: (0.005-0.1).
13. method according to claim 6 is characterized in that, the pH of described urea-containing TiO 2 sol is 5-6.
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