CN101638297A - Method for preparing full nanometer granule visible light area antireflection film by layer upon layer self-assembly method - Google Patents
Method for preparing full nanometer granule visible light area antireflection film by layer upon layer self-assembly method Download PDFInfo
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Abstract
The invention relates to a method for preparing a full nanometer granule visible light area antireflection film by a layer upon layer self-assembly method, which comprises steps of: (1) scouring, alkali washing and drying a glass or quartzes substrate; (2) (a) soaking in colloid of magnalium layered double hydroxide for 3-20 minutes; (3) soaking in silicon dioxide sol or titanium dioxide sol for 3-20 minutes; (c) repeating the steps of (a) and (b) in sequence; (d) sintering for 0.5-4 hours in the temperature of 400-500 DEG C, thus obtaining the antireflection film. The method uses simple devices, has low cost and is suitable for industrialization production. The antireflection film has obvious effect in the visible light area; a multi-layer antireflection film formed on the surface of theglass can reach 97.4% of transmission rate at wave length of 550nm; and a multi-layer film containing titanium dioxide can reach no less than 93.7% of transmission rate at wave length of 550nm.
Description
Technical field
The invention belongs to the preparation field of antireflective coating, particularly relate to a kind of usefulness layer by layer self-assembly method prepare the method for full nanometer granule visible light area antireflection film.
Background technology
The smooth material of smooth surface often has in various degree reflection, result can cause light pollution, forms the image of not wishing to see, need use more large-area glass window etc. for guaranteeing indoor lightness on daytime the light that is radiated at material surface.Also reduced the optical efficiency of catching of battery material for reflection effects such as silica-based solar cell, dye sensitization solar batterys, their photoelectric transformation efficiency is reduced.On a lot of optical component surfaces,, directly influenced the sensitivity and the resolving power of instrument because the transmitance that reflection causes reduces.Shield glass also has the specular reflection above 10%, can influence officer's the visual field, influences the safety traffic of automobile.So, reduce the reflection of material, in some application-specific, can play multiple effects such as synergy and energy-conservation, raising security.
In order to reduce the specular reflection of smooth planarizing material, can be by solving at the special construction of material surface formation certain roughness or the coating of specific refractive index and thickness.Then there is basic principle to follow to a kind of method in back, as: specific refractory power and thickness need to satisfy n respectively
f 2=n
s* n
a, d=λ/4 (n
f, n
s, n
aBe respectively the specific refractory power of film, base material and air, d and λ are respectively the thickness and the incident light wavelength of antireflective coating).The specific refractory power of materials such as white glass is about 1.5, is 1.22 so require the specific refractory power of mould material.But the specific refractory power of many inorganic materials all is higher than 1.5, and usually fine and close inorganic materials is not adapted at forming antireflective coating on the base material such as glass.Can retrieve the patent of the fluorine-containing polymkeric substance of many usefulness now at formation antireflective coating on glass.Although fluoropolymer itself also is very stable, relatively the work-ing life of glass, the stability of fluoropolymer still has deficiency, and developing long lasting glass antireflective coating material has important and wide prospect.Layer-by-Layer (LbL) self-assembly (translations self-assembly layer by layer usually) is a kind of accurately method of controlled function film of thickness for preparing, and its development has the history of more than ten years.The material of washes clean is immersed in the dielectric medium; then in being immersed in the colloid that has with the polyelectrolyte ion opposite charges; by electrostatic interaction, the micelle in the colloid can be deposited on electrolyte molecule or ionic outside, and assembling so in layer can obtain the function film of different thickness.After calcining, can burn polymkeric substance, only remaining inorganic glue granulosa.Cebeci etc. have reported the antireflective coating that obtains having anti-fog function with cation type polymer ionogen and electronegative silicon dioxide colloid by the LbL assembling.Although what they pointed out that the material of film uses is silicon-dioxide, because silicon-dioxide is vesicular structure, its specific refractory power drops near 1.25, thereby has tangible anti-reflective effect [F.
Cebeci, Z.Z.Wu, L.Zhai, R.E.Cohen, and M.F.Rubner, Nanoporosity-Driven Superhydrophilicity:AMeans to Create Multifunctional Antifogging Coatings, Langmuir 2006,22,2856-2862].Lee etc. have proposed to utilize the titanium dioxide micelle of positively charged and the full nano-particular film that electronegative silica particle LbL self-assembly has obtained having the antireflective function.This LbL prepares in the engineering of film and does not use polymer dielectric, that use is the silicon-dioxide that has the xenogenesis electric charge and two kinds of mineral colloids of the titanium dioxide [D.Y.Lee that waits the pH value, M.F.Rubner andR.E.Cohen, All-Nanoparticle Thin-Film Coatings, Nano Letters, 2006,6 (10), 2305-2312].
Adopt methods such as spraying, evaporation, sputter that material is deposited on the substrate, also can obtain to have the single thin film of antireflective function.Chinese patent 1085919A is disclosed to deposit inorganic metal (tantalum, titanium, niobium, tungsten etc.) the oxynitride antireflection coatings that one or more layers specific refractory power is higher than the substrate material specific refractory power, anti-reflective effect on the contour refractive index materials of silicon with dc magnetron sputtering method on substrate.The preparation method of the antireflective coating that the visible light transmissivity that Chinese patent CN 101157522A discloses is higher is unitary film, and the wavelength region that plays the antireflective effect is narrower.
Summary of the invention
Technical problem to be solved by this invention provide a kind of usefulness layer by layer self-assembly method prepare the method for full nanometer granule visible light area antireflection film, this preparation equipment is simple, cost is low, is suitable for suitability for industrialized production; The gained antireflective coating has tangible anti-reflective effect at visible region.
A kind of usefulness of the present invention self-assembly method layer by layer prepares the method for full nanometer granule visible light area antireflection film, comprising:
(1) cleaning of substrate
Substrate such as glass or quartz carries out pickling, alkali cleaning, drying.
(2) the LbL self-assembly of multilayer, heterogeneous membrane
Unless stated otherwise, substrate two sides used among the present invention all deposits multilayer, heterogeneous membrane equally, specially one side is not sealed or handle especially to prepare the single face film.Adopt LbL self-assembly method deposit multilayer, heterogeneous membrane on the glass white of cleaning or quartz glass plate, concrete steps are:
A), be immersed in the colloid of magnalium laminar double-hydroxide time 3-20 minute with above-mentioned glass or quartz substrate, soak back with deionized water rinsing or rinsing, remove the unnecessary nano particle that accumulates in the surface, dry in nitrogen or cleaned air, obtain having the surface of positive electricity.
Liquid medium is a deionized water in the magnalium double-hydroxide colloid, and the mass percent that contains the magnalium double-hydroxide is: 0.01wt%～1wt%, the pH scope is 7-10.
B) substrate with positively charged in the step (a) is immersed in silicon dioxide gel or the TiO 2 sol, soak time was controlled at 3-20 minute, soak back with deionized water rinsing or rinsing, remove the unnecessary nano particle that accumulates in the surface, dry in nitrogen or cleaned air, obtain having the surface of negative electricity.
Liquid medium in silicon dioxide colloid or the colloidal tio 2 is a deionized water, and the massfraction that contains silicon-dioxide or titanium dioxide is: 0.01wt%～1wt%, and the pH scope is 7-10; Silica particle solutions of weak acidity under the alkaline condition its surperficial electrokinetic potential for negative; The anatase phase titanium dioxide colloid is negative in neutrality to the alkaline condition lower surface.
C) above-mentioned repeatedly successively (a) or (b) step obtain the surface of positively charged or negative electricity respectively, and obtain the film of the different numbers of plies.
D) the negative electricity layer is selected silicon-dioxide or colloidal tio 2 for use, or prepares the layered double-hydroxide/titanium dioxide of the certain number of plies of refabrication behind the layered double-hydroxide/silicon-dioxide of certain number of plies.
The composition of film is described as like this: (layered double-hydroxide/silicon-dioxide) n; (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2Or (layered double-hydroxide/titanium dioxide) n, 1≤n≤20,2≤n
1+ n
2≤ 20,1≤n
1≤ 15,1≤n
1≤ 5.
E) with above-mentioned through 400-500 ℃ sintering 0.5-4 hour, layered double-hydroxide partly resolves into corresponding oxide compound behind the sintering, the composition of silicon-dioxide and titanium dioxide does not change.
F) thickness of film: multilayer film (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2, or (layered double-hydroxide/titanium dioxide) n thickness be: 10～500nm, can be easily by regulating n, n
1, n
2Realize.
Described step (1) pickling is to be immersed in the mixing solutions of 70-100 ℃ sulfuric acid and hydrogen peroxide, according to volume ratio be 7: 3 with 98%H
2SO
4With 30%H
2O
2Mix, soak time is 15 to 25 minutes, soaks the back and cleans up with deionized water.
Described step (1) alkali cleaning is to adopt 1: 4: 20 25-28% strong aqua of volume ratio: 30% hydrogen peroxide: the deionized water mixing solutions, washing by soaking is 15 to 25 minutes under room temperature, soaks the back and cleans up with deionized water.
The preparation of described magnalium laminar double-hydroxide colloidal: with the magnalium mol ratio is nitrate, vitriol or the muriate of 2: 1 magnesium and aluminium is mixed with concentration 0.3M-1.5M with deionized water solution, be heated to 70 ℃, with concentration is that the alkali such as sodium hydroxide, potassium hydroxide or ammoniacal liquor of 0.5M-1.5M neutralize, base excess, pH after the titration is greater than 9, resulting precipitation is removed water miscible excess amount of ions through the deionized water repetitive scrubbing, after the drying, obtain the layered double-hydroxide powder;
When preparation magnalium carbonate double-hydroxide, being used for the neutral basic solution is the mixing solutions of sodium hydroxid and yellow soda ash, sodium hydroxid and salt of wormwood or potassium hydroxide and yellow soda ash, because magnalium carbonate oxyhydroxide is more stable, carbonate and nitrate ion, chlorion or sulfate ion take advantage when competing, what obtain is the double-hydroxide precipitation of magnalium carbonate, after washing of precipitation process and the drying, obtain corresponding layered double-hydroxide powder.
Above-mentioned layered double-hydroxide powder is mixed with the suspension that weight percent is 1%-10% with deionized water, and 110-150 ℃ of hydrothermal treatment consists of process is 2～24 hours in water heating kettle, obtains the colloid that particle size is about the layered double-hydroxide of 100 nanometers.The powder through hydrothermal treatment consists can directly not be dispersed in the deionized water, and the ultrasonic cent of process is diffusing or clarifixator is broken, obtains stability colloid preferably.Because layered double-hydroxide micelle surface in very wide pH scope all has stronger positive electricity (electrokinetic potential), the Coulomb repulsion effect is strong, and colloid has stability preferably.
In the preparation of colloidal tio 2, adopt the presoma of water miscible titanium to come hydrolysis, used presoma is dihydroxyl lactic acid titanium ammonium or stable butyl (tetra) titanate or the isopropyl titanate of methyl ethyl diketone of 50wt%.After with deionized water above-mentioned substance being mixed with the aqueous solution that titaniferous concentration is 0.1M-1.0M, add urea as precipitation agent, the mol ratio of urea and titanium is 2: 1-20: 1, urea can not be urged the hydrolysis of materials such as dihydroxyl lactic acid titanium ammonium under the normal temperature, by mixing solutions is heated to 90 degrees centigrade or more than, and refluxed 2 hours or more than, obtain the colloidal sol or the precipitation of anatase phase titanium dioxide.Colloidal sol still precipitates by reflux temperature, reactant concn and return time and decides.If what obtain is precipitation, with the careful washed twice of deionized water, add again in the deionized water through ultra-sonic dispersion and can obtain transparent anatase titanic oxide sol, be weakly alkaline colloidal sol, add a spot of acid or alkali and further regulate its potential of hydrogen.If what obtain is colloid, then remove excessive foreign ion with the method for dialysis.In the dialysis process with colloid to going in the dialysis bag that permeable membrane makes to be immersed in the deionized water, the volume ratio of colloid and deionized water is 1: 5.Soak the deionized water that renews aquatic foods after 24 hours again, three times repeatedly, the colloid of titanium dioxide is able to purifying.
Silicon dioxide gel has commercially available multiple product, and silicon-dioxide primary particle does not wherein wait to 50nm at 7nm, has the product of different company, the different trades mark available.
Common white glass generally is respectively 89% and 11% at transmitance and the reflectivity of wavelength 550nm, and by preparation double-sided multi-layer film, its transmitance and reflectivity at 550nm is respectively greater than 95% with less than 5%.
Glass or quartzy iso-electric point are about pH=2.0, and in pH＞2.0 o'clock, glass or quartz surfaces are electronegative, attract the laminated double hydroxide nanometer particle of positively charged by electrostatic interaction.
The present invention utilizes pH in 2 to 11 scope; it is positive electricity layer that the micelle surface is positively charged layered double-hydroxide; is negative electricity layer to the electronegative silica particle of alkaline range internal surface or in neutrality to the electronegative anatase phase titanium dioxide micelle of weakly alkaline scope internal surface with slightly acidic, has prepared (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n by the LbL self-assembly method
1/ (layered double-hydroxide/titanium dioxide) n
2, (layered double-hydroxide/titanium dioxide) n heterogeneous multi-layer antireflective coating.Compare with the individual layer antireflective coating, the present invention can significantly widen the wavelength region of its effect of antireflective, improves anti-reflective effect interior between whole visible region.The grain-size of used layered double-hydroxide is big (20-100nm), just can obtain the rete that thickness is 200nm by LbL self-assembly several times, and, need not to use electrolyte molecule or ion in the preparation process.
Beneficial effect
(1) making equipment of the present invention is simple, cost is low, good practical values is arranged, and layered double-hydroxide, silicon-dioxide, titanium dioxide are inorganic materials, and stable in properties, good heat resistance are suitable for long-acting anti-reflection film, the controllable thickness of film;
(2) the present invention does not use polymer dielectric in the process of preparation film, by having the mineral ion self-assembly of xenogenesis electric charge, even without calcining, does not have possibility to influence the ionogen of performance in the film yet;
(3) size of the nano particle of layered double-hydroxide is bigger, thereby just can obtain thicker film by simple the repetition several times, obtains the better antireflection film of anti-reflective effect; Multilayer film (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2, (layered double-hydroxide/titanium dioxide) n is porous-film, has tangible anti-reflective effect at visible region;
(4) the common silica membrane number of plies is very little the time, and relatively poor in the anti-reflective effect of red light district, the number of plies is poor in anti-reflective effect purple, blue light region for a long time.Multilayer film (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2, (layered double-hydroxide/titanium dioxide) n is porous-film, can take into account the anti-reflective effect between visible region.
Description of drawings
Fig. 1: (a) glass/(magnalium carbonate double-hydroxide/silicon-dioxide) n (n=4) and (b) transmittance curve of glass/(magnalium carbonate double-hydroxide/titanium dioxide) n (n=4); Fig. 1 a can reach 94.9% in wavelength 800nm place transmitance, the raising of Fig. 1 b transmitance is obvious not as a, the titanium dioxide refractive index ratio that may be interpreted as in the multilayer film is bigger, and the specific refractory power of the porous-film of formation has departed from the ideal value 1.22 of white glass or silica glass antireflective coating;
Fig. 2: the electron scanning micrograph (a) and the atomic force microscope photo (b) of glass/(magnalium carbonate double-hydroxide/silicon-dioxide) 4, scanning electron microscope has shown its vesicular structure, and atomic force microscope has also further confirmed its vesicular structure, film forming particulate fine structure;
Fig. 3: glass/(magnalium carbonate double-hydroxide/silicon-dioxide) n
1+ (magnalium carbonate double-hydroxide/titanium dioxide) n
2Transmittance curve (n
1=4, n
2=2), dried film and be that the transmitance at 800nm place is respectively 95.6%, 94.7% at wavelength through the incinerating film is that 550nm place transmitance then is respectively 96.4% and 96.7% at wavelength;
Fig. 4: the atomic force microscope photo of glass/(magnalium carbonate double-hydroxide/titanium dioxide) n (n=4);
Fig. 5: the transmittance curve of glass/(magnalium carbonate double-hydroxide/titanium dioxide) n; Dried film and be that the transmitance at 800nm place is respectively 93.1%, 91.8% at wavelength through the incinerating film is that 550nm place transmitance then is respectively 95.3% and 93.9% at wavelength.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
After glass substrate carried out pickling, alkali cleaning, drying, the white glass substrate was about 89% in the transmitance of visible region.Preparation contains the colloid of magnalium double-hydroxide, and colloid is made up of magnalium double-hydroxide powder and water, wherein the mass percent of magnalium double-hydroxide: 0.082wt%.Preparation contains silicon dioxide colloid, and commercially available silicon dioxide gel is obtained with the deionized water dilution, and wherein the mass percent of silicon-dioxide is: 0.028wt%.Under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains the magnalium double-hydroxide 10 minutes, uses rinsed with deionized water after 5 minutes then, be immersed in the silicon dioxide colloid 15 minutes again, this is one deck.Repeatedly 4 times successively, make it reach 4 layers.Its transmitance is measured in dry back.
Rete becomes water white transparency, and its transmitance can reach more than 95%, and transmitance can reach 97.4% at wavelength 550nm place, shown in its transmitance Fig. 1 a.Cut a fritter sample and carry out the surface topography analysis with scanning electronic microscope, film is a vesicular structure, shown in Fig. 2 a.Fig. 2 b has provided the atomic force microscope photo of film, and the surface is similarly vesicular structure.
Embodiment 2
After glass substrate carried out the pickling drying, the visible light transmissivity of glass substrate was 89%.Under the room temperature normal pressure, at first will long 76.2mm, the sheet glass of wide 25.4mm, thick 1mm is immersed in the colloid that contains the magnalium double-hydroxide 20 minutes, use rinsed with deionized water after 5 minutes then, dry, be immersed in the colloid of titanium dioxide 10 minutes again, used rinsed with deionized water then 5 minutes, this is one deck for a drying.Repeatedly 8 times successively, make it reach 8 layers.Colloidal tio 2 is self-control, and titanium dioxide wherein is the anatase octahedrite phase, and grain-size is about 7nm, and wherein the mass percent of titanium dioxide is 0.053wt%.Magnalium carbonate double-hydroxide colloid is formulated by magnalium carbonate double-hydroxide powder and water ultra-sonic dispersion, wherein the mass percent 0.065wt% of magnalium carbonate double-hydroxide.
Rete shows oyster white slightly, and its transmitance surpasses 92%, wavelength 380nm to the transmitance of 800nm shown in Fig. 1 b.
Embodiment 3
After glass substrate carried out pickling, alkali cleaning, drying, the white glass substrate was about 89% in the transmitance of visible region.Preparation contains the colloid of magnalium double-hydroxide, and colloid is made up of magnalium double-hydroxide powder and water, wherein the mass percent of magnalium double-hydroxide: 0.082wt%.Preparation contains silicon dioxide colloid, and commercially available silicon dioxide gel is obtained with the deionized water dilution, and wherein the mass percent of silicon-dioxide is: 0.028wt%.Under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains the magnalium double-hydroxide 10 minutes, uses rinsed with deionized water after 5 minutes then, be immersed in the silicon dioxide colloid 15 minutes again, this is one deck.Repeatedly 4 times successively, make it reach 4 layers, count glass/(magnalium carbonate double-hydroxide/silicon-dioxide) 4.
Glass/(magnalium carbonate double-hydroxide/silicon-dioxide) 4 is immersed in the colloid that contains the magnalium double-hydroxide 15 minutes, use rinsed with deionized water after 5 minutes then, dry, be immersed in the colloid of titanium dioxide 10 minutes again, used rinsed with deionized water then 5 minutes, drying, this is one deck.Repeatedly 2 times successively, make it reach 2 layers.Colloidal tio 2 is self-control, and titanium dioxide wherein is the anatase octahedrite phase, and grain-size is about 7nm, and wherein the mass percent of titanium dioxide is 0.050wt%.Magnalium carbonate double-hydroxide colloid is formulated by magnalium carbonate double-hydroxide powder and water ultra-sonic dispersion, wherein the mass percent 0.065wt% of magnalium carbonate double-hydroxide.The film of making can be counted: glass/(magnalium carbonate double-hydroxide/silicon-dioxide) 4+ (magnalium carbonate double-hydroxide/titanium dioxide) 2, its transmitance is measured in dry back.
In the preparation of the colloidal tio 2 of herein using, adopting the dihydroxyl lactic acid titanium ammonium of water miscible 50wt% is precursor.After with deionized water above-mentioned substance being mixed with the aqueous solution that titaniferous concentration is 0.5M, add urea as precipitation agent.The mol ratio of urea and titanium is 5: 1, and mixing solutions is heated to 90 degrees centigrade, and refluxes 5 hours, obtains the precipitation of anatase phase titanium dioxide.Remove unnecessary ion with the method for dialysis, pass through ultrasonicly again, obtain the colloidal sol of titanium dioxide, wherein titanium dioxide is the anatase octahedrite phase, and grain-size is about 5nm.
Rete becomes water white transparency, and its transmitance can reach more than 95%, and transmitance can reach 96.4% at wavelength 550nm place, and its transmitance is shown in Fig. 3 a.
With glass/(magnalium carbonate double-hydroxide/silicon-dioxide) 4+ (magnalium carbonate double-hydroxide/titanium dioxide) 2, after the drying,, measure the transmitance and the surface topography of film through 400 ℃ of calcinings 2 hours.Its transmitance is shown in Fig. 3 b, and atomic force microscope such as Fig. 4 of its surface topography are represented.
Embodiment 4
After glass substrate carried out pickling, alkali cleaning, drying, the white glass substrate was about 89% in the transmitance of visible region.Preparation contains the colloid of magnalium double-hydroxide, and colloid is made up of magnalium double-hydroxide powder and water, wherein the mass percent of magnalium double-hydroxide: 0.08wt%.Preparation contains silicon dioxide colloid, and commercially available silicon dioxide gel is obtained with the deionized water dilution, and wherein the mass percent of silicon-dioxide is: 0.03wt%.Under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains the magnalium double-hydroxide 10 minutes, uses rinsed with deionized water after 5 minutes then, be immersed in the silicon dioxide colloid 15 minutes again, this is one deck.Repeatedly 4 times successively, make it reach 4 layers.The colloid of magnalium double-hydroxide adopted magnalium laminar double-hydroxide is diluted to 5wt% with deionized water, through 120 degrees centigrade of hydro-thermals 12 hours.After being cooled to room temperature, be diluted to 0.08wt%, regulate the pH value to pH=8 with deionized water.
Dry back is its transmitance directly, perhaps through 500 degrees centigrade of calcinings 4 hours, measures its transmitance, transmitance result as shown in Figure 5, wherein Fig. 5 a be dry back without the incinerating film, Fig. 5 b is through 500 degrees centigrade of incinerating films.
Claims (5)
1. one kind prepares the method for full nanometer granule visible light area antireflection film with self-assembly method layer by layer, comprising:
(1) glass or quartz substrate carry out pickling, alkali cleaning, drying;
(2) the LbL self-assembly of multilayer, heterogeneous membrane
A) with above-mentioned glass or quartz substrate, be immersed in the colloid of magnalium laminar double-hydroxide, time 3-20 minute, the immersion back is with deionized water rinsing or rinsing, and was dry in nitrogen or cleaned air, obtained having the surface of positive electricity;
B) substrate with positively charged in the step (a) is immersed in silicon dioxide gel or the TiO 2 sol, and soak time was controlled at 3-20 minute, soaks the back with deionized water rinsing or rinsing, and is dry in nitrogen or cleaned air, obtains having the surface of negative electricity;
C) above-mentioned repeatedly successively (a) or (b) step obtain the surface of positively charged or negative electricity respectively, and obtain the film of the different numbers of plies, are expressed as (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2, or (layered double-hydroxide/titanium dioxide) n, wherein 1≤n≤20,2≤n
1+ n
2≤ 20,1≤n
1≤ 15,1≤n
1≤ 5;
D) with above-mentioned through 400-500 ℃ sintering 0.5-4 hour, promptly.
2. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for full nanometer granule visible light area antireflection film, it is characterized in that: described step (1) pickling is to be immersed in the mixing solutions of 70-100 ℃ sulfuric acid and hydrogen peroxide, according to volume ratio be 7: 3 with 98%H
2SO
4With 30%H
2O
2Mix, soak time is 15 to 25 minutes, soaks the back and cleans up with deionized water; Alkali cleaning is to adopt 1: 4: 20 25-28% strong aqua of volume ratio: 30% hydrogen peroxide: the deionized water mixing solutions, washing by soaking is 15 to 25 minutes under room temperature, soaks the back and cleans up with deionized water.
3. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for full nanometer granule visible light area antireflection film, it is characterized in that: described step (2) (a) magnalium double-hydroxide is the subsalt of carbonate, muriate, nitrate or the vitriol of magnalium, liquid medium in the magnalium double-hydroxide colloid is a deionized water, the mass percent that contains the magnalium double-hydroxide is: 0.01wt%～1wt%, the pH scope is 7-10.
4. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for full nanometer granule visible light area antireflection film, it is characterized in that: described step (2) (b) liquid medium in silicon dioxide colloid or the colloidal tio 2 is a deionized water, the massfraction that contains silicon-dioxide or titanium dioxide is: 0.01wt%～1.5wt%, the pH scope is 7-10.
5. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for full nanometer granule visible light area antireflection film, it is characterized in that: described step (2) (c) in (layered double-hydroxide/silicon-dioxide) n, (layered double-hydroxide/silicon-dioxide) n
1+ (layered double-hydroxide/titanium dioxide) n
2, or (layered double-hydroxide/titanium dioxide) n thickness be: 10～500nm, by regulating n, n
1, n
2Realize.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101879442A (en) * | 2010-06-04 | 2010-11-10 | 西南科技大学 | Method for preparing titanium-silicon-aluminum sol with photocatalytic property from blast furnace titanium slag |
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| CN103803812A (en) * | 2014-02-11 | 2014-05-21 | 东南大学 | Antireflection optical film material and preparation method thereof |
| CN105439459A (en) * | 2014-08-29 | 2016-03-30 | 北京有色金属研究总院 | Antireflection film with compact and porous surface, and making method thereof |
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| CN105862396B (en) * | 2016-05-05 | 2018-03-23 | 苏州大学 | A kind of surface modification of aramid fiber and preparation method thereof |
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| CN108440022B (en) * | 2018-05-14 | 2020-08-18 | 陕西科技大学 | Preparation method of inorganic structural color coating for ceramic glaze |
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