CN103589339A - Polysilazane coating solution and method for preparing composite coating containing metallic oxide-SiO2 - Google Patents

Polysilazane coating solution and method for preparing composite coating containing metallic oxide-SiO2 Download PDF

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CN103589339A
CN103589339A CN201310571850.2A CN201310571850A CN103589339A CN 103589339 A CN103589339 A CN 103589339A CN 201310571850 A CN201310571850 A CN 201310571850A CN 103589339 A CN103589339 A CN 103589339A
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polysilazane
solution
coating
inorganic polysilazane
coating solution
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徐彩虹
肖凤艳
罗永明
张宗波
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The invention discloses a polysilazane coating solution containing metallic elements and a method for preparing a high-transparency composite coating containing metallic oxide-SiO2. The polysilazane coating solution containing the metallic elements comprises polysilazane, a metallic compound, a solvent and a catalyst. The method for preparing the transparent composite coating containing the metallic oxide-SiO2 on the basis of the coating solution comprises the steps as follows: a substrate is coated with the coating solution; and high-temperature treatment is performed after low-temperature treatment and hydrolysis are performed for certain time. A mixture of one or more of SiO2/TiO2, SiO2/ZrO2, SiO2/HrO2 and SiO2/ZnO composite coatings can be prepared with the method. Compared with the prior art, the method is simpler, the application is wider, the surface of the coating layer is dense and even, the transparency is good, and the visible light transmittance is above 90%.

Description

Polysilazane coating solution and prepare containing metal oxide-SiO 2the method of compound coating
Technical field
The present invention relates to a kind of polysilazane coating solution of containing metal element and for the preparation of the method for the transparent containing metal oxide-silicon-dioxide of height compound coating, belong to material technology field.
Background technology
Metal oxide-silicon-dioxide (SiO 2) compound coating is good with its chemical stability, electrical property and good mechanical performance, and all have the advantages such as good light transmission to be widely used in fields such as optics, microtronics, photochemical catalysis, protection against corrosions to visible and near infrared light.As SiO 2/ TiO 2compound coating is often used to insulating coating, optical waveguide film of antireflecting coating, antireflection coatings, highly-reflective coating, semiconducter device etc.; SiO 2/ ZrO 2and SiO 2/ HfO 2compound coating aspect the interlayer dielectric of oxidation resistant coating, semiconducter device application widely, SiO in addition 2/ ZrO 2coating is also shown up prominently in fire-resistant coating field; SiO 2/ ZnO coating has excellent corrosion resistance.
Prepare metal oxide-SiO 2the traditional method of compound coating mainly comprises sol-gel method, physical vaporous deposition, chemical Vapor deposition process and electrochemical deposition method etc., but all there are some intrinsic shortcomings in these traditional methods, as this three class of physical vapor deposition, chemical vapour deposition and electrochemical deposition, prepare coating process and need specific installation, preparation technology's more complicated, cost is high, is unfavorable for extensive preparation and application; Although sol-gel method is without special valuable equipment, cost is relatively low, but its shortcoming is the poor adhesive force of coating and matrix, in coating preparation process, need in addition add-on of strictly controlling in pH value, water etc., otherwise the coating of preparation easily chaps, even before uncoated, colloidal sol PhastGel, produce precipitation, cannot implement to apply.Therefore for high transparent metal oxide-SiO 2the preparation of compound coating, does not also have a kind of preparation technology relatively simple at present, is suitable for the method for extensive preparation.
CN1694936A discloses a kind of coating solution, it comprises 0.1 to 35 % by weight and has repeating unit as shown in Equation 2, and dissolve in 0.1 to the 10 % by weight catalyzer that the inorganic or organic polysilazane in solvent and the pure polysilazane content of take are benchmark (as 4,4 '-trimethylene two (1-methyl piperidine)).By coating solution being administered on the surface of base material (as metal, plastics, glass, pottery, timber, cement, mortar, brick etc.), can form the SiO being adhered to by force on base material 2coating, it is excellent aspect erosion resistance and anti-drawing property of wiping.But the refractive index of this coating and wetting property still have the great space of improving.
In order to overcome the deficiencies in the prior art, special proposition the present invention.
Summary of the invention
First object of the present invention is, a kind of polysilazane coating solution of containing metal element is provided.
Another object of the present invention is, provides a kind of above-mentioned coating solution for the preparation of the transparent containing metal oxide-SiO of height 2the method of compound coating, high transparent metal oxide-SiO provided by the invention 2the preparation method of compound coating is than existing metal oxide-SiO 2preparation method of composite coating is simpler, is very suitable for extensive preparation.
For realizing goal of the invention of the present invention, adopt following technical scheme:
A polysilazane coating solution for element, comprises polysilazane, metallic compound and solvent.
The polysilazane coating solution chemical stability of containing metal element provided by the invention is good, the coating of preparing with this coating solution can powerful be attached to the surface of basic unit, there is excellent electrical property and mechanical property, as wear resistance, high thermal resistance, lasting didirtresistance, erosion resistance, static resistance etc., particularly the performance such as refractive index, wetting property improves, the scope of its refractive index is wider, and visible and near infrared light are all had to extraordinary light transmission, and light transmission reaches more than 90%.
For polysilazane coating solution, when selecting the polysilazane of ad hoc structure, make after coating solution, the coating made from this coating solution has comparatively fixing refractive index and wetting property, the present invention adds metal oxide in polysilazane coating solution, and by regulating the content of metal oxide to regulate the performances such as refractive index, wetting property of coating, prepare according to demand the coating of specified property.
Described polysilazane dissolves in described solvent, and has the repeating unit shown in following general formula:
Figure BDA0000414459750000021
Wherein, R 1, R 2and R 3independently represent respectively hydrogen atom, alkyl,-oxyl, containing the silyl of alkyl, containing the amino of alkyl, containing the alkoxyl group of alkyl, containing alkoxy carbonyl or the halogen of alkyl, and R 1, R 2in at least one represents hydrogen atom.
Preferably, R 1, R 2and R 3complete is hydrogen atom, as shown in Equation 2:
Figure BDA0000414459750000022
The coating of preparing with this coating solution is easily solidified, and has greatly promoted chemical stability, electrical property, mechanical property and the light transmission of the coating of preparation.
Described alkyl can be aliphatic hydrocarbyl and aromatic hydrocarbyl.Described aliphatic hydrocarbyl can be chain alkylene and cyclic hydrocarbon group; Aromatic hydrocarbyl comprises aryl and aralkyl.
Described chain alkylene comprises alkyl group; Described cyclic hydrocarbon group comprises cycloalkyl, cycloalkenyl group.Described alkyl group comprises methyl, ethyl, propyl group, butyl, amyl group or octyl group etc.; Described cycloalkyl comprises cyclohexyl etc.; Described cycloalkenyl group comprises cyclohexyl etc.Described aryl comprises phenyl, tolyl, xylyl, naphthyl etc.; Described aralkyl comprises styroyl etc.But above-mentioned substituting group is only the example of explanation use, is not limited to the substituting group of these particular examples.
Described polysilazane can make by currently known methods in this area.
The scope of described polysilazane number-average molecular weight is 100-100000g/mol.When described polysilazane is the repeating unit shown in formula 2, the scope of described polysilazane number-average molecular weight is 700-1500g/mol.
In the polysilazane coating solution of containing metal element of the present invention, described solvent can be dewater, alcohols, amine or the outer any organic solvent that can dissolve inorganic polysilazane and metallic compound of ketone, as toluene, tetrahydrofuran (THF), methylene dichloride, dimethylbenzene, ether, butyl ether, dme, normal hexane, Skellysolve A, ethyl acetate, butylacetate etc.But these solvents are only the example of explanation use, are not limited to the solvent of these particular examples.In addition, these solvents can be used separately, and form that also can mixture is used.
In the polysilazane coating solution of containing metal element of the present invention, described metallic compound can be the titanium compound that dissolves in above-mentioned solvent, zirconium compounds, hafnium compound, zn cpds one or several mixture wherein.The present invention adds metallic compound in coating solution, on the whole, the performances such as its refractive index, wetting property significantly improve, in addition, adding different metallic compounds can also be with serving different characteristics, as adopt titanium compound to also help to improve the refractive index of compound coating, and adopt zn cpds to also help the erosion resistance that improves compound coating, adopt zirconium compounds and hafnium compound to also help the oxidation-resistance that improves compound coating.
Above-mentioned various soluble metal compounds comprise metal alkoxide, metallo-chelate, organometallic compound and metal halide.
Above-mentioned metal alkoxide can be represented by general formula 3:
Figure BDA0000414459750000031
In above formula, x is 0 or 1, R 4, R 5, R 6, R 7represent alkyl, alkyl comprises those that represent in general formula 1.M represents wherein a kind of of Ti, Zr, Hf, Zn.
Above-mentioned metallo-chelate can be acetyl acetone salt, as titanium acetylacetone, methyl ethyl diketone zirconium, methyl ethyl diketone hafnium, zinc acetylacetonate etc.
Above-mentioned metal halide can be represented by general formula 4:
MX z(formula 4)
Wherein M represents wherein a kind of of Ti, Zr, Hf, Zn, and z is 2 or 4.X represents wherein a kind of of Cl, Br, I, F.
The reaction that can be hydrolyzed in being prepared into the process of coating solution of above-mentioned metal alkoxide, metallo-chelate, organometallic compound and metal halide, is transformed into metal oxide, and with SiO 2combination better, not only can improve the stability of coating solution, can also further improve the performances such as refractive index that meet coating of final preparation.
In coating solution of the present invention, the mass percent that metallic compound accounts for polysilazane metallizing thing total amount is for being greater than 0 and be less than 100; It is preferably 10%～65%, more preferably 25%～65% years old.Specifically can be 25%, 35%, 50%, 65%.
The present invention is by adding metallic compound to regulate the performances such as refractive index, wetting property of its coating of preparing in polysilazane coating solution, and by regulating the content etc. of metallic compound to obtain the adjustable coating of refractive index.If metallic compound accounts for the mass percent of polysilazane metallizing thing total amount while being less than 10%, in the coating of preparation, the content of metal oxide is less, compare with coating prepared by simple polysilazane, the performances such as its refractive index do not have clear improvement, and while being greater than 65%, the coating of preparation easily cracks, even come off, when the mass percent that accounts for polysilazane metallizing thing total amount when metallic compound is 10%～65%, not only greatly improved the refractive index of the coating of preparation, the performances such as wetting property, and this coating has extraordinary chemical stability, electrical property and mechanical property.
In coating solution involved in the present invention, the mass percent that polysilazane metallizing thing accounts for whole solution system can be 1%～40%, and preferably 5%～30%.Specifically can be 5%, 10%, 30%.
In described polysilazane coating solution, also comprise catalyzer, described catalyst content is with 0～20% of polysilazane content meter; Preferably, described catalyzer is one or more in N-heterogeneous ring compound, organic or inorganic acid, metal carboxylate, acetyl acetone complex, metallic fine particle, superoxide, metal chloride or organometallic compound.
The present invention adds catalyzer in polysilazane coating solution, to regulate the set time of coating solution.
Described N-heterogeneous ring compound preferably includes 1-methylpiperazine, 1-methyl piperidine, 4-4 '-trimethylene-bis-piperidines, 4,4 '-trimethylene two (1-methyl piperidine), diazabicylo [2.2.2] octanes, cis-2,6-dimethyl-piperizine, 4-(4-methyl piperidine) pyridine, pyridine, dipyridyl, piperidines, lutidine, pyrimidine, pyridazine, pyrazine, quinoline, triazine, pyrroles, 3-pyrroline, imidazoles, triazole, tetrazolium and 1-crassitude.
Described organic or inorganic acid preferably includes acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, stearic acid, spirit of salt, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid and hypochlorous acid.
Described metal carboxylate is with formula (R 12cOO) xm 1the compound representing, wherein R 8represent ester group or ester cyclic group containing 1-22 carbon atom, M 1for being selected from least one metal in Ni, Ti, Pt, Rh, Co, Fe, Ru, Os, Pd, Ir and Al, x is M 1valency.
Described acetyl acetone complex is preferably with (CH 3cOCHCOCH 3) ym 2represent, wherein y is M 2valency, metal M 2preferably include Ni, Pt, Al, Pd and Rh.
The particulate of the preferred Au of metallic fine particle, Ag, Pd or Ni.The particle diameter of metallic fine particle is preferably less than 0.3 micron.
The preparation method of coating solution of the present invention is as follows: polysilazane is joined in the container of dry and inert atmosphere protection, inject described organic solvent dissolution, stir, obtain the solution that polysilazane/organic solvent mixes, described metallic compound is joined in the solution of polysilazane/organic solvent mixing, and the total mass that adds described machine solvent adjustment polysilazane metallizing thing accounts for the mass percent of whole solution system, magnetic agitation 10-14h, obtain the polysilazane solution of transparent containing metal element, described catalyzer is joined in the polysilazane solution of above-mentioned containing metal element, obtain coating solution.
The present invention also provides a kind of compound coating of being prepared by described coating solution.This compound coating is high transparent containing metal oxide-SiO 2compound coating, with respect to the SiO of containing metal oxide not 2coating, has better resistance to elevated temperatures and wear resistance, and particularly the performance such as refractive index, wetting property improves, and has the wider refractive index of adjustable scope.
The invention provides a kind of high transparent containing metal oxide-SiO 2the preparation method of compound coating, detailed process comprises the steps: described coating solution to be coated in substrate, low temperature pre-treatment, hydrolysis certain hour, then pyroprocessing.
Provided by the invention that coating solution is prepared into the method technique of coating is simple, low for equipment requirements, only need can implement to apply by simple dip-coating, spraying, spin coating etc.; Can on complex component, apply, so the method is applicable to extensive preparation and the application of coating.In addition, the coating structure of preparation is fine and close, also energy strong binding, on the surface of basic unit, has good physical and chemical performance.
Transparent containing metal oxide-the SiO of above-mentioned height 2described in compound coating preparation, coating method can be any method that applicating liquid applies, and as trowelling, spraying, flow coat, spin coating, roller coat, dip-coating etc., but coating method is not limited to these exemplary method.
Transparent containing metal oxide-the SiO of above-mentioned height 2described in compound coating preparation, substrate can be any material of resistance to set treatment temp, as metal (iron, stainless steel, copper, molybdenum, chromium, nickel and their alloy etc.), pottery, macromolecular material etc., but can coated substrate be not limited to the substrate of these particular examples.
Transparent containing metal oxide-the SiO of above-mentioned height 2in compound coating preparation, described low temperature pretreatment temperature is 30～150 ℃, and preferably temperature is 50～100 ℃.
Low temperature pretreatment time is 5～60min; Preferred 5～30min.
Transparent containing metal oxide-the SiO of above-mentioned height 2in compound coating preparation, described hydrolysis can be soaks in water or is placed in the steam-laden air atmosphere of certain temperature.
While adopting in water soaking technology, the temperature of water is for being greater than 0 ℃ and be no more than 100 ℃; In the steam-laden atmosphere of certain temperature, temperature can be for being greater than 20 ℃ and be no more than 100 ℃, and humidity is for being greater than 0.1% and be no more than 100%, and preferably humidity is 50%-100%.
Hydrolysis time can be 0～5h, but is not 0.
Transparent containing metal oxide-the SiO of above-mentioned height 2in compound coating preparation, described pyroprocessing is 1～10 ℃/min for controlling temperature rise rate, and the coating that pre-treatment is obtained is heated to described thermal treatment temp.Specifically can be 1 ℃/min, 5 ℃/min, 10 ℃/min.
Described high-temperature heat treatment temperature can be 100～900 ℃; Specifically can be 100 ℃, 200 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃.The soaking time of each pyroprocessing temperature is 1～5h; Specifically can be 1h, 3h, 5h.
Described pyroprocessing is carried out in air atmosphere.
Transparent containing metal oxide-the SiO of the height of being prepared by aforesaid method provided by the invention 2compound coating, described containing metal oxide-SiO 2compound coating surface compact is even, and without hole and defects i.e.cracks, thickness is 10nm～500nm; Specifically can be 79nm, 80nm, 85nm, 87nm, 91nm, 93nm, 95nm, 96nm, 100nm, 106nm, 118nm, 124nm, 131nm, 138nm, 142nm, 189nm, 190nm, 223nm, 245nm, 300nm, 340nm, 343nm, 350nm, 380nm, 420nm.Visible ray is shown to the good transparency, and transmitance all reaches more than 90%, and when pyroprocessing temperature is 100～700 ℃, the transmitance of visible ray is reached more than 95%; Refractive index is 1.45-1.72; Specifically can be 1.45,1.46,1.48,1.49,1.51,1.52,1.53,1.57,1.60,1.61,1.62,1.63,1.64,1.66,1.70; And can be by regulating the mass ratio of polysilazane metallizing thing, mass concentration that polysilazane metallizing thing accounts for whole solution system, pyroprocessing temperature, temperature rise rate etc. to regulate coat-thickness, refractive index and the transparency etc., according to the suitable preparation technology of the different choice of application purpose, prepare the coating of different performance.
Compared with prior art, the present invention has overcome the deficiency of existing coat preparing technology, its outstanding advantage is, the polysilazane coating solution that contains metallic compound provided by the invention, be difficult for gel, precipitation, its coating of preparing can not chap, and has extraordinary chemical stability, electrical property and mechanical property and light transmission, and particularly the performance such as refractive index, wetting property improves; And by polymer molecule, design, can access the different ceramic coating material of chemical composition and structure.The technique of preparing coating with above-mentioned coating solution is simple, low for equipment requirements, only need can implement to apply by simple dip-coating, spraying, spin coating etc.; Can on complex component, apply, so the method is applicable to extensive preparation and the application of coating.
Embodiment
Specific embodiments of the invention only make further explanation content of the present invention, not to Composition of contents restriction of the present invention.In following embodiment, comparative example, material used, reagent etc., if no special instructions, all can obtain from commercial channels.In addition, polysilazane of the present invention also all can obtain from commercial channels.
Embodiment 1: prepare inorganic polysilazane
3000ml there-necked flask, is equipped with mechanical stirring, ultra-low temperature cold condenser, ammonia ingress pipe and prolong.Vacuumize logical High Purity Nitrogen three times, add 1800ml methylene dichloride, then whole system is dropped to-30 ℃, add about 1000g H 2siCl 2rear slowly logical ammonia carries out ammonia solution, to ammonia, no longer absorbs and (after reaction unit, has a bubbling gas, as ammonia no longer absorbs, the ammonia passing into is overflowed through bubbler), reduce ammonia and pass into speed, continue logical 2h, i.e. stopped reaction, remove by filter ammonium chloride, and with methylene chloride washing 3 times, by decompression method, except desolventizing and oligomer, obtain colourless transparent liquid and be inorganic polysilazane, productive rate is about 70%, and the number-average molecular weight of the inorganic polysilazane preparing is about 700.
Embodiment 2: prepare inorganic polysilazane
3000ml there-necked flask, is equipped with mechanical stirring, ultra-low temperature cold condenser, ammonia ingress pipe and prolong.Vacuumize logical High Purity Nitrogen three times, add 1800ml methylene dichloride, then whole system is dropped to-30 ℃, add about 1000g HSiCl 3rear slowly logical ammonia carries out ammonia solution, to ammonia, no longer absorb and (after reaction unit, have a bubbling gas, as ammonia no longer absorbs, the ammonia passing into is overflowed through bubbler), reduce ammonia and pass into speed, continue logical 2h, be stopped reaction, remove by filter ammonium chloride, and wash 3 times by methylene chloride, by decompression method, except desolventizing and oligomer, obtain colourless transparent liquid and be inorganic polysilazane.Productive rate is about 70%, and the number-average molecular weight of the inorganic polysilazane preparing is about 1500.
The organic polysilazane of embodiment 3 preparation
3000ml there-necked flask, is equipped with mechanical stirring, ultra-low temperature cold condenser, ammonia ingress pipe and prolong.Vacuumize logical High Purity Nitrogen three times, add 1800ml methylene dichloride, then whole system is dropped to-30 ℃, add about 1000g CH 3siHCl 2rear slowly logical ammonia carries out ammonia solution, to ammonia, no longer absorbs and (after reaction unit, has a bubbling gas, as ammonia no longer absorbs, the ammonia passing into is overflowed through bubbler), reduce ammonia and pass into speed, continue logical 2h, i.e. stopped reaction, remove by filter ammonium chloride, and with methylene chloride washing 3 times, by decompression method, except desolventizing and oligomer, obtain colourless transparent liquid and be organic polysilazane, wherein R1 is methyl, and R2 and R3 are H.Productive rate is about 70%, and the number-average molecular weight of the organic polysilazane preparing is about 3000.
The organic polysilazane of embodiment 4 preparation
This enforcement adopts the preparation method of embodiment 1, and difference is the H in embodiment 1 2siCl 2be changed to CH 3oSiHCl 2, preparing organic polysilazane, in this polysilazane, R1 is methoxyl group, R2 and R3 are H.
Embodiment 5, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/xylene solution, and add 49g dimethylbenzene to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 190nm, 630nm wavelength place refractive index is about 1.49, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 6, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g toluene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.1g iso-butyl titanate (iso-butyl titanate account for inorganic polysilazane and iso-butyl titanate total amount 25%) is joined in inorganic polysilazane/toluene solution, and add 49g toluene to regulate inorganic polysilazane and iso-butyl titanate total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt rolling method that precoating solution is coated onto on the quartz plate (transparency test with), 10mm * 10mm monocrystalline silicon piece (refractive index test with) and 100mm * 100mm Kapton of 30mm * 10mm, and be placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and iso-butyl titanate of pre-treatment is put in the 100ml beaker of 15 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, be raised to 100 ℃, insulation 5h, obtain surperficial zero defect, with the sticking power of Kapton high (cross-hatching test is 9H), thickness is about 343nm, 630nm wavelength place refractive index is about 1.51, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 7, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g methylene dichloride, stir inorganic polysilazane/dichloromethane solution that certain hour obtains 10%Wt.1g titanium tetrachloride (titanium tetrachloride account for inorganic polysilazane and titanium tetrachloride total amount 25%) is joined in inorganic polysilazane/dichloromethane solution, and add 49g methylene dichloride to regulate inorganic polysilazane and titanium tetrachloride total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spraying method that precoating solution is coated onto on the quartz plate (transparency test with), 10mm * 10mm monocrystalline silicon piece (refractive index test with) and 10mm * 10mm stainless steel substrates of 30mm * 10mm, and be placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and titanium tetrachloride of pre-treatment is put in the 100ml beaker of 15 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, be raised to 200 ℃, insulation 3h, obtain surperficial zero defect, with the sticking power of stainless steel substrates high (cross-hatching test is 9H), thickness is about 420nm, 630nm wavelength place refractive index is about 1.52, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 8, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g tetrahydrofuran (THF), stir inorganic polysilazane/tetrahydrofuran solution that certain hour obtains 10%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/tetrahydrofuran solution, and add 9g tetrahydrofuran (THF) to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 35 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 223nm, 630nm wavelength place refractive index is about 1.49, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 9, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 7g ether, stir inorganic polysilazane/diethyl ether solution that certain hour obtains 30%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/diethyl ether solution, and add about 2.33g ether to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 30% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 245nm, 630nm wavelength place refractive index is about 1.51, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 10, high transparent SiO 2/ HfO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g ethyl acetate, stir inorganic polysilazane/ethyl acetate solution that certain hour obtains 10%Wt.By 1.62g HfBr 4(HfBr 4account for inorganic polysilazane and HfBr 4total amount 35%) join in inorganic polysilazane/ethyl acetate solution, and add about 14.6g ethyl acetate to regulate inorganic polysilazane and HfBr 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and HfBr 4substrate be put in the 100ml beaker of 1 ℃ of deionized water that 50ml is housed and be hydrolyzed 5h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 189nm, 630nm wavelength place refractive index is about 1.48, and the transmitance of visible ray is reached to more than 90% SiO 2/ HfO 2compound coating.
Embodiment 11, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g normal hexane, stir inorganic polysilazane/hexane solution that certain hour obtains 10%Wt.By 3g TiBr 4(TiBr 4account for inorganic polysilazane and TiBr 4total amount 50%) join in inorganic polysilazane/hexane solution, and add 27g normal hexane to regulate inorganic polysilazane and TiBr 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and TiBr 4substrate be put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and be hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 100nm, 630nm wavelength place refractive index is about 1.70, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 12, high transparent SiO 2/ ZrO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.By 5.6g ZrBr 4(ZrBr 4account for inorganic polysilazane and ZrBr 4total amount 65%) join in inorganic polysilazane/xylene solution, and add 50.4g dimethylbenzene to regulate inorganic polysilazane and ZrBr 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and ZrBr 4substrate be put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and be hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 91nm, 630nm wavelength place refractive index is about 1.66, and the transmitance of visible ray is reached to more than 90% SiO 2/ ZrO 2compound coating.
Embodiment 13, high transparent SiO 2/ HfO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.3g methyl ethyl diketone hafnium (methyl ethyl diketone hafnium account for inorganic polysilazane and methyl ethyl diketone hafnium total amount 50%) is joined in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and methyl ethyl diketone hafnium total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and methyl ethyl diketone hafnium of pre-treatment is put in the 100ml beaker that 50ml boiling deionized water (100 ℃) is housed, and adopts heating jacket to keep water boiling, hydrolysis 0.5h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 800 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 93nm, 630nm wavelength place refractive index is about 1.63, and the transmitance of visible ray is reached to more than 90% SiO 2/ HfO 2compound coating.
Embodiment 14, high transparent SiO 2/ HfO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.By 3g HfCl 4(HfCl 4account for inorganic polysilazane and HfCl 4total amount 50%) join in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and HfCl 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and HfCl 4substrate to be put into temperature be 100 ℃, the climatic chamber hydrolysis 2h that humidity is 50%.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 96nm, 630nm wavelength place refractive index is about 1.64, and the transmitance of visible ray is reached to more than 90% SiO 2/ HfO 2compound coating.
Embodiment 15, high transparent SiO 2the preparation of/ZnO compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.3g tert.-butoxy zinc (tert.-butoxy zinc account for inorganic polysilazane and tert.-butoxy zinc total amount 50%) is joined in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and tert.-butoxy zinc total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tert.-butoxy zinc of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 1 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 95nm, 630nm wavelength place refractive index is about 1.64, and the transmitance of visible ray is reached to more than 90% SiO 2/ ZnO compound coating.
Embodiment 16, high transparent SiO 2/ ZrO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.By 3g ZrCl 4(ZrCl4 accounts for inorganic polysilazane and ZrCl 4total amount 50%) join in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and ZrCl 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and ZrCl 4substrate be put in the 100ml beaker that 50ml deionized water is housed and be hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 600 ℃, insulation 2h, obtains surperficial zero defect, and thickness is about 106nm, 630nm wavelength place refractive index is about 1.60, and the transmitance of visible ray is reached to more than 95% SiO 2/ ZrO 2compound coating.
Embodiment 17, high transparent SiO 2the preparation of/ZnO compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.By 3gZnCl 2(ZnCl 2account for inorganic polysilazane and ZnCl 2total amount 50%) join in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and ZnCl 2total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and ZnCl 2substrate be put in the 100ml beaker that 50ml deionized water is housed and be hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 600 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 124nm, 630nm wavelength place refractive index is about 1.60, and the transmitance of visible ray is reached to more than 95% SiO 2/ ZnO compound coating.
Embodiment 18, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.By 3g TiCl 4(TiCl 4account for inorganic polysilazane and TiCl 4total amount 50%) join in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and TiCl 4total mass accounts for 10% of whole solution system, and magnetic agitation 12h obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then by pre-treatment good scribble inorganic polysilazane and TiCl 4substrate be put in the 100ml beaker that 50ml deionized water is housed and be hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 500 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 131nm, 630nm wavelength place refractive index is about 1.62, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 19, high transparent SiO 2/ ZrO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.3g tetrabutyl zirconate (tetrabutyl zirconate account for inorganic polysilazane and tetrabutyl zirconate total amount 50%) is joined in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and tetrabutyl zirconate total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl zirconate of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 400 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 142nm, 630nm wavelength place refractive index is about 1.57, and the transmitance of visible ray is reached to more than 95% SiO 2/ ZrO 2compound coating.
Embodiment 20, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection; inject 27g dimethylbenzene as solvent; and the triethylamine of 0.5%Wt is as crosslinking catalyst, stirs certain hour and obtains inorganic polysilazane/xylene solution that 10%Wt contains catalyzer.3g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 50%) is joined in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 400 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 138nm, 630nm wavelength place refractive index is about 1.61, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 21, high transparent SiO 2/ ZrO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.3g methyl ethyl diketone zirconium (methyl ethyl diketone zirconium account for inorganic polysilazane and methyl ethyl diketone zirconium total amount 50%) is joined in inorganic polysilazane/toluene solution, and add 27g toluene to regulate inorganic polysilazane and methyl ethyl diketone zirconium total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and methyl ethyl diketone zirconium of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 87nm, 630nm wavelength place refractive index is about 1.65, and the transmitance of visible ray is reached to more than 90% SiO 2/ ZrO 2compound coating.
Embodiment 22, high transparent SiO 2/ HfO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.3g tetra-tert.-butoxy hafniums (four tert.-butoxy hafniums account for inorganic polysilazane and four tert.-butoxy hafnium total amounts 50%) are joined in inorganic polysilazane/xylene solution, and add 27g dimethylbenzene to regulate inorganic polysilazane and four tert.-butoxy hafnium total masses to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 150 ℃.Then the good substrate that scribbles inorganic polysilazane and four tert.-butoxy hafniums of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 85nm, 630nm wavelength place refractive index is about 1.63, and the transmitance of visible ray is reached to more than 90% SiO 2/ HfO 2compound coating.
Embodiment 23, high transparent SiO 2the preparation of/ZnO compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.3g zinc acetylacetonate (zinc acetylacetonate account for inorganic polysilazane and titanium acetylacetone total amount 50%) is joined in inorganic polysilazane/toluene solution, and add 27g toluene to regulate inorganic polysilazane and zinc acetylacetonate total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 50min in the baking oven of 50 ℃.Then the good substrate that scribbles inorganic polysilazane and zinc acetylacetonate of pre-treatment being put into temperature is 100 ℃, the climatic chamber hydrolysis 5h that humidity is 1%.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 80nm, 630nm wavelength place refractive index is about 1.60, and the transmitance of visible ray is reached to more than 90% SiO 2/ ZnO compound coating.
Embodiment 24, high transparent SiO 2/ TiO 2the preparation of/ZnO compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.1.5g tetrabutyl titanate and 1.5g zinc acetylacetonate (tetrabutyl titanate and zinc acetylacetonate total amount account for inorganic polysilazane, tetrabutyl titanate and zinc acetylacetonate total amount 50%) are joined respectively in inorganic polysilazane/toluene solution, and add 27g toluene to regulate inorganic polysilazane and zinc acetylacetonate total mass to account for 10% of whole solution system, magnetic agitation 14h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 30min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and zinc acetylacetonate of pre-treatment being put into temperature is 90 ℃, the climatic chamber hydrolysis 0.5h that humidity is 100%.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 79nm, 630nm wavelength place refractive index is about 1.63, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2/ ZnO compound coating.
Embodiment 25, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 2 is joined in the container of dry and inert atmosphere protection, inject 4g toluene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.0.33g iso-butyl titanate (iso-butyl titanate account for inorganic polysilazane and iso-butyl titanate total amount 10%) is joined in inorganic polysilazane/toluene solution, and add 1g toluene to regulate inorganic polysilazane and iso-butyl titanate total mass to account for 40% of whole solution system, magnetic agitation 10h, obtains transparent precoating solution.Adopt rolling method that precoating solution is coated onto on the quartz plate (transparency test with), 10mm * 10mm monocrystalline silicon piece (refractive index test with) and 100mm * 100mm Kapton of 30mm * 10mm, and be placed on pre-treatment 60min in the baking oven of 30 ℃.Then the good substrate that scribbles inorganic polysilazane and iso-butyl titanate of pre-treatment being put into temperature is 20 ℃, the climatic chamber hydrolysis 2h that humidity is 100%.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, be raised to 100 ℃, insulation 5h, obtain surperficial zero defect, with the sticking power of Kapton high (cross-hatching test is 9H), thickness is about 350nm, 630nm wavelength place refractive index is about 1.46, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 26, high transparent SiO 2the preparation of/ZnO compound coating
3g synthetic inorganic polysilazane in reference example 3 is joined in the container of dry and inert atmosphere protection, inject 94g dimethylbenzene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.3g zinc acetylacetonate (zinc acetylacetonate account for inorganic polysilazane and zinc acetylacetonate total amount 50%) is joined in inorganic polysilazane/toluene solution, and add 500g toluene to regulate inorganic polysilazane and zinc acetylacetonate total mass to account for 1% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and zinc acetylacetonate of pre-treatment is put in the 100ml beaker of 75 ℃ of deionized waters that 50ml is housed and is hydrolyzed 1h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 80nm, 630nm wavelength place refractive index is about 1.60, and the transmitance of visible ray is reached to more than 90% SiO 2/ ZnO compound coating.
Embodiment 27, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 4 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/xylene solution, and add 49g dimethylbenzene to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 190nm, 630nm wavelength place refractive index is about 1.51, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 28, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g toluene, stir inorganic polysilazane/toluene solution that certain hour obtains 10%Wt.1g iso-butyl titanate (iso-butyl titanate account for inorganic polysilazane and iso-butyl titanate total amount 25%) is joined in inorganic polysilazane/toluene solution, and add 49g toluene to regulate inorganic polysilazane and iso-butyl titanate total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt rolling method that precoating solution is coated onto on the quartz plate (transparency test with), 10mm * 10mm monocrystalline silicon piece (refractive index test with) and 100mm * 100mm Kapton of 30mm * 10mm, and be placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and iso-butyl titanate of pre-treatment is put in the 100ml beaker of 15 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, be raised to 100 ℃, insulation 5h, obtain surperficial zero defect, with the sticking power of Kapton high (cross-hatching test is 9H), thickness is about 340nm, 630nm wavelength place refractive index is about 1.52, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 29, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g methylene dichloride, stir inorganic polysilazane/dichloromethane solution that certain hour obtains 10%Wt.1g titanium tetrachloride (titanium tetrachloride account for inorganic polysilazane and titanium tetrachloride total amount 25%) is joined in inorganic polysilazane/dichloromethane solution, and add 49g methylene dichloride to regulate inorganic polysilazane and titanium tetrachloride total mass to account for 5% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spraying method that precoating solution is coated onto on the quartz plate (transparency test with), 10mm * 10mm monocrystalline silicon piece (refractive index test with) and 10mm * 10mm stainless steel substrates of 30mm * 10mm, and be placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and titanium tetrachloride of pre-treatment is put in the 100ml beaker of 15 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, be raised to 200 ℃, insulation 3h, obtain surperficial zero defect, with the sticking power of stainless steel substrates high (cross-hatching test is 9H), thickness is about 300nm, 630nm wavelength place refractive index is about 1.53, and the transmitance of visible ray is reached to more than 95% SiO 2/ TiO 2compound coating.
Embodiment 30, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 3 is joined in the container of dry and inert atmosphere protection, inject 27g tetrahydrofuran (THF), stir inorganic polysilazane/tetrahydrofuran solution that certain hour obtains 10%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/tetrahydrofuran solution, and add 9g tetrahydrofuran (THF) to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 10% of whole solution system, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 35 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 223nm, 630nm wavelength place refractive index is about 1.49, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Embodiment 31, high transparent SiO 2/ TiO 2the preparation of compound coating
3g synthetic inorganic polysilazane in reference example 2 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.1g tetrabutyl titanate (tetrabutyl titanate account for inorganic polysilazane and tetrabutyl titanate total amount 25%) is joined in inorganic polysilazane/xylene solution, and add 49g dimethylbenzene to regulate inorganic polysilazane and tetrabutyl titanate total mass to account for 5% of whole solution system, be incorporated as 20% 1-methylpiperazine of polysilazane quality, magnetic agitation 12h, obtains transparent precoating solution.Adopt spin-coating method (2000rpm, 20s) precoating solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane and tetrabutyl titanate of pre-treatment is put in the 100ml beaker of 25 ℃ of deionized waters that 50ml is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 190nm, 630nm wavelength place refractive index is about 1.49, and the transmitance of visible ray is reached to more than 90% SiO 2/ TiO 2compound coating.
Comparative example 1: high transparent SiO 2the preparation of coating
3g synthetic inorganic polysilazane in reference example 1 is joined in the container of dry and inert atmosphere protection, inject 27g dimethylbenzene, stir inorganic polysilazane/xylene solution that certain hour obtains 10%Wt.Adopt spin-coating method (2000rpm, 20s) inorganic polysilazane/xylene solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 380nm, the refractive index at 630nm wavelength place is about 1.45, and the transmitance of visible ray is reached to more than 95% SiO 2coating.
Comparative example 2: high transparent SiO 2the preparation of coating
The inorganic polysilazane that 3g is synthesized in reference example 1 and the DMPP(catalyzer of 1g) join in the container of dry and inert atmosphere protection, inject 11g tetrahydrofuran (THF), stir inorganic polysilazane/tetrahydrofuran solution that certain hour obtains 20%Wt.Adopt spin-coating method (2000rpm, 20s) inorganic polysilazane/tetrahydrofuran solution is coated onto to the quartz plate (transparency test with) of 30mm * 10mm and 10mm * 10mm monocrystalline silicon piece (other test except transparency test with) upper, and is placed on pre-treatment 5min in the baking oven of 100 ℃.Then the good substrate that scribbles inorganic polysilazane of pre-treatment is put in the 100ml beaker that 50ml deionized water is housed and is hydrolyzed 4h.After being hydrolyzed, substrate is put in the tube furnace of blowing air, with 5 ℃/min temperature rise rate, is raised to 900 ℃, insulation 1h, obtains surperficial zero defect, and thickness is about 382nm, the refractive index at 630nm wavelength place is about 1.45, and the transmitance of visible ray is reached to more than 95% SiO 2coating.
Above-mentioned experimental example and comparative example show, after the structural formula of polysilazane is selected, the refractive index of the coating of preparation is substantially fixing, and refractive index is not subject to the impact of the factors such as catalyzer, preparation method, but by add metal oxide in preparing the raw material of coating solution, can further regulate the refractive index of the coating of preparation, a wider range of the refractive index of this coating, can meet different needs, obtain the coating of specific refractive index.

Claims (14)

1. a polysilazane coating solution for containing metal element, comprises polysilazane, metallic compound and solvent.
2. the polysilazane coating solution of containing metal element according to claim 1, is characterized in that: described polysilazane dissolves in described solvent, and has the repeating unit shown in following general formula:
Figure FDA0000414459740000011
Wherein, R 1, R 2and R 3independently represent respectively hydrogen atom, alkyl,-oxyl, containing the silyl of alkyl, containing the amino of alkyl, containing the alkoxyl group of alkyl, containing alkoxy carbonyl or the halogen of alkyl, and R 1, R 2in at least one represents hydrogen atom.
3. the polysilazane coating solution of containing metal element according to claim 2, is characterized in that: R 1, R 2and R 3complete is hydrogen atom, as shown in Equation 2
Figure FDA0000414459740000012
4. the polysilazane coating solution of containing metal element according to claim 1, is characterized in that: described solvent be dewater, any organic solvent that can dissolve described polysilazane and described metallic compound beyond alcohols, amine or ketone; Described solvent is preferably one or more mixing in toluene, tetrahydrofuran (THF), methylene dichloride, dimethylbenzene, ether, butyl ether, dme, normal hexane, Skellysolve A, ethyl acetate, butylacetate.
5. coating solution according to claim 1, is characterized in that: described metallic compound is one or several the mixture in soluble titanium compound, zirconium compounds, hafnium compound and zn cpds.
6. the coating solution of stating according to claim 1 or 5, is characterized in that: the mass percent that described metallic compound accounts for polysilazane and described metallic compound total amount is for being greater than 0 and be less than 100; It is preferably 10%～65%.
7. according to the coating solution described in claim 1 or 6, it is characterized in that: the mass percent that described polysilazane and described metallic compound account for whole solution system can be 1%～40%; It is preferably 5%～30% years old.
8. according to the coating solution of claim 1, it is characterized in that: in described polysilazane coating solution, also comprise catalyzer, described catalyst content is with 0～20% of polysilazane content meter; Preferably, described catalyzer is one or more in N-heterogeneous ring compound, organic or inorganic acid, metal carboxylate, acetyl acetone complex, metallic fine particle, superoxide, metal chloride or organometallic compound.
9. a preparation method who prepares the arbitrary described coating solution of claim 1-8, comprise the steps: polysilazane to join in the container of dry and inert atmosphere protection, inject described organic solvent dissolution, stir, obtain the solution that polysilazane/organic solvent mixes, described metallic compound is joined in the solution of polysilazane/organic solvent mixing, and the total mass that adds described machine solvent adjustment polysilazane metallizing thing accounts for the mass percent of whole solution system, magnetic agitation 10-14h, obtain the polysilazane solution of transparent containing metal element, described catalyzer is joined in the polysilazane solution of above-mentioned containing metal element, obtain coating solution.
10. a compound coating of being prepared by the coating solution described in claim 1-9 any one.
The preparation method of 11. 1 kinds of compound coatings claimed in claim 10, comprises the steps: the coating solution described in claim 1-9 any one to be coated in substrate, low temperature pre-treatment, hydrolysis certain hour, then pyroprocessing.
12. methods according to claim 11, is characterized in that: low temperature pretreatment temperature is 30～150 ℃, and its preferred temperature is 50～100 ℃; Pretreatment time is 5～60min, preferably 5～30min.
13. preparation methods according to claim 11, is characterized in that: described in be hydrolyzed in water and soak or to be placed in the steam-laden air atmosphere of certain temperature, hydrolysis time is for being greater than 0h and being no more than 5h; While adopting in water soaking technology, the temperature of water is for being greater than 0 ℃ and be no more than 100 ℃; In the steam-laden atmosphere of certain temperature, temperature is for being greater than 20 ℃ and be no more than 100 ℃, and humidity is for being greater than 0.1% and be no more than 100%, and preferably humidity is 50%-100%.
14. preparation methods according to claim 11, is characterized in that: described pyroprocessing is warming up to 100～900 ℃, insulation 1h～5h by the speed of 1 ℃/min～10 ℃/min for coating that pre-treatment is obtained; Described pyroprocessing is carried out in air atmosphere.
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CN105859304A (en) * 2016-03-30 2016-08-17 航天材料及工艺研究所 Preparation method for three-dimensional carbon fiber preform interface coating
CN106299375A (en) * 2016-09-30 2017-01-04 江苏长园华盛新能源材料有限公司 A kind of carbon fibre composite of silicon cladding and its preparation method and application
CN107307745A (en) * 2017-07-20 2017-11-03 广东工业大学 Application of the polysilazane as coating on cooker
CN109790078A (en) * 2016-09-13 2019-05-21 安多里尼·路易吉与C.股份公司 Method for treating a substrate made of stone
CN111362587A (en) * 2020-04-28 2020-07-03 东莞南玻太阳能玻璃有限公司 High-hardness moisture-proof anti-reflection solar glass and preparation method thereof
CN112760036A (en) * 2019-11-05 2021-05-07 中国科学院化学研究所 Atomic oxygen resistant coating with ultraviolet shielding and visible light permeability enhancing properties and preparation method thereof
CN113683818A (en) * 2021-08-27 2021-11-23 上海材料研究所 Core-shell structure modified boron nitride and preparation method thereof
CN114605916A (en) * 2022-02-25 2022-06-10 武汉苏泊尔炊具有限公司 Non-stick paint, non-stick coating and non-stick cooker
CN115558323A (en) * 2021-07-02 2023-01-03 宁波激智科技股份有限公司 Antibacterial polytitanium azane coating composition and preparation method thereof

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CN105859304B (en) * 2016-03-30 2018-06-19 航天材料及工艺研究所 A kind of three-dimensional carbon fiber precast body interface coating preparation method
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CN109790078B (en) * 2016-09-13 2021-12-21 安多里尼·路易吉与C.股份公司 Method for treating a substrate made of stone
CN109790078A (en) * 2016-09-13 2019-05-21 安多里尼·路易吉与C.股份公司 Method for treating a substrate made of stone
CN106299375B (en) * 2016-09-30 2019-05-07 江苏长园华盛新能源材料有限公司 A kind of carbon fibre composite and its preparation method and application of silicon cladding
CN106299375A (en) * 2016-09-30 2017-01-04 江苏长园华盛新能源材料有限公司 A kind of carbon fibre composite of silicon cladding and its preparation method and application
CN107307745A (en) * 2017-07-20 2017-11-03 广东工业大学 Application of the polysilazane as coating on cooker
CN112760036A (en) * 2019-11-05 2021-05-07 中国科学院化学研究所 Atomic oxygen resistant coating with ultraviolet shielding and visible light permeability enhancing properties and preparation method thereof
CN111362587A (en) * 2020-04-28 2020-07-03 东莞南玻太阳能玻璃有限公司 High-hardness moisture-proof anti-reflection solar glass and preparation method thereof
CN111362587B (en) * 2020-04-28 2022-05-24 东莞南玻太阳能玻璃有限公司 High-hardness moisture-proof anti-reflection solar glass and preparation method thereof
CN115558323A (en) * 2021-07-02 2023-01-03 宁波激智科技股份有限公司 Antibacterial polytitanium azane coating composition and preparation method thereof
CN115558323B (en) * 2021-07-02 2023-12-22 宁波激智科技股份有限公司 Antibacterial poly-titanium-nitrogen-alkane coating composition and preparation method thereof
CN113683818A (en) * 2021-08-27 2021-11-23 上海材料研究所 Core-shell structure modified boron nitride and preparation method thereof
CN114605916A (en) * 2022-02-25 2022-06-10 武汉苏泊尔炊具有限公司 Non-stick paint, non-stick coating and non-stick cooker

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