CN102951852A - Preparation method of glass with surface having transparent conductive film - Google Patents
Preparation method of glass with surface having transparent conductive film Download PDFInfo
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- CN102951852A CN102951852A CN2011102423134A CN201110242313A CN102951852A CN 102951852 A CN102951852 A CN 102951852A CN 2011102423134 A CN2011102423134 A CN 2011102423134A CN 201110242313 A CN201110242313 A CN 201110242313A CN 102951852 A CN102951852 A CN 102951852A
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Abstract
The invention relates to a preparation method of glass with the surface having a transparent conductive film. The method comprises the following steps: 1, preparing an aqueous solution of indium chloride; 2, preparing a tin chloride solution; 3, ingredient mixing: carrying out dispersion mixing of the aqueous solution of indium chloride prepared in step 1 and the organic solution of tin chloride prepared in step 2 to obtain an oil-water type liquid-liquid dispersion system material; 4, injecting an adhesive to the surface of the base of glass; 5, carrying out heat treatment to form a film; and 6, carrying out air cooling to obtain the glass with the surface having the transparent conductive film. The preparation method has the advantages of reasonable and convenient preparation technology, low production cost, safe and reliable preparation process, thorough reaction, good prepared product quality, high raw material utilization rate, and benefiting for the large-scale industrialized production. The preparation method provides conditions for the process industrialization, and the preparation method is simple, convenient and rapid.
Description
Technical field
The present invention relates to the method for glass preparation that a kind of surface has the electrically conducting transparent function film.The present invention mainly is applicable to photovoltaic cell, electric light source uses.The invention belongs to the functional glass technical field.
Background technology
Special glass with characteristics such as high transmission rate, certain electroconductibility and the clear sexual functions of clean surfaces, it is the important foundation material that use in the fields such as novel thin film solar cell (photovoltaic cell) and photoelectric device (electrode light-emitting device), through further adopt epitaxy technology to process at the functional glass substrate material, make photovoltaic cell and photoelectric device.
Transparent conductive oxide (Transparent Conductive Oxide is called for short TCO) film is metal oxide, is again semiconductor film material, also is optical material.Film is mainly by oxide compound and the composite multi-component oxide film material thereof of In, Sn, Sb, Zn and Cd, the common light electrical characteristic such as have that the forbidden band is wide, the visible range optical transmittance is high and resistivity is low are widely used in that solar cell, plane show, specific function window coating and other field of photoelectric devices.
At present, indium and tin oxide film is the most excellent transparent conductive film material of over-all properties, has a series of special performances, has lower resistivity, and transmittance is high, and processing characteristics is good, is convenient to etching, and film hardness is high, not only the advantage such as wear-resisting but also resistance to chemical attack.
The ITO nesa coating is to obtain in the matrix surface deposition with physics or chemical method, and body material generally adopts glass, therefore be referred to as ITO film transparent conducting glass.The preparation method of transparent conductive oxide film has magnetron sputtering, pulsed laser deposition, sol-gel, thermospray chemical vapour deposition, reacting heat evaporation, atomic layer epitaxy etc.Wherein sol-gel (Sol-Gel) method is a kind of new method of preparation material in the wet chemical method, this technology is that the metallic compound (inorganic salt or metal alkoxide) that will be easy to be hydrolyzed is given birth to reaction with steeping in water for reconstitution in certain solvent, pass through hydrolysis and polycondensation process and gradually gelation, the processing such as drying, sintering makes required material at last again.The main raw material that sol-gel method has prepared the ITO nesa coating is:
Indium-111 chloride (Indium Trichloride): molecular formula is InCl
3, be white plates crystallization or yellow crystal, density 3.46g/cm
3, 586 ℃ of fusing points, soluble in water, be slightly soluble in alcohol, ether, easily deliquescence.Distillation when being heated to 300 ℃, volatilization in the time of 600 ℃.
Tin tetrachloride
(Tin (IV) chloride; Stannic chloride)
:Molecular formula is SnCl
4, colourless liquid, fusing point-33 ℃, 114.1 ℃ of boiling points, density is 2.226 g/cm
3, volatile, in wet air, be fuming because of hydrolysis, be soluble in some non-polar solvent.Tin tetrachloride is water-soluble, hydrolytic action occurs and separate out the α stannic acid, and continue adding distil water and generate Tin tetrachloride pentahydrate, and water-soluble, ionization produces Sn (H
2O)
5 4+Ion.
Alkyl glycoside is the glucosides class new non-ionic surfactants that fatty alcohol and glucose generates through condensation reaction, glucose polymerization degree DP value in the alkyl polyglycoside molecule structure is generally 1.3-2.8, alkyl glycoside is generally white powder, similar to vitreum, there is not clear and definite fusing point, begin to yield point a wider melting range is arranged from softening temperature, generally beginning thermolysiss greater than 270 ℃.
The different purposes of transparent conductive oxide film have different requirements to crystalline orientation, surface finish, electroconductibility, optical property and the gas sensing property etc. of film, and these characteristics of film are to be determined by the processing parameter of preparation process.Therefore, the research and development new preparation process, obtain certain function film performance, to reduce preparation temperature, improve control accuracy, reduce preparation cost and adapt to integrated be the development trend of transparent conductive oxide film, and the control of preparation method, particularly technique and parameter then should be according to the performance requriements of film with different application purposes and difference.
Though although sol-gel technology energy Large-Area-Uniform film forming, but the viscosity of film thickness and precursor aqueous solution and lift or spin coating speed has direct relation, difficult accurately control, and the film front end of crystal pulling method preparation also has certain difference with the thin film center zone of rear end or spin-coating method preparation and the thickness of outer rim, affected the high homogeneity of performance.In addition, manage to reduce the temperature that this technique subsequent anneal is processed, improve quality and the photoelectric properties of film, the broadened application field remains this technique and prepares the main direction that film is worth further effort.Therefore, the special glass that research and development have a specific function is that the critical function material of photovoltaic cell and photoelectric device is important developing direction, significant, for film photovoltaic cell and photoelectric device provide base mateiral, acquisition has the core technology of independent intellectual property right, will promote the core competitiveness of China.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, provide a kind of preparation technology rationally convenient, a kind of novel surface that production cost is low, safe preparation process is reliable, reaction is thorough, the preparing product quality is good, yield is high have the method for glass preparation of electrically conducting transparent function film.
Realize that the above-mentioned purpose technical scheme is: a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and the quality percentage composition that obtains the indium chloride aqueous solution is 1～5% InCl
3With 0.2～0.5% alkyl glycoside;
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and the quality percentage composition that obtains tin chloride solution is 0.1～1.0% SnCl
4Organic solution;
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution that the indium chloride aqueous solution that the first step preparation is obtained and second step obtain is carried out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material;
(4) glass baseplate surface injecting glue: profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue through on the glass baseplate of surface preparation, is formed glued membrane on the surface of glass baseplate;
(5) thermal treatment film forming: the injecting glue glass baseplate with previous step prepares forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate;
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air cooling annealing or quenching, obtains the glass that the surface has the electrically conducting transparent function film.
Further, alkyl glucoside surfactant described in the preparation of the first step indium chloride aqueous solution is any one in octyl glucosides, decyl glucosides, Dodecyl Glucoside, tetradecyl glucosides, n-Hexadecane glucoside and the octadecyl glucosides, perhaps be arbitrarily several combination, the glucose polymerization degree DP value of alkyl glucose is 1.6～2.6.
Further, the organic solvent described in the preparation of second step tin chloride solution is any one in kerosene, gasoline or the C6-C18 alkane.
Further, the profit shape liquid-liquid dispersion system that obtains described in the 3rd step batching is mixed is with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:20～50.
Further, liquid-liquid dispersion mixing equipment described in the 3rd step batching is mixed is any one in stirring tank, ultraemulsifier or the static mixer.
Further, the 4th step glass baseplate surface injecting glue is injecting glue on the glue injecting film on glass baseplate surface, and injecting glue employing method is any one in dipping, spin coating or the spraying method.
Further, the glass baseplate through surface preparation is the glass baseplate that surface process oil removing and ash disposal are processed described in the 4th step glass baseplate surface injecting glue.
Further, the roasting drying temperature described in the 5th step thermal treatment film forming is 500～600 ℃.
Further, described in the 5th step thermal treatment film forming to obtain the thickness of glass that the surface has the electrically conducting transparent function film be 1～20 μ m.
Principal reaction principle of the present invention: the reaction equation that indium tin oxide film forms is:
2InCl
3+3H
2O→In
2O
3+6HCl
SnCl
4+2H
2O→SnO
2+4HCl
InCl
3And SnCl
4The condition that exists at water issues the reaction of unboiled water solution, the SnO that obtains
2The In that mixes
2O
3Sull.
Technical scheme of the present invention is mainly innovated in the following areas:
(1) the standby indium chloride aqueous solution of preparation forms water material and tin chloride organic solution solution formation oil phase material respectively, for condition has been created in the preparation of liquid-liquid dispersion system;
(2) in the indium chloride aqueous solution, add alkyl glucoside surfactant, preparation profit shape liquid-liquid dispersion emulsion system;
(3) adopt New-liquid dispersion technology, preparation profit shape emulsion system;
(4) adopt dipping, spin coating or spraying technology, on treated glass substrate surface, form glued membrane by preparation profit shape emulsion system injecting glue.
Realize that the main technique equipment that the present invention needs is: solution preparation equipment, liquid-liquid dispersion mixing equipment, roasting drying plant etc.
The present invention adopts the advantage of technique scheme to be:
(1) takes full advantage of alkyl glucoside surfactant and have high surface, strong, the anti-strong acid of compatibleness, anti-hard water, characteristic that salt resistance is strong.In the indium chloride aqueous solution, add alkyl glucoside surfactant and form the water material, anhydrous stannic chloride is dissolved in the organic solution tin chloride to be made into organic solution and to form oil phase material, then with water material and oil phase material dispersing and mixing, obtain profit shape liquid-liquid dispersion emulsion system, for the preparation of presoma in the sol-gel technology process provides very favorable condition, further be convenient to form tin indium oxide ITO transparent conductive film at glass baseplate for the glass baseplate injecting glue and created condition.
(2) take full advantage of and obtain fine (micron dimension) droplet that profit shape liquid-liquid dispersion emulsion system has, obtaining profit shape liquid-liquid dispersion emulsion system satisfies on the glass substrate upper berth and carries out, reduce simultaneously the volatilization loss of tin chloride in the thermal decomposition process deposition, it is abundant that deposition reaction is carried out in thermolysis, easily obtain thickness very evenly, the good high-quality TCO film of photoelectric properties.
(3) be sprayed onto on the glass substrate of heating with the liquid-liquid dispersion emulsion system, the processing parameters such as the temperature of easy adjusting glass substrate, substrate translational speed, spray amount size, Large-Area-Uniform film forming on the substrate can deposit uniform tin indium oxide ITO transparent conductive film at substrate.
(4) adopting sol-gel technology to prepare sull can carry out under normal pressure, need not vacuum, and the material choice scope is wide, easily realizes mixing, and can realize the big area film forming, is easy to the advantages such as industrialization.
(5) the technological process temperature is low, and the material preparation process is easy to control, can make some and be difficult to obtain with traditional method or basic unavailable material;
(6) sull good uniformity, purity are high, and process operation is simple, security, reliability are high, and production cost is low, is beneficial to practical large-scale and uses.
Preparation technology of the present invention is rationally convenient, and production cost is low, and safe preparation process is reliable, and reaction is thorough, and the preparing product quality is good, and yield is high, is conducive to large-scale, industrialization production.The present invention provides condition for process industrial, and preparation method of the present invention is simple, and is easy to prepare quick.
Description of drawings
Accompanying drawing is process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Main technique equipment is: indium chloride aqueous solution dosing apparatus, tin chloride solution dosing apparatus, liquid-liquid dispersion mixing equipment, roasting drying plant etc., and wherein the liquid-liquid dispersion mixing equipment is stirring tank, the roasting drying plant is retort furnace.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts the octyl glucosides.During preparation, in the 1000mL water with 10g indium chloride, 2g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 1% InCl
3With 0.2% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 1.6.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is kerosene, and tin chloride is 0.5mL during preparation, and kerosene is 1000mL, and the quality percentage composition that obtains tin chloride solution is 0.1% SnCl
4Kerosin.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 500mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:21.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt pickling process, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 500 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air natural cooling annealing, and the surface that obtains thickness and be 1 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
Embodiment two
Main technique equipment is: basic identical with embodiment one, different is that the liquid-liquid dispersion mixing equipment is ultraemulsifier.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts the decyl glucosides.During preparation, in the 1000mL water with 50g indium chloride, 5g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 5% InCl
3With 0.5% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 2.6.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is gasoline, and tin chloride is 5mL during preparation, and gasoline is 1000mL, and the quality percentage composition that obtains tin chloride solution is 1.0% SnCl
4Gasoline solution.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 120mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be approximately 1:44.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt spin-coating method, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 600 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air quenching, and the surface that obtains thickness and be 20 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
Embodiment three
Main technique equipment is: basic identical with embodiment one, different is that the liquid-liquid dispersion mixing equipment is static mixer.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts the combination of two kinds in Dodecyl Glucoside and tetradecyl glucosides.During preparation, in the 1000mL water with 30g indium chloride, 3g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 3% InCl
3With 0.3% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 2.0.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is C6 alkane, and tin chloride is 2.5mL during preparation, and C6 alkane is 1000mL, and the quality percentage composition that obtains tin chloride solution is 0.5% SnCl
4The C6 alkane solution.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 250mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be approximately 1:25.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt spraying method, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 550 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air natural cooling annealing, and the surface that obtains thickness and be 10 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
Embodiment four
Main technique equipment is: identical with embodiment one.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts the combination of three kinds in octyl glucosides, Alkyl Polyglycoside of Hexadecyl and octadecyl glucosides.During preparation, in the 1000mL water with 20g indium chloride, 4g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 2% InCl
3With 0.4% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 1.8.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is C18 alkane, and tin chloride is 4mL during preparation, and C18 alkane is 1000mL, and the quality percentage composition that obtains tin chloride solution is 0.8% SnCl
4The C18 alkane solution.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 60mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:44.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt pickling process, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 580 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air quenching, and the surface that obtains thickness and be 5 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
Embodiment five
Main technique equipment is: identical with embodiment two.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts Dodecyl Glucoside.During preparation, in the 1000mL water with 40g indium chloride, 2.5g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 4% InCl
3With 0.25% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 2.2.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is C8 alkane, and tin chloride is 1.5mL during preparation, and C8 alkane is 1000mL, and the quality percentage composition that obtains tin chloride solution is 0.3% SnCl
4The C8 alkane solution.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 300mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:47.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt spin-coating method, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 520 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air natural cooling annealing, and the surface that obtains thickness and be 15 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
Embodiment six
Main technique equipment is: identical with embodiment three.
As shown in the figure, a kind of surface has the method for glass preparation of electrically conducting transparent function film, and described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and alkyl glycoside adopts octyl glucosides and decyl glucosides.During preparation, in the 1000mL water with 15g indium chloride, 3g alkyl glycoside and the salinization of employing hydrochloric acid, be made into the 1000mL indium chloride aqueous solution, the quality percentage composition that obtains the indium chloride aqueous solution is 1.5% InCl
3With 0.3% alkyl glycoside.The glucose polymerization degree DP value of alkyl glucose is 2.0.
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and organic solvent is C10 alkane, and tin chloride is 1.5mL during preparation, and C10 alkane is 1000mL, and the quality percentage composition that obtains tin chloride solution is 0.3% SnCl
4The C10 alkane solution.
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution 250mL that the indium chloride aqueous solution 1000mL that the first step preparation is obtained and second step obtain carries out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material; This dispersion system is the dispersion emulsion system.In this dispersion system, with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:21.
(4) glass baseplate surface injecting glue: adopt hard borosilicate glass as glass baseplate, with the washing of hard borosilicate glass substrate surface process, oil removing, ash disposal and washing pre-treatment, behind 105 ℃ of drying 10 min, obtain cleaning, transparent, traceless glass substrate first.Adopt spraying method, profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue on the glue injecting film through the glass baseplate surface of surface preparation, is formed glued membrane on the surface of glass baseplate.
(5) thermal treatment film forming: the injecting glue glass baseplate that previous step is prepared is placed in the retort furnace, begins heating from room temperature, reaches cooling behind 560 ℃ of the maturing temperatures, forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate.
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air quenching, and the surface that obtains thickness and be 12 μ m has the glass of electrically conducting transparent function film.This product is used or electric light source function glassy product as solar-energy photo-voltaic cell.
In addition to the implementation, embodiments of the invention are many in addition, alkyl glucoside surfactant described in the preparation of the first step indium chloride aqueous solution also can adopt any one in octyl glucosides, decyl glucosides, Dodecyl Glucoside, tetradecyl glucosides, n-Hexadecane glucoside and the octadecyl glucosides, perhaps be other arbitrarily several combinations, the glucose polymerization degree DP value of alkyl glycoside can also be other value in 1.6～2.6.Organic solvent described in the preparation of second step tin chloride solution can also be other alkane in the C6-C18 alkane.The profit shape liquid-liquid dispersion system that a certain amount of indium chloride aqueous solution of employing that obtains described in the 3rd step batching is mixed and a certain amount of tin chloride organic solution form is with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio can also be other numerical value in 1:20～50.Roasting drying temperature described in the 5th step thermal treatment film forming can also be other numerical value in 500～600 ℃.Obtaining the thickness of glass that the surface has the electrically conducting transparent function film and can also be other numerical value among 1～20 μ m described in the 5th step thermal treatment film forming.
Except the various embodiments described above, embodiment of the present invention also have a lot, can't be exhaustive, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (9)
1. a surface has the method for glass preparation of electrically conducting transparent function film, it is characterized in that described method steps is as follows:
(1) indium chloride aqueous solution preparation: indium chloride and water and alkyl glucoside surfactant are made into the aqueous solution, and the quality percentage composition that obtains the indium chloride aqueous solution is 1～5% InCl
3With 0.2～0.5% alkyl glycoside;
(2) tin chloride solution preparation: tin chloride and organic solvent are made tin chloride solution, and the quality percentage composition that obtains tin chloride solution is 0.1～1.0% SnCl
4Organic solution;
(3) batching is mixed: in the liquid-liquid dispersion mixing equipment, the tin chloride organic solution that the indium chloride aqueous solution that the first step preparation is obtained and second step obtain is carried out dispersing and mixing, obtains profit shape liquid-liquid dispersion system material;
(4) glass baseplate surface injecting glue: profit shape liquid-liquid dispersion obtained in the previous step system material injecting glue through on the glass baseplate of surface preparation, is formed glued membrane on the surface of glass baseplate;
(5) thermal treatment film forming: the injecting glue glass baseplate with previous step prepares forms tin indium oxide ITO transparent conductive film by the roasting drying at glass baseplate;
(6) air cooling: the glass baseplate with tin indium oxide ito thin film obtained in the previous step is cooled to 80～90 ℃ through air cooling annealing or quenching, obtains the glass that the surface has the electrically conducting transparent function film.
2. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the alkyl glucoside surfactant described in the preparation of the first step indium chloride aqueous solution is any one in octyl glucosides, decyl glucosides, Dodecyl Glucoside, tetradecyl glucosides, n-Hexadecane glucoside and the octadecyl glucosides, perhaps be arbitrarily several combination, the glucose polymerization degree DP value of alkyl glucose is 1.6～2.6.
3. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the organic solvent described in the preparation of second step tin chloride solution is any one in kerosene, gasoline or the C6-C18 alkane.
4. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the profit shape liquid-liquid dispersion system that obtains described in the 3rd step batching is mixed, and with SnCl
4And InCl
3Meter, SnCl
4With InCl
3Mol ratio be 1:20～50.
5. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: liquid-liquid dispersion mixing equipment described in the 3rd step batching is mixed is any one in stirring tank, ultraemulsifier or the static mixer.
6. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the 4th step glass baseplate surface injecting glue is injecting glue on the glue injecting film on glass baseplate surface, and injecting glue employing method is any one in dipping, spin coating or the spraying method.
7. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the glass baseplate of processing through oil removing and ash disposal for the surface through the glass baseplate of surface preparation described in the 4th step glass baseplate surface injecting glue.
8. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: the roasting drying temperature described in the 5th step thermal treatment film forming is 500～600 ℃.
9. described surface has the method for glass preparation of electrically conducting transparent function film according to claim 1, it is characterized in that: described in the 5th step thermal treatment film forming to obtain the thickness of glass that the surface has the electrically conducting transparent function film be 1～20 μ m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962436A (en) * | 2018-07-06 | 2018-12-07 | 无锡众创未来科技应用有限公司 | The method for manufacturing transparent conductive film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6936100B2 (en) * | 2002-09-30 | 2005-08-30 | Fuji Photo Film Co., Ltd. | Method of producing a crystalline ITO dispersed solution |
| CN1801400A (en) * | 2005-01-07 | 2006-07-12 | 中南大学 | In203-Sn02 nano film coating material and its preparing method |
| US20060247354A1 (en) * | 2004-12-15 | 2006-11-02 | Ping He | Method of manufacturing nanoscale metal oxide particles |
| CN101056716A (en) * | 2004-11-10 | 2007-10-17 | 大日本印刷株式会社 | Process for forming metal oxide films |
| CN101631746A (en) * | 2007-03-19 | 2010-01-20 | 韩国电子通信研究院 | Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same |
| US8679587B2 (en) * | 2005-11-29 | 2014-03-25 | State of Oregon acting by and through the State Board of Higher Education action on Behalf of Oregon State University | Solution deposition of inorganic materials and electronic devices made comprising the inorganic materials |
-
2011
- 2011-08-23 CN CN2011102423134A patent/CN102951852A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6936100B2 (en) * | 2002-09-30 | 2005-08-30 | Fuji Photo Film Co., Ltd. | Method of producing a crystalline ITO dispersed solution |
| CN101056716A (en) * | 2004-11-10 | 2007-10-17 | 大日本印刷株式会社 | Process for forming metal oxide films |
| US20060247354A1 (en) * | 2004-12-15 | 2006-11-02 | Ping He | Method of manufacturing nanoscale metal oxide particles |
| CN1801400A (en) * | 2005-01-07 | 2006-07-12 | 中南大学 | In203-Sn02 nano film coating material and its preparing method |
| US8679587B2 (en) * | 2005-11-29 | 2014-03-25 | State of Oregon acting by and through the State Board of Higher Education action on Behalf of Oregon State University | Solution deposition of inorganic materials and electronic devices made comprising the inorganic materials |
| CN101631746A (en) * | 2007-03-19 | 2010-01-20 | 韩国电子通信研究院 | Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962436A (en) * | 2018-07-06 | 2018-12-07 | 无锡众创未来科技应用有限公司 | The method for manufacturing transparent conductive film |
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