CN103803808A - Method for large-area preparation of transparent conductive film glass - Google Patents
Method for large-area preparation of transparent conductive film glass Download PDFInfo
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- CN103803808A CN103803808A CN201410062731.9A CN201410062731A CN103803808A CN 103803808 A CN103803808 A CN 103803808A CN 201410062731 A CN201410062731 A CN 201410062731A CN 103803808 A CN103803808 A CN 103803808A
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Abstract
The invention relates to a method for large-area preparation of transparent conductive film glass, which comprises the steps that a glass plate (1) enters a first liquid-phase roller coating film plating (5a) and is coated with a silicon oxide liquid precursor to form a middle film layer with thickness of 30-150nm; the glass plate enters a second liquid-phase roller coating film plating machine (5b), and the middle film layer of the glass plate is coated with a tin oxide-doped liquid precursor to form a tin oxide-doped transparent conductive film with thickness of 360-1,200nm; the glass plate is subjected to heat treatment for at least 3 minutes at a temperature of 400-700 DEG C. By adopting the method provided by the invention, the obtained transparent conductive film has the characteristics of high transmittance, high conductivity and self-suede structure, and is widely applied to thin-film solar cells and low-radiation energy-saving glass. The method provided by the invention realizes simple, low-cost and large-area uniform preparation of transparent conductive film glass.
Description
Technical field
The present invention relates to a kind of big area and prepare the method for transparent conducting film glass, this glass is mainly used in the field such as thin-film solar cells and low radiation energy-saving glass.
Background technology
Along with being on the rise of energy dilemma and traditional energy environmental pollution; develop renewable clear energy sources and become one of Major Strategic problem in international coverage; sun power is inexhaustible, nexhaustible clear energy sources; therefore, researches and exploitation sun power becomes the energy strategy decision-making of countries in the world government Sustainable development.Wherein, thin-film solar cells is with advantages such as its low cost, easy big area realizations, in solar cell, occupy critical positions, have a extensive future, and doped sno_2 nesa coating has advantages of high permeability, high conductivity and self suede structure, it is used widely in thin-film solar cells and low radiation energy-saving glass.
Chinese patent CN1962510 sets forth a kind of method of utilizing spray pyrolysis to prepare tin oxide transparent conductive film.The method is utilized SnCl
22H
2o and NH
4f has obtained the SnO 2 thin film of resistance 20 Ω/, but the method film forming speed is too low, need be through repeatedly repeatedly spraying the nesa coating that just can be met requirement.Chinese patent CN101140143 has set forth method and the equipment of ultrasound nebulization method preparing large area transparent conductive film.The method is passed through supersonic spraying, on static hot glass surface, deposit doped sno_2 fluorine nesa coating, rete specific conductivity and transmitance are higher, but the method does not relate to the preparation of intershield layer, simultaneously, the sample rete that the method obtains is even not and size is less, should not carry out suitability for industrialized production.Chinese patent CN101188149 has set forth a kind of method of radio-frequency magnetron sputter method at the AZO nesa coating of glass surface codeposition Ce doping of utilizing, and having obtained resistivity is 7～8 × 10
-4Ω cm, in 400～800nm visible-range, average transmittances reaches 80～90% nesa coating, but the nesa coating that the method obtains itself does not have suede structure, need after matte is processed, just can be applied to electrode of solar battery.Chinese patent CN1145882 has set forth a kind of mode by chemical vapour deposition on the mobile sheet glass of 630～640 ℃ or float glass matrix, utilizes tin tetrachloride and water pre-mixing to form single air-flow, the method for deposition stannic oxide rete.The reactive material that the method relates to requires at high temperature moment decomposition reaction, wayward, complex process.
Summary of the invention
The object of the invention is the deficiency existing in order to overcome prior art, a kind of preparation method of large-area transparent conductive film glass is provided.
The present invention has adopted following technical scheme:
a kind of big area is prepared the method for transparent conducting film glass, it is characterized in that comprising the following steps:
(1). sheet glass enters the first liquid phase roller coat coating equipment, utilizes liquid phase rolling method, applies silicon oxide liquid precursor on sheet glass, then enters and in levelling section, carries out levelling surface drying, the intermediate thin rete that to form thickness be 30～150nm;
(2). the sheet glass of levelling surface drying enters second liquid phase roller coat coating equipment, utilizes liquid phase rolling method, on the intermediate thin rete of sheet glass, applies doped sno_2 liquid precursor, the doped sno_2 transparent conductive film that formation thickness is 360-1200nm;
(3). the sheet glass that has plated film is sent in aftertreatment section and is heat-treated, and post-processing temperature is 400～700 ℃, and heat treatment time is no less than 3 minutes.
On the basis of technique scheme, can there is following further technical scheme:
(1). the chemical formula of described silicon oxide liquid precursor is R
uo
vsi
m, wherein R is straight or branched or cycloalkyl, u=3-8, v=0-4, m=1-4;
(2). described doped sno_2 liquid precursor comprises:
Stannic oxide liquid precursor, its chemical formula is R
nsnCl
4-n, wherein R is straight or branched or cycloalkyl, n=0,1 or 2, Xi Yuan be R
nsnCl
4-n;
Doping liquid precursor, comprises and the precursor of fluorine mainly contains trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, Neutral ammonium fluoride; The precursor of antimony, mainly contains butter of antimony, antimony pentachloride;
Solvent in liquid precursor is water, alcohols or its mixture.
The preferred tin tetrachloride of stannic oxide liquid precursor or monobutyl-tin-trichloride;
The preferred tetraethoxy of silicon oxide liquid precursor or methyl silicate.
In the present invention, the main component of nesa coating is SnO 2 thin film, in order to improve the electric conductivity of rete, need in rete, adulterate and form semi-conductor conductive film, and the composition of doping has fluorine, antimony etc.; Meanwhile, the stannic oxide in the present invention is mixed at least 360nm of thickness of fluorine nesa coating, is preferably not less than 400nm, and the upper limit of thickness has no particular limits, and is generally no more than 1200nm.
In the present invention, between glass substrate and top layer SnO 2 thin film, deposit one deck intermediate thin rete, the object of this intermediate thin rete, on the one hand, be in nesa coating, to cause conducting film alkalosis in order to prevent that alkalimetal ion in glass substrate is diffused into, thereby affect specific conductivity and the light transmission of rete; On the other hand, be the interference of light striped in order to eliminate rete.
Intermediate film is deposited upon on sheet glass, and the main component of this rete is silicon-dioxide etc.The suitable thickness of middle rete is 30～150nm, and preferably 50～100nm, if rete is too thin, can not play alkalimetal ion shielding effect, thereby affect the specific conductivity of transparency conducting layer 3, middle layer can not be too thick simultaneously, the too thick visible light transmissivity that can affect electropane.
In the present invention, the post-processing temperature that applies doped sno_2 transparent conducting film glass with liquid phase rolling method is 400～700 ℃, and in order to obtain higher specific conductivity, at least 500 ℃ of general temperature, are preferably no less than 550 ℃.Heat treated object is to promote the abundant growth of film crystal grain to cultivate.Heat treatment time is no less than 3 minutes, is preferably no less than 8 minutes.
In the present invention, the chemical formula of preparing nesa coating stannic oxide liquid precursor used is R
nsnCl
4-n, wherein R is straight or branched or cycloalkyl, n=0,1 or 2; Tin source R
nsnCl
4-nconventional as organotins such as inorganic tin or monobutyl-tin-trichloride such as tin tetrachloride.
The chemical formula of the liquid precursor of silicon oxide is R
uo
vsi
m, wherein R is straight or branched or cycloalkyl, u=3-8, v=0-4, m=1-4.Typical in tetraethoxy (TEOS), methyl silicate (TMOS) etc.
The precursor of fluorine comprises trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, Neutral ammonium fluoride etc.; The precursor of antimony comprises butter of antimony, antimony pentachloride etc.There is the specific conductivity that can improve FTO nesa coating as doping in them.
Solvent in liquid precursor liquid is water, alcohols (ethanol, propyl alcohol etc.) or its mixture.
The present invention, by changing the formula of precursor mixed solution, can control the quality of rete, improves the function of rete.
Technique of the present invention is simple, and equipment and raw materials cost are low, and easy handling is convenient to industrialized mass.The present invention adopts suitable liquid precursor to be coated with doped sno_2 transparent conductive oxide film at mobile glass surface, the nesa coating obtaining has the feature of high permeability, high conductivity and self suede structure, and in thin-film solar cells and low radiation energy-saving glass, application is extremely wide.The present invention realizes simply, low cost, Large-Area-Uniform are prepared transparent conducting film glass.
Fig. 1 is the film layer structure schematic diagram of nesa coating of the present invention;
Fig. 2 is process flow diagram of the present invention.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, the present invention is simultaneously not restricted to these embodiment.
The flow process of technique of the present invention is with reference to Fig. 1, Fig. 2, sheet glass 1 enters liquid phase roller coat coating equipment 5a by upper slice platform 4 by transfer roller 8, on sheet glass 1, apply one deck intermediate thin rete 2, then enter and in levelling section 6, carry out levelling surface drying, and then glass enters liquid phase roller coat coating equipment 5b, apply herein certain thickness doped sno_2 functional layer film 3, the glass that has finally plated film is sent in aftertreatment section 7 and is heat-treated, in order to guarantee that rete nucleus obtains fully growth and cultivates, thermal treatment temp need be set in advance in a suitable temperature range.
In the present embodiment, glass substrate is 3.2mm ultra-clear glasses; Utilize first liquid phase roller coat coating equipment, at a normal atmosphere, temperature is 25 ℃, under the environment of humidity 40%, sheet glass translational speed 6m/min, roller rotating speed 7m/min, has been coated with layer of silicon dioxide intermediate thin rete with the hydrolysate silicon dioxide gel of tetraethoxy at glass surface; Then utilize second liquid phase roller coat coating equipment, at a normal atmosphere, temperature is 25 ℃, under the environment of humidity 40%, sheet glass translational speed 4m/min, roller rotating speed 8m/min, by the mixing solutions of tin tetrachloride and Neutral ammonium fluoride (ethanol is solvent), be coated on glass surface, form stannic oxide and mix fluorine (FTO) nesa coating.The post-processing temperature of glass substrate is 560 ℃, and finishing time is 10min;
After measured, intermediate layer thickness is 85nm, and FTO electrically conducting transparent layer thickness is 670nm, and the square resistance of rete is 7.6 Ω/, and the carrier concentration of rete is that n is 7.8 × 10
20/ cm
3, the visible light transmissivity of FTO transparent conducting film glass is 82%.Therefore known, this FTO transparent conducting film glass has good optics, electric property, can be applicable to thin-film solar cells and low radiation energy-saving glass completely.
In the present embodiment, glass substrate is 4mm ultra-clear glasses; Utilize first liquid phase roller coat coating equipment, at a normal atmosphere, temperature is 27 ℃, under the environment of humidity 44%, sheet glass translational speed 7m/min, roller rotating speed 8m/min, has been coated with layer of silicon dioxide intermediate thin rete with the hydrolysate silicon dioxide gel of methyl silicate at glass surface; Then utilize second liquid phase roller coat coating equipment, at a normal atmosphere, temperature is 27 ℃, under the environment of humidity 44%, sheet glass translational speed 6m/min, roller rotating speed 9m/min, is coated in the mixing solutions of monobutyl-tin-trichloride and butter of antimony (mixed solution of the third alcohol and water is solvent) on glass surface, forms stannic oxide and mixes antimony (ATO) nesa coating.The post-processing temperature of glass substrate is 580 ℃, and finishing time is 12min;
After measured, intermediate layer thickness is 106nm, and ATO electrically conducting transparent layer thickness is 710nm, and the square resistance of rete is 7.0 Ω/, and the carrier concentration of rete is that n is 8.1 × 10
20/ cm
3, the visible light transmissivity of ATO transparent conducting film glass is 79%.Therefore known, this ATO transparent conducting film glass has good optics, electric property, can be applicable to thin-film solar cells and low radiation energy-saving glass completely.
Claims (4)
1. big area is prepared a method for transparent conducting film glass, it is characterized in that comprising the following steps:
(1). sheet glass enters the first liquid phase roller coat coating equipment, utilizes liquid phase rolling method, applies silicon oxide liquid precursor on sheet glass, then enters and in levelling section, carries out levelling surface drying, the intermediate thin rete that to form thickness be 30～150nm;
(2). the sheet glass of levelling surface drying enters second liquid phase roller coat coating equipment, utilizes liquid phase rolling method, on the intermediate thin rete of sheet glass, applies doped sno_2 liquid precursor, the doped sno_2 transparent conductive film that formation thickness is 360-1200nm;
(3). the sheet glass that has plated film is sent in aftertreatment section and is heat-treated, and thermal treatment temp is 400～700 ℃, and heat treatment time is no less than 3 minutes.
2. a kind of big area according to claim 1 is prepared the method for transparent conducting film glass, it is characterized in that:
(1). the chemical formula of described silicon oxide liquid precursor is R
uo
vsi
m, wherein R is straight or branched or cycloalkyl, u=3-8, v=0-4, m=1-4;
(2). described doped sno_2 liquid precursor, comprising:
A, stannic oxide liquid precursor, its chemical formula is R
nsnCl
4-n, wherein R is straight or branched or cycloalkyl, n=0,1 or 2, Xi Yuan be R
nsnCl
4-n;
B, doping liquid precursor, comprise and the precursor of fluorine mainly contain trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, Neutral ammonium fluoride;
Solvent in c, liquid precursor is water, alcohols or its mixture.
3. a kind of big area according to claim 2 is prepared the method for transparent conducting film glass, it is characterized in that:
The preferred tin tetrachloride of stannic oxide liquid precursor or monobutyl-tin-trichloride;
The preferred tetraethoxy of silicon oxide liquid precursor or methyl silicate.
4. a kind of big area according to claim 2 is prepared the method for transparent conducting film glass, it is characterized in that: described in comprise the precursor of fluorine, replace with the precursor of antimony, mainly contain butter of antimony, antimony pentachloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310790A (en) * | 2014-09-28 | 2015-01-28 | 中国建材国际工程集团有限公司 | Preparation method of large-area transparent conducting film glass |
| CN104445987A (en) * | 2014-10-30 | 2015-03-25 | 中国建材国际工程集团有限公司 | Method for preparing thermochromism intelligent membrane glass |
| CN104529537A (en) * | 2015-01-08 | 2015-04-22 | 河南耀发光电有限公司 | Production method for conductive ceramic |
| CN106542743A (en) * | 2016-10-27 | 2017-03-29 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of Graphene glass |
| CN106542746A (en) * | 2016-10-27 | 2017-03-29 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of nano-silver thread transparent conducting film glass |
| CN106886114A (en) * | 2017-04-06 | 2017-06-23 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of electrochromic intelligent glass |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310790A (en) * | 2014-09-28 | 2015-01-28 | 中国建材国际工程集团有限公司 | Preparation method of large-area transparent conducting film glass |
| CN104445987A (en) * | 2014-10-30 | 2015-03-25 | 中国建材国际工程集团有限公司 | Method for preparing thermochromism intelligent membrane glass |
| CN104529537A (en) * | 2015-01-08 | 2015-04-22 | 河南耀发光电有限公司 | Production method for conductive ceramic |
| CN104529537B (en) * | 2015-01-08 | 2018-10-30 | 河南耀发光电有限公司 | A kind of production method of conductivity ceramics |
| CN106542743A (en) * | 2016-10-27 | 2017-03-29 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of Graphene glass |
| CN106542746A (en) * | 2016-10-27 | 2017-03-29 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of nano-silver thread transparent conducting film glass |
| CN106886114A (en) * | 2017-04-06 | 2017-06-23 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of electrochromic intelligent glass |
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Application publication date: 20140521 |
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