CN102424533B - Difunctional coated glass capable of reducing visible light reflection and reflecting near infrared ray and preparation method thereof - Google Patents
Difunctional coated glass capable of reducing visible light reflection and reflecting near infrared ray and preparation method thereof Download PDFInfo
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- CN102424533B CN102424533B CN201110273053.7A CN201110273053A CN102424533B CN 102424533 B CN102424533 B CN 102424533B CN 201110273053 A CN201110273053 A CN 201110273053A CN 102424533 B CN102424533 B CN 102424533B
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Abstract
The invention relates to a difunctional coated glass capable of reducing visible light reflection and reflecting near infrared ray and a preparation method thereof. A film structure of the difunctional coated glass is one of the following two: a. a one side coated glass: using glass as a substrate and arranging a layer of silica isolated film, a layer of transparent conductive semiconductor oxide film and a layer of porous silica film successively; b. a double-faced coated glass: using glass as a substrate and successively arranging a layer of silica separating layer, a layer of transparent conductive semiconductor oxide film and a layer of porous silica film on two sides of the glass respectively. Compared with an uncoated photovoltaic seal glass, the difunctional coated glass has a visible light transmissivity raised by 2.0-4.0% and near infrared ray reflectivity raised by 70-75%. The invention can be widely applied to silicon system solar cell packaging and glass for building industry and has a promising prospect.
Description
Technical field
The invention belongs to for silicon is the fields such as packaging glass of solar cell, is specifically related to a kind of coated glass simultaneously on glass substrate with antireflective visible ray and the difunctional composite film of reflection near infrared ray and preparation method thereof.
Background technology
Along with human society carbon emission amount day by day increase and conventional energy resources day by day exhausted, greatly developing cleaning new energy has become that social sustainable development is realized in countries in the world and the civilized only way of marching toward.Photovoltaic is one of clean energy, has obtained using widely.Silicon is solar cell at present, comprises monocrystaline silicon solar cell, polysilicon solar cell and non-crystalline silicon/microcrystalline silicon film battery, has obtained application on a large scale.Crystalline silicon band gap is about 1.12eV, and corresponding 1087nm wavelength, that is to say, the solar spectrum that is less than 1087nm can produce photovoltaic effect, and its optimal response wavelength is in 800～900nm scope; The band gap of non-crystalline silicon is in about 1.7eV, corresponding 730nm wavelength, and the solar spectrum that is less than 730nm can produce photovoltaic effect, and its optimal response wavelength is in 450～650nm scope.Observe on the ground
solar radiationspectral band scope is approximately 295～2500nm, is shorter than 295nm and the solar radiation that is greater than 2500nm wavelength, and the strong absorption because of ozone, aqueous vapor and other atmospheric molecules in earth atmosphere, can not arrive ground.The solar spectral that arrives ground mainly contains three parts and forms, and its middle-ultraviolet lamp accounts for 3% left and right, visible ray accounts for 42% left and right and infrared rays accounts for 55% left and right.Visible ray and ultraviolet ray add up to the spectrum of 45% left and right to produce photovoltaic response, and 55% near infrared ray makes cell piece heating, heats up.Crystal silicon is that the temperature power coefficient of solar cell is :-(0.35～0.50) %/℃, 1 ℃ of the every rising of temperature, output rating declines 0.35～0.50%, and the temperature power coefficient of amorphous silicon film battery is :-0.20%/℃, 1 ℃ of the every rising of temperature, output rating declines 0.20%.Therefore, at silicon, be in solar module, need to avoid or slow down silicon chip or silicon film temperature and rise, this just needs to stop or reduces infrared transmission in sunlight in silicon cell or thin film silicon.
Meanwhile, in order to improve battery efficiency, need visible ray to be as often as possible transmitted in silicon cell or thin film silicon.At the uncoated photovoltaic encapsulation antireflective visible ray film that is coated with on glass, can improve the generated output of battery.According to statistics, the transmission of visible light of packaged glass improves 2%, just can increase by 1～2% generated output.
Therefore, in order to improve as much as possible the photovoltaic effect that silicon is solar cell, improve photovoltaic efficiency of conversion, packaged glass needs the near infrared ray in reflection (or cut-off) solar spectrum, to prevent that the infrared rays that is transmitted to cell piece from causing cell piece temperature to raise, reduce the efficiency of conversion of battery; Need to improve the transmission of visible light of packaged glass simultaneously, improve the efficiency of conversion of battery.It is difunctional with reflection near infrared ray that this just needs the packaged glass of battery to have antireflective visible ray simultaneously.Object of the present invention is invented a kind of have antireflective visible ray and reflection near infrared ray bifunctional coated glass and preparation method thereof exactly simultaneously.
By By consulting literatures, contrast, bifunctional coated glass has " having bifunctional transparent coating glass of the static of preventing and ultraviolet-cutoff and preparation method thereof " (application (patent) number: 201010562026.7) at present, " coated glass with dual function of cutting-off ultraviolet ray/reflecting infrared ray and preparation method thereof " (patent of invention ZL200410061018.9), " visible light anti-reflection and ultraviolet radiation cut-off bifunctional coated glass and preparation method thereof " (patent of invention 200710053367.X), and sputtering method prepare only have single function and expensive ITO " heat insulation, the preparation method of frost-removing coated glass " (application number: 98100128.9), metallic membrane is as reflective coating and the coated glass of the durable use of monolithic for a long time.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of simultaneously have antireflective visible ray and reflection near infrared ray bifunctional coated glass and preparation method thereof.This coated glass has that near infrared ray reflective rate is high, visible reflectance is low simultaneously, and (or transmission of visible light is high) is difunctional; And the preparation method of visible light anti-reflection/near infrared ray reflective bifunctional coated glass simply, does not need expensive vacuum sputtering equipment, only take chemical process: one side spraying method or the preparation of two-sided dip-coating method, and the rete of preparation, 610～650 ℃ of thermal treatments 2.5～3.0 minutes, makes rete good endurance.
Technical scheme: the film layer structure of antireflective visible ray of the present invention and reflection near infrared ray bifunctional coated glass is one of following two kinds:
A. one-side coated glass: take glass as substrate, in order on glass, silicon-dioxide separating film layer, electrically conducting transparent conductor oxidate rete, porous silica film layer are set;
B. double-sided coated glass: take glass as substrate, order arranges silicon-dioxide sealing coat, electrically conducting transparent conductor oxidate rete, porous silica film layer respectively on the two sides of glass.
In described silicon-dioxide separating film layer, volume hole is between 5～20%, and thicknesses of layers is: 10～25 nanometers.
Described electrically conducting transparent conductor oxidate rete, comprises stannic oxide composite zinc oxide or fluorine-doped tin oxide F:SnO
2, thicknesses of layers is: 75～400 nanometers.
In described porous silica film layer, volumetric porosity is at 15-30%, and thicknesses of layers is: 80～180 nanometers.
When antireflective visible ray of the present invention is one-side coated glass employing one side spraying method with the preparation method who reflects near infrared ray bifunctional coated glass, first clean glass sheet is heated to 300～450 ℃, then spray the silica containing spray coating liquor of the first layer, form silicon-dioxide separating film layer; On the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, form electrically conducting transparent conductor oxidate rete; Then on the second layer, spray the 3rd layer of silica containing spray coating liquor, utilize the volatile quantity of liquid in spray coating liquor to form porous silica film layer; Finally plate state trilamellar membrane sheet glass 610～650 ℃ of thermal treatments 2.5～3.0 minutes.
The preparation method of antireflective visible ray of the present invention and reflection near infrared ray bifunctional coated glass is that double-sided coated glass is while adopting two-sided dip-coating method, first clean glass sheet being flooded to the first layer is silica containing steeping fluid, after lifting, at 150 ℃, be dried, form silicon-dioxide sealing coat; Then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, after lifting, at 150 ℃, be dried, form electrically conducting transparent conductor oxidate rete; On the second layer, flooding the 3rd layer is silica containing steeping fluid again, utilizes the volatile quantity of liquid in steeping fluid to form porous silica film layer, finally plate state trilamellar membrane sheet glass 610～650 ℃ of thermal treatments 2.5～3.0 minutes.
The spray coating liquor of electrically conducting transparent conductor oxidate or steeping fluid adopt fluorine-doped tin oxide F:SnO
2, by SnCl
45H
2o, NH
4f, second alcohol and water form, and inhibitor is made in acid, and second alcohol and water is solvent, is converted into molar ratio to be: Sn:F=1:0.1～0.3, fluorine-doped tin oxide F:SnO in spray coating liquor or steeping fluid
2solid content concentration is at 0.5mol/L.
The spray coating liquor of electrically conducting transparent conductor oxidate or steeping fluid adopt stannic oxide composite zinc oxide, by SnCl
45H
2o, Zn (CH
3cOO)
22H
2o, second alcohol and water form, and second alcohol and water is solvent, fluorine-doped tin oxide F:SnO in spray coating liquor or steeping fluid
2solid content concentration is at 0.5mol/L, mol ratio Zn:Sn=2:1～2.5:1.
Beneficial effect: plate on glass substrate with spraying or dip-coating method: the effect of the first tunic is the metal ion diffusion cutting off in glass, in case affect the performance of the second layer; The effect of the second tunic is reflection near infrared ray; The specific refractory power of the 3rd layer of porous silica film is low, and its effect is to mate, reduce the reflectivity (raising visible light transmissivity) of visible ray on face with the first and second tunics.It is difunctional with reflection near infrared ray that coated glass of the present invention can have antireflective visible ray simultaneously, and preparation method's technique simple and flexible; Compare with sputter coating method, cost of equipment is low.Adopt 610～650 ℃ of thermal treatment plated films, can make the combination of film and glass more firm, rete good endurance.
The transmission of visible light of coated glass of the present invention is compared with uncoated, and the transmission of visible light in solar spectrum improves 2.0～4.0%, and near infrared ray reflective rate reaches 70～75%.
The present invention is that solar cell encapsulation has a wide range of applications aspect glass material and building industry at silicon, has a extensive future.
Embodiment
Visible light anti-reflection/near infrared ray reflective bifunctional coated glass, comprises glass substrate, is coated with successively silicon-dioxide sealing coat, electrically conducting transparent conductor oxidate rete, porous silica film layer on glass substrate.
In described silicon-dioxide separating film layer, volumetric porosity is at 5-20%, and thicknesses of layers is 10～25 nanometers; Described electrically conducting transparent conductor oxidate rete, comprises stannic oxide composite zinc oxide layer or fluorine-doped tin oxide (F:SnO
2) layer, thicknesses of layers is 75～400 nanometers; In described porous silica film layer, volumetric porosity is at 15-30%, and thicknesses of layers is 80～180 nanometers.
The preparation method of visible light anti-reflection/near infrared ray reflective coated glass, is characterized in that comprising the steps:
1) first treating film-coated glass substrate cleans, is dried.
2) then with spraying method temperature be in 300～450 ℃ of clean glass sheet or dipping method of pulling up in room temperature clean glass sheet, be coated with respectively single face film or two-sided rete:
A) preparation is for being coated with spray coating liquor or the steeping fluid of silicon-dioxide sealing coat, spray coating liquor or steeping fluid are by organosilicon (for example: tetraethoxy), second alcohol and water forms, with acid, as catalyzer, after in liquid, silicone content is converted into silicon-dioxide, shared mass percent is: 3～10%.
B) preparation is for being coated with spray coating liquor or the steeping fluid of electrically conducting transparent conductor oxidate, wherein fluorine: the spray coating liquor of stannic oxide rete or steeping fluid are by SnCl
45H
2o, NH
4f, second alcohol and water (ethanol: water=10:1(mol ratio)) form, and inhibitor is made in acid, is converted into molar ratio to be: Sn:F=1:0.1～0.3, strength of fluid 0.5mol/L; The spray coating liquor of stannic oxide-zinc oxide film or steeping fluid are by SnCl
45H
2o, Zn (CH
3cOO)
22H
2o, second alcohol and water (ethanol: water=10:1(mol ratio)) form, and strength of fluid is at 0.5mol/L, the mol ratio Zn:Sn=2:1 of Zn and Sn in liquid.
C) preparation is for being coated with spray coating liquor or the steeping fluid of porous silica film layer, spray coating liquor or steeping fluid are by silicon ester (for example: tetraethoxy), water and ethanol forms, with ammoniacal liquor, make catalyzer, in spray coating liquor or steeping fluid, the content of silicon is converted into the massfraction of silicon-dioxide and is: 3～10%.
D) pickling process plated film: under normal pressure, first in clean glass sheet, flood the first layer containing the steeping fluid of silicon-dioxide sealing coat, lift and 150 ℃ dry 1 minute, then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, lift and 150 ℃ dry 1 minute, on the second layer, flood again the 3rd layer of steeping fluid containing silica coating, finally the sheet glass of plating trilamellar membrane 610～650 ℃ of thermal treatments 2.5～3.0 minutes.
E) or use spraying method plated film: under normal pressure, first clean glass sheet is heated to 300～450 ℃, then spray the first layer containing silicon-dioxide sealing coat spray coating liquor, on the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, then on the second layer, spray the 3rd layer of spray coating liquor containing silica coating, finally the sheet glass of plating trilamellar membrane 610～650 ℃ of thermal treatments 2.5～3.0 minutes.
F) according to thicknesses of layers, determine that spray time or dipping lift number of times.
Example:
Treating film-coated glass substrate cleans, is dried; Glass substrate is of a size of: 500 * 500 * 3.2, and transmission of visible light is 91.60%.
Example 1:
The coated glass simultaneously with spraying method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation spray coating liquor.In the first layer spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 3.0%.In second layer spray coating liquor, the molar ratio of Sn and F is: Sn:F=1:0.1.In the 3rd layer of spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 3.0%.
2) under normal pressure, first clean glass substrate is heated to 300 ℃, then spray the first layer containing the spray coating liquor of silicon-dioxide sealing coat, on the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, then on the second layer, spray the 3rd layer of spray coating liquor containing silica coating, finally the glass substrate of plating trilamellar membrane 610 ℃ of thermal treatments 2.5 minutes.Fig. 1 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 10nm, volumetric porosity 5%; Second layer thickness 80nm; The volumetric porosity 15% of the 3rd layer of porous silica film layer, thickness 80nm; Visible light transmissivity 93.7%, near infrared ray reflective rate 70%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 2:
The coated glass simultaneously with dip-coating method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation steeping fluid.In the first layer steeping fluid, silicone content is converted into the shared mass percent of silicon-dioxide and is: 3.0%.In second layer steeping fluid, Sn and F molar ratio are: Sn:F=1:0.1.In the 3rd layer of steeping fluid, silicone content is converted into the shared mass percent of silicon-dioxide and is: 3.0%.
2) under normal pressure, first in clean glass sheet, flooding the first layer contains silicon-dioxide sealing coat steeping fluid, lifts and is dried 1 minute at 150 ℃, then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, lift and 150 ℃ dry 1 minute, on the second layer, flood again the 3rd layer of steeping fluid containing silica coating, finally the glass substrate of plating trilamellar membrane 610 ℃ of thermal treatments 2.5 minutes.Fig. 2 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 10nm, volumetric porosity 5%; Second layer thickness 80nm; The volumetric porosity 15% of the 3rd layer of porous silica film layer, thickness 80nm; Visible light transmissivity 94.2%, near infrared ray reflective rate 72%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 3:
The coated glass simultaneously with spraying method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation spray coating liquor.In the first layer spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 5.0%.In second layer spray coating liquor, the molar ratio of Sn and F is: Sn:F=1:0.2.In the 3rd layer of spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 6.0%.
2) under normal pressure, first clean glass sheet is heated to 400 ℃, then spray the first layer containing silicon-dioxide sealing coat spray coating liquor, on the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, then on the second layer, spray the 3rd layer of spray coating liquor containing silica coating, finally the sheet glass of plating trilamellar membrane 630 ℃ of thermal treatments 2.7 minutes.Fig. 1 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 20nm, volumetric porosity 15%; Second layer thickness 300nm; The volumetric porosity 25% of the 3rd layer of porous silica film layer, thickness 130nm; Visible light transmissivity 94.1%, near infrared ray reflective rate 73%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 4:
The coated glass simultaneously with dip-coating method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation steeping fluid.In the first layer spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 5.0%.In second layer spray coating liquor, the molar ratio of Sn and F is: Sn:F=1:0.2.In the 3rd layer of spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 6.0%.
2) under normal pressure, first in clean glass sheet, flooding the first layer contains silicon-dioxide sealing coat steeping fluid, lifts and is dried 1 minute at 150 ℃, then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, lift and 150 ℃ dry 1 minute, on the second layer, flood again the 3rd layer of steeping fluid containing silica coating, finally the sheet glass of plating trilamellar membrane 630 ℃ of thermal treatments 2.7 minutes.Fig. 2 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 20nm, volumetric porosity 15%; Second layer thickness 300nm; The volumetric porosity 25% of the 3rd layer of porous silica film layer, thickness 130nm; Visible light transmissivity 94.9%, near infrared ray reflective rate 74%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 5:
The coated glass simultaneously with spraying method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation spray coating liquor.In the first layer spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.In second layer spray coating liquor, the molar ratio of Sn and F is: Sn:F=1:0.3.In the 3rd layer of spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.
2) under normal pressure, first clean glass sheet is heated to 450 ℃, then spray the first layer containing silicon-dioxide sealing coat spray coating liquor, on the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, then on the second layer, spray the 3rd layer of spray coating liquor containing silica coating, finally the sheet glass of plating trilamellar membrane 650 ℃ of thermal treatments 3 minutes.Fig. 1 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 25nm, volumetric porosity 20%; Second layer thickness 400nm; The volumetric porosity 30% of the 3rd layer of porous silica film layer, thickness 180nm; Visible light transmissivity 94.5%, near infrared ray reflective rate 74%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 6:
The coated glass simultaneously with dip-coating method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation steeping fluid.In the first layer steeping fluid, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.In second layer spray coating liquor, the molar ratio of Sn and F is: Sn:F=1:0.3.In the 3rd layer of spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.
2) under normal pressure, first in clean glass sheet, flooding the first layer contains silicon-dioxide sealing coat steeping fluid, lifts and is dried 1 minute at 150 ℃, then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, lift and 150 ℃ dry 1 minute, on the second layer, flood again the 3rd layer of steeping fluid containing silica coating, finally the sheet glass of plating trilamellar membrane 650 ℃ of thermal treatments 3.0 minutes.Fig. 2 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 25nm, volumetric porosity 20%; Second layer thickness 400nm; The volumetric porosity 30% of the 3rd layer of porous silica film layer, thickness 180nm; Visible light transmissivity 95.6%, near infrared ray reflective rate 75%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 7:
The coated glass simultaneously with spraying method preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation spray coating liquor.In the first layer spray coating liquor, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.In second layer spray coating liquor, mol ratio Zn:Sn=2:1.In the 3rd layer of spray coating liquor, the massfraction of silicon is: 10%.
2) under normal pressure, first clean glass substrate is heated to 450 ℃, then spray the first layer containing silicon-dioxide sealing coat spray coating liquor, on the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, then on the second layer, spray the 3rd layer of spray coating liquor containing silica coating, finally the glass substrate of plating trilamellar membrane 640 ℃ of thermal treatments 2.5 minutes.Fig. 1 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 25nm, volumetric porosity 20%; Second layer thickness 400nm; The volumetric porosity 30% of the 3rd layer of porous silica film layer, thickness 180nm; Visible light transmissivity 93.7%, near infrared ray reflective rate 70%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Example 8:
The coated glass simultaneously with pickling process preparation with the difunctional composite film of visible light anti-reflection/near infrared ray reflective, comprises the steps:
1) preparation steeping fluid.In the first layer steeping fluid, silicone content is converted into the shared mass percent of silicon-dioxide and is: 10%.In second layer steeping fluid, mol ratio Zn:Sn=2:1.In the 3rd layer of steeping fluid, the massfraction of silicon is: 10%.
2) under normal pressure, first on clean glass substrate, flood the first layer containing the steeping fluid of silicon-dioxide sealing coat, lift and 150 ℃ dry 1 minute, then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, lift and 150 ℃ dry 1 minute, on the second layer, flood again the 3rd layer of steeping fluid containing silica coating, finally the sheet glass of plating trilamellar membrane 640 ℃ of thermal treatments 2.5 minutes.Fig. 2 is shown in by film layer structure schematic diagram after glass heat is processed.
3) performance of the coated glass of the difunctional composite film of visible light anti-reflection/near infrared ray reflective obtaining is as follows: the first layer thickness 25nm, volumetric porosity 20%; Second layer thickness 400nm; The volumetric porosity 30% of the 3rd layer of porous silica film layer, thickness 180nm; Visible light transmissivity 94.7%, near infrared ray reflective rate 72%; The physicochemical property of coated glass meets the national standard of regulation in " coated glass physicochemical property testing standard ".
Claims (3)
1. antireflective visible ray and a reflection near infrared ray bifunctional coated glass, the film layer structure that it is characterized in that this bifunctional coated glass is one of following two kinds:
A. one-side coated glass: take glass as substrate, in order on glass, silicon-dioxide separating film layer, electrically conducting transparent conductor oxidate rete, porous silica film layer are set;
B. double-sided coated glass: take glass as substrate, order arranges silicon-dioxide sealing coat, electrically conducting transparent conductor oxidate rete, porous silica film layer respectively on the two sides of glass;
In described silicon-dioxide separating film layer, volumetric porosity is between 5～20%, and thicknesses of layers is: 10～25 nanometers;
Described electrically conducting transparent conductor oxidate rete, comprises stannic oxide composite zinc oxide or fluorine-doped tin oxide F:SnO
2, thicknesses of layers is: 75～400 nanometers;
In described porous silica film layer, volumetric porosity is at 15-30%, and thicknesses of layers is: 80～180 nanometers.
2. the preparation method of an antireflective visible ray as claimed in claim 1 and reflection near infrared ray bifunctional coated glass, it is characterized in that one-side coated glass adopts one side spraying method, first clean glass sheet is heated to 300～450 ℃, then spray the silica containing spray coating liquor of the first layer, form silicon-dioxide separating film layer; On the first layer, spray again the second layer containing the spray coating liquor of electrically conducting transparent conductor oxidate, form electrically conducting transparent conductor oxidate rete; Then on the second layer, spray the 3rd layer of silica containing spray coating liquor, utilize the volatile quantity of liquid in spray coating liquor to form porous silica film layer; Finally plate state trilamellar membrane sheet glass 610～650 ℃ of thermal treatments 2.5～3.0 minutes;
The spray coating liquor of electrically conducting transparent conductor oxidate adopts fluorine-doped tin oxide F:SnO
2, by SnCl
45H
2o, NH4F, second alcohol and water form, and inhibitor is made in acid, and second alcohol and water is solvent, is converted into molar ratio to be: Sn:F=1:0.1～0.3, fluorine-doped tin oxide F:SnO in spray coating liquor or steeping fluid
2solid content concentration is at 0.5mol/L;
Or the spray coating liquor of electrically conducting transparent conductor oxidate adopts stannic oxide composite zinc oxide, by SnCl
45H
2o, Zn (CH
3cOO)
22H
2o, second alcohol and water form, and second alcohol and water is solvent, mol ratio Zn:Sn=2:1～2.5:1.
3. the preparation method of an antireflective visible ray as claimed in claim 1 and reflection near infrared ray bifunctional coated glass, it is characterized in that double-sided coated glass adopts two-sided dip-coating method, first clean glass sheet being flooded to the first layer is silica containing steeping fluid, after lifting, at 150 ℃, be dried, form silicon-dioxide sealing coat; Then on the first layer, flood the second layer containing the steeping fluid of electrically conducting transparent conductor oxidate, after lifting, at 150 ℃, be dried, form electrically conducting transparent conductor oxidate rete; On the second layer, flooding the 3rd layer is silica containing steeping fluid again, utilizes the volatile quantity of liquid in steeping fluid to form porous silica film layer, finally plate state trilamellar membrane sheet glass 610～650 ℃ of thermal treatments 2.5～3.0 minutes;
The steeping fluid of electrically conducting transparent conductor oxidate adopts fluorine-doped tin oxide F:SnO
2, by SnCl
45H
2o, NH
4f, second alcohol and water form, and inhibitor is made in acid, and second alcohol and water is solvent, is converted into molar ratio to be: Sn:F=1:0.1～0.3, fluorine-doped tin oxide F:SnO in steeping fluid
2solid content concentration is at 0.5mol/L;
Or the steeping fluid of electrically conducting transparent conductor oxidate adopts stannic oxide composite zinc oxide, by SnCl
45H
2o, Zn (CH
3cOO)
22H
2o, second alcohol and water form, and second alcohol and water is solvent, mol ratio Zn:Sn=2:1～2.5:1.
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