CN102190912A - Manufacturing method, coating material and photovoltaic device of antireflective film used in solar cell, and solar cell module - Google Patents
Manufacturing method, coating material and photovoltaic device of antireflective film used in solar cell, and solar cell module Download PDFInfo
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- CN102190912A CN102190912A CN2010101248858A CN201010124885A CN102190912A CN 102190912 A CN102190912 A CN 102190912A CN 2010101248858 A CN2010101248858 A CN 2010101248858A CN 201010124885 A CN201010124885 A CN 201010124885A CN 102190912 A CN102190912 A CN 102190912A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a manufacturing method, a coating material and a photovoltaic device of an antireflective film used in a solar cell, and a solar cell module. The coating material is cheap, and can easily form an antireflective film on the solar cell. With the coating material, antireflective performance of the antireflective film on the solar cell lighted surface is improved, and the light energy loss is reduced. According to the present invention, relative to the total solid constituent of the coating material for the antireflective film, the material comprises components of, by mass: 40% to 65% of hollow silica; 0.1% to 3.5% of organosilan or hydrolysate of organosilan, wherein only solid constituent when organosilan or hydrolysate of organosilan is reformed as silicon oxide is calculated; relative to the total solid constituent of the coating material for the antireflective film, 0.1% to 0.8% of silicane coupling agent; relative to the total solid constituent of the coating material for the antireflective film, 0.01% to 0.5% of organosilicon surfactant; and rest constituents of solvents and inevitable impurities.
Description
Technical field
The present invention relates to easily to obtain solar cell sunlight sensitive surface the antireflection film that antireflection property improves and optical energy loss is little be used to form the coating of solar cell with antireflection film, use this to be used to form solar cell is used antireflection film with the solar cell of the coating of antireflection film manufacture method, the solar cell antireflection film that obtains by this manufacture method, and have this solar cell with the solar cell of antireflection film with photovoltaic device, solar battery module.
Background technology
In the past, for solar cell,, carry out on the sensitive surface of sunlight, forming antireflection film in order to improve the transformation efficiency of sunlight to electric energy, the material of the formation of this antireflection film, antireflection film, coating process, coating condition etc. are carried out various researchs, and implement.
For example, as the formation of antireflection film, utilized magnesium fluoride (MgF
2), the unitary film of low-index material such as perfluorinated resin, hollow-particle, lamination the different multiwalled multilayer film of specific refractory power, perhaps be provided with formation of tiny texture (texture) structure etc. on these unitary films, the multilayer film or on base material the most surperficial.
Generally speaking, multilayer film needs physical property ground to constitute the thickness of each layer, and as its film, drying process can be used vapour deposition method, sputtering method, CVD method etc., damp process can be used spin-coating method, dip coating, rod and be coated with method, rolling method, intaglio plate coating method etc., and a large amount of motions is arranged.
And about unitary film, motion has the tunicle (patent documentation 1) that contains the silicon dioxide microparticle of hollow sphere in the matrix such as polyester, and also motion has by rod and is coated with the method (patent documentation 2) that contains the tunicle of silicon-dioxide hollow minute particle in the legal system resin.
On the other hand, about identical unitary film, in order to form the low-refraction transparent thin film layer, also motion has the coating fluid that will contain silicon alkoxide (Silicon Alkoxide) as binder constituents and/or its hydrolysate, alcohols and water to use the method (patent documentation 3) of spraying legal system film.
Patent documentation 1: TOHKEMY 2001-233611 communique
Patent documentation 2: TOHKEMY 2003-201443 communique
Patent documentation 3: TOHKEMY 2000-351939 communique
But, antireflection film in the past, because the smoothness on film surface is insufficient, thereby the film thickness distribution in the face is big, so there is the problem inhomogeneous, deviation that is easy to generate in the reflecting properties aspect.
And, as mentioned above, though it is effective utilizing the film of drying process, damp process, but with regard to drying process, the complex structure and the price of evaporation coating device, sputter equipment, CVD device etc. are also high, and the limited amount of the antireflection film that once obtains, so the productivity of film is low, still there are variety of issue in equipment aspect, production management aspect, manufacturing cost etc.
On the other hand, with regard to damp process, though the price of production unit etc. is compared with drying process and is tended to cheapness, but the big more paint film defect that causes because of dust etc. of surface covered becomes problem more, therefore there be not filming of defective in order to make, need to prepare the high coating environment of cleanliness factor such as clean room, the existence problems identical such as equipment aspect, production management aspect, manufacturing cost with drying process.
And when utilizing spraying method to make the antireflection film of individual layer, deviation is big in the face of thickness, and existence can not obtain the problem of sufficient anti-reflection effect.
This problem becomes more remarkable when making the multiwalled antireflection film.
Summary of the invention
The present invention In view of the foregoing finishes, purpose be to be provided for to form solar cell with the coating of antireflection film, solar cell with antireflection film and manufacture method thereof and solar cell with photovoltaic device and solar battery module, described coating can be easily and the antireflection property that on solar cell, forms the sensitive surface of sunlight at an easy rate improve and the little antireflection film of optical energy loss.
The inventor furthers investigate repeatedly in order to address the above problem, found that if be used to form the coating system film of solar cell with antireflection film, the antireflection property of can be easily and obtaining the sensitive surface of sunlight at an easy rate improves and the little antireflection film of optical energy loss, thereby finished the present invention, the above-mentioned coating that is used to form solar cell with antireflection film, become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solids in the coating, the solids component that contains when being converted into silicon oxide is more than the 0.1 quality % and the organosilane below the 3.5 quality % or its hydrolysate with respect to the total mass of above-mentioned coating, total mass with respect to above-mentioned coating contains more than the 0.1 quality % and the silane coupling agent below the 0.8 quality %, total mass with respect to above-mentioned coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, and surplus is solvent and unavoidable impurities.
Promptly, the coating that is used to form solar cell with antireflection film of the present invention, it is characterized in that, become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solids in the coating, the solids component that contains when being converted into silicon oxide is more than the 0.1 quality % and the organosilane below the 3.5 quality % or its hydrolysate with respect to the total mass of above-mentioned coating, total mass with respect to above-mentioned coating contains more than the 0.1 quality % and the silane coupling agent below the 0.8 quality %, total mass with respect to above-mentioned coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, and surplus is solvent and unavoidable impurities.
The solar cell of the present invention manufacture method of antireflection film, it is characterized in that, use has the spraying plant of one or more two-fluid mixing nozzles, and the air supply pressure in above-mentioned two-fluid mixing nozzle is more than the 0.1MPa and below the 1.0MPa, the feeding liquid amount is 10cm
3/ minute more than and 70cm
3/ minute below, the translational speed of above-mentioned two-fluid mixing nozzle is more than 800m/ minute and under the condition below 1600m/ minute, the solar cell that is used to form of the present invention is applied to by on surface of any one or compound two kinds and the base material that forms in glass, the resin or two surfaces with the coating of antireflection film, then, more than 150 ℃ and the temperature lower calcination below 350 ℃.
Solar cell antireflection film of the present invention is characterized in that, obtains by the manufacture method of solar cell of the present invention with antireflection film.
Solar cell photovoltaic device of the present invention is characterized in that, has solar cell antireflection film of the present invention.
Solar battery module of the present invention is characterized in that, has solar cell photovoltaic device of the present invention.
The invention effect
Utilize the coating that is used to form solar cell with antireflection film of the present invention, owing to become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solids in the coating, the solids component that contains when being converted into silicon oxide is more than the 0.1 quality % and the organosilane below the 3.5 quality % or its hydrolysate with respect to the total mass of above-mentioned coating, total mass with respect to above-mentioned coating contains more than the 0.1 quality % and the silane coupling agent below the 0.8 quality %, total mass with respect to above-mentioned coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, surplus is solvent and unavoidable impurities, therefore can be easily and the film thickness distribution that obtains at an easy rate in the face little, the reflecting properties aspect does not produce inhomogeneous and antireflection film deviation.
Utilize the manufacture method of solar cell of the present invention with antireflection film, owing to use the spraying plant with one or more two-fluid mixing nozzles, the air supply pressure in above-mentioned two-fluid mixing nozzle is more than the 0.1MPa and below the 1.0MPa, the feeding liquid amount is 10cm
3/ minute more than and 70cm
3/ minute below, the translational speed of above-mentioned two-fluid mixing nozzle is more than 800m/ minute and under the condition below 1600m/ minute, the solar cell that is used to form of the present invention is applied to by on surface of any one or compound two kinds and the base material that forms in glass, the resin or two surfaces with the coating of antireflection film, then, more than 150 ℃ and the temperature lower calcination below 350 ℃, therefore can be easily and make the antireflection film that film thickness distribution is little, the reflecting properties aspect does not produce inhomogeneous and deviation in the face at an easy rate.
Embodiment
Describe with antireflection film and solar cell mode with the manufacture method of antireflection film and solar cell with the coating of antireflection film, solar cell being used to implement the solar cell that is used to form of the present invention with photovoltaic device, solar battery module.
And this mode is the mode that specifically describes in order to understand the purport of invention better, does not have special qualification, to the present invention without limits.
[being used to form the coating of solar cell] with antireflection film
The solar cell that is used to form of present embodiment is following coating with the coating of antireflection film: become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solids in the coating, the solids component that contains when being converted into silicon oxide (silicon-dioxide) is more than the 0.1 quality % and the organosilane below the 3.5 quality % or its hydrolysate with respect to the total mass of above-mentioned coating, total mass with respect to above-mentioned coating contains more than the 0.1 quality % and the silane coupling agent below the 0.8 quality %, total mass with respect to above-mentioned coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, contain catalyzer as required, surplus is solvent and unavoidable impurities.
At this, the total solids in the coating becomes component to be meant, the total amount of the solids component amount of hollow silica, the solids component amount when organosilane or its hydrolysate are converted into silicon oxide and the solids component amount when silane coupling agent is converted into silicon oxide.
This coating is in order for example to improve solar cell with the antireflection property of the sensitive surface of the sunlight of employed solar cells such as photovoltaic device, solar battery module with suppress optical energy loss and use.
As hollow silica, so long as inside is that hollow silicon dioxide granule gets final product, its surface can be level and smooth surface, also can be vesicular.And the external diameter of this hollow silica does not have particular restriction, but need have can be in solvent equably dispersive disperse particle diameter, as disperseing particle diameter, preferred 50nm～60nm.
The containing ratio of this hollow silica, preferably becoming component with respect to the total solids in the coating is more than the 40 quality % and below the 65 quality %, more preferably more than the 45 quality % and below the 60 quality %.
At this, the reason that the containing ratio of hollow silica is limited in the above-mentioned scope is, if become component less than 40 quality % with respect to the total solids in the coating, then can not obtain sufficient anti-reflection effect, on the other hand, if become component greater than 65 quality % with respect to the total solids in the coating, the Strong degree of then can not being filmed fully.
Organosilane has the function of tackiness agent for hollow silica, therefore as this organosilane, can enumerate for example tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS), vinyltrimethoxy silane, methyltrimethoxy silane, phenyl triethoxysilane, xenyl triethoxyl silane (diphenyltriethoxysilane), tetraisopropoxysilan etc.These can only use a kind separately, also can mix use more than 2 kinds.
The containing ratio of this organosilane or its hydrolysate, the solids component when preferably this organosilane or its hydrolysate being converted into silicon oxide is more than the 0.1 quality % and below the 3.5 quality % with respect to the total mass of coating.
At this, the reason that the containing ratio of organosilane or its hydrolysate is limited in the above-mentioned scope is, if the solids component when being converted into silicon oxide with respect to the total mass of coating less than 0.1 quality %, then can not form fully and film, on the other hand, if with respect to the total mass of coating greater than 3.5 quality %, the then smoothness that can not obtain filming, inner evenness.
Silane coupling agent adds in order to improve the dispersion and the dispersion in the matrix (silica binder) of system behind the film of hollow silica in coating, therefore as this silane coupling agent, can enumerate for example methyltrimethoxy silane, Union carbide A-162, phenyl triethoxysilane, the n-propyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the n-hexyl triethoxyl silane, the n-octyl triethoxyl silane, positive decyl Trimethoxy silane, phenyltrimethoxysila,e, dimethoxydiphenylsilane silane coupling agents such as (diphenyldimethoxysilane); Vinyl silicane coupling agent such as vinyltrimethoxy silane, vinyltriethoxysilane; 3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-amino silicane coupling agents such as 3-aminopropyl methyl dimethoxysilane; Acryloxy silane coupling agents such as 3-acryloxy propyl trimethoxy silicane; Methacryloxy silane coupling agents such as 3-methacryloxypropyl trimethoxy silane; Mercaptosilane coupling agents such as 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane etc.These can only use a kind separately, also can mix use more than 2 kinds.
The containing ratio of this silane coupling agent, preferably the total mass with respect to coating is more than the 0.1 quality % and below the 0.8 quality %, more preferably more than the 0.15 quality % and below the 0.19 quality %.
At this, the reason that the containing ratio of silane coupling agent is limited in the above-mentioned scope is, if with respect to the total mass of coating less than 0.1 quality %, then can not obtain the dispersion effect of hollow silica fully, on the other hand, if greater than 0.8 quality %, then can not obtain sufficient anti-reflection effect with respect to the total mass of coating.
Organic silicon surfactant is by filming of improving that coating composition obtains the wettability of base material to be improved the smoothness of filming, thereby the inner evenness that improves thickness adds, therefore as this organic silicon surfactant, can enumerate for example polyether modified siloxane, polyether-modified polydimethylsiloxane etc.These can only use a kind separately, also can mix use more than 2 kinds.
The containing ratio of this organic silicon surfactant, preferably the total mass with respect to coating is more than the 0.01 quality % and below the 0.5 quality %, more preferably more than the 0.03 quality % and below the 0.10 quality %, further more than the preferred 0.06 quality % and below the 0.08 quality %.
At this, the reason that the containing ratio of organic silicon surfactant is limited in the above-mentioned scope is, if with respect to the total mass of coating less than 0.01 quality %, then can not obtain sufficient smoothness or be coated with effect uniformly, on the other hand, if greater than 0.5 quality %, then can hinder the smoothness of filming, or can not obtain the Strong degree of filming fully with respect to the total mass of coating.
As solvent; can enumerate for example methyl alcohol; ethanol; the 1-propyl alcohol; 2-propyl alcohol (Virahol: IPA); butanols; amylalcohol; hexanol; octanol; alcohols such as Pyranton; vinyl acetic monomer; N-BUTYL ACETATE; ethyl lactate; propylene glycol methyl ether acetate; propylene glycol monoethyl ether acetate; ester classes such as gamma-butyrolactone; ether; ethylene glycol monomethyl ether (methylcyclohexane); ethylene glycol monoethyl ether (ethyl cellosolve); ethylene glycol monobutyl ether (ethylene glycol butyl ether); diethylene glycol monomethyl ether; ethers such as diethylene glycol monoethyl ether; acetone; methylethylketone (MEK); methyl iso-butyl ketone (MIBK) (MIBK); methyl ethyl diketone; ketones such as pimelinketone; dimethyl formamide; N; N-dimethyl ethanoyl ethanamide; amidess such as N-Methyl pyrrolidone, ethylene glycol; Diethylene Glycol; glycolss such as propylene glycol etc.These can only use a kind separately, also can mix use more than 2 kinds.
As catalyzer, can enumerate an acidic catalysts such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, basic catalysts such as ammoniacal liquor, sodium hydroxide etc.
This coating except above-mentioned composition, also can contain organic polymers such as dispersion agent, resin etc. according to purposes, technical requirements.
[the solar cell manufacture method of antireflection film]
The solar cell of the present embodiment manufacture method with antireflection film is described.
At first, with present embodiment be used to form solar cell with the coating of antireflection film, use spraying plant with one or more two-fluids (gas and liquid) mixing nozzle, be applied on the surface (surface) or two surfaces of base material, formation is filmed.
This spraying plant can suitably select to use the device of SATA company, DeVilbiss company, Spraying Systems company etc.
At this, as base material, the base material that the sheet that preferred use is made of glass or resin, membranaceous, tabular base material or the matrix material that is obtained by compound glass and resin constitute.
Condition during as this coating above-mentioned coating is supplied to the two-fluid mixing nozzle time air supply pressure, preferred 0.1MPa is above and below the 1.0MPa, more preferably 0.5MPa is above and below the 0.7MPa.
In addition, the amount of liquid when this coating is supplied to the two-fluid mixing nozzle, preferred 10cm
3/ minute more than and 70cm
3/ minute below, more preferably 20cm
3/ minute more than and 40cm
3/ minute below.
The translational speed of this two-fluid mixing nozzle on substrate surface, preferred more than 800m/ minute and below 1600m/ minute, more preferably more than 900m/ minute and below 1050m/ minute.
When this is coated with, the usage quantity of the coating by making per unit area is few, paint spray is become tiny drop or base material is coated the shape control of the face that adheres to become shapes such as flat (flat) (ellipse), circular (circle), annulus, can form good and smooth the filming of inner evenness.Particularly, under the situation of present embodiment, the attachment surface shape is preferably flat (ellipse).
Then, dry this filmed.
Drying temperature for example is a normal temperature (25 ℃)～100 ℃ so long as the temperature that contained solvent fully dissipates in the coating gets final product.
In this drying process, the thorough drying of filming gets final product, can seasoning, can pass through heat drying, the empty mood of also can jetting.Particularly, the air blast of the normal temperature of can jetting, the warm wind below 100 ℃ of also can jetting.
Then, with this dried coating under the air atmosphere, more than 150 ℃ and below 350 ℃, preferred more than 200 ℃ and the temperature lower calcination below 300 ℃.
Operation can access the solar cell antireflection film of present embodiment like this.
And, as required, coating contains the coating of glass on filming, with this be coated with glass film under the air atmosphere, more than 600 ℃ and below 800 ℃, preferred more than 650 ℃ and the temperature below 750 ℃ heat-treat, can access solar cell antireflection film thus with the coated glass of glass coating after with antireflection film Strongization.
[solar cell photovoltaic device and solar battery module]
Be arranged on antireflection film on the photovoltaic device of solar cell by solar cell, the solar cell photovoltaic device with the antireflection film that film thickness distribution is little, the reflecting properties aspect does not produce inhomogeneous and deviation in the face can be provided present embodiment.
Be arranged on the solar battery module with photovoltaic device by solar cell, the solar battery module of the photovoltaic device with the antireflection film that film thickness distribution is little, the reflecting properties aspect does not produce inhomogeneous and deviation in the face of being provided with can be provided present embodiment.
Embodiment
Below, specifically describe the present invention by embodiment and comparative example, but the present invention is not limited to these embodiment.
As the hollow silica of using among this embodiment 1～12, use the 2-propanol dispersion liquor COSNICA205 (day waves catalyst and changes into corporate system) of the hollow silica that contains 20.5 quality %.The specific refractory power of this hollow silica is 1.30.
Embodiment 1
(being used to form the making of solar cell) with the coating of antireflection film
Will be with the convert hollow silica of 1.13 mass parts of silicon-dioxide, with the convert tetramethoxy-silicane (TMOS) of 1.19 mass parts of silicon-dioxide, with convert 3-methacryloxypropyl methyl dimethoxysilane (chemical industrial company of the SHIN-ETSU HANTOTAI system as silane coupling agent of 0.18 mass parts of silicon-dioxide, KBM-502), 79.58 the 2-propyl alcohol of mass parts, 1.94 the ethanol of mass parts, 2.76 the methyl alcohol of mass parts, 0.04 the methylethylketone of mass parts (MEK), 4.78 the water of mass parts, 8.33 the ethylene glycol of mass parts, 0.07 the organic silicon surfactant BYK346 of mass parts (PVC ッ Network ケ ミ one ジ ャ パ Application society system) mixes, then, the limit is stirred this mixed solution limit carry out thermal treatment in 3 hours under 60 ℃.Cooling immediately after the thermal treatment, make with respect to total solids become component contain 45 quality % hollow silica embodiment 1 be used to form the coating A of solar cell with antireflection film.
(the solar cell making of antireflection film)
Use has the spraying plant (SATA corporate system) of two-fluid (gas and liquid) mixing nozzle, and the above-mentioned solar cell that is used to form is applied on the surface that thickness is the blue or green sheet glass of 1.5mm (face) with the coating A of antireflection film, and formation is filmed.This time substrate temperature is 65 ℃, and the distance of two-fluid mixing nozzle and blue or green sheet glass is 115mm, and the air supply pressure when coating A is supplied to the two-fluid mixing nozzle is 0.6MPa, and the feed rate of coating A is 20cm
3/ minute, the translational speed of a direction is 1.9m/ minute in the face of blue or green sheet glass, the translational speed of two-fluid mixing nozzle is 975m/ minute.
Then, this is filmed in down seasoning of normal temperature (25 ℃), then under air atmosphere, 260 ℃ of calcinings 5 minutes down, that makes embodiment 1 has the substrate A of solar cell with antireflection film.
Then, measure this and have the transmitance of solar cell with the substrate A of antireflection film.
At this, owing to be subjected to optical efficiency as problem with solar cell, for having the transmitance of solar cell with the substrate A of antireflection film, use non-integrating sphere type spectrophotometer U-4100 (the Ha ィ テ of Hitachi Network ノ ロ ジ one society's system), be determined at the average transmittances (%) in the scope of measuring wavelength 500nm～1100nm.Consequently, average transmittances is 83.8%.
Embodiment 2
(being used to form the making of solar cell) with the coating of antireflection film
Will be with the convert hollow silica of 1.30 mass parts of silicon-dioxide, with the convert tetramethoxy-silicane (TMOS) of 1.05 mass parts of silicon-dioxide, with convert 3-methacryloxypropyl methyl dimethoxysilane (chemical industrial company of the SHIN-ETSU HANTOTAI system as silane coupling agent of 0.15 mass parts of silicon-dioxide, KBM-502), 80.28 the 2-propyl alcohol of mass parts, 1.94 the ethanol of mass parts, 2.39 the methyl alcohol of mass parts, 0.04 the methylethylketone of mass parts (MEK), 4.45 the water of mass parts, 8.33 the ethylene glycol of mass parts, 0.07 the organic silicon surfactant BYK346 of mass parts (PVC ッ Network ケ ミ one ジ ャ パ Application society system) mixes, then, the limit is stirred this mixed solution limit carry out thermal treatment in 3 hours under 60 ℃.Cooling immediately after the thermal treatment, make with respect to total solids become component contain 52 quality % hollow silica embodiment 2 be used to form the coating B of solar cell with antireflection film.
Then, use this to be used to form the coating B of solar cell, make the substrate B that solar cell is used antireflection film that has of embodiment 2 according to the method for embodiment 1 with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate B of antireflection film.Consequently, average transmittances is 83.9%.
Embodiment 3
(being used to form the making of solar cell) with the coating of antireflection film
Will be with the convert hollow silica of 1.50 mass parts of silicon-dioxide, with the convert tetramethoxy-silicane (TMOS) of 0.81 mass parts of silicon-dioxide, with convert 3-methacryloxypropyl methyl dimethoxysilane (chemical industrial company of the SHIN-ETSU HANTOTAI system as silane coupling agent of 0.19 mass parts of silicon-dioxide, KBM-502), 80.98 the 2-propyl alcohol of mass parts, 1.94 the ethanol of mass parts, 2.02 the methyl alcohol of mass parts, 0.04 the methylethylketone of mass parts (MEK), 4.12 the water of mass parts, 8.33 the ethylene glycol of mass parts, 0.07 the organic silicon surfactant BYK346 of mass parts (PVC ッ Network ケ ミ one ジ ャ パ Application society system) mixes, then, the limit is stirred this mixed solution limit carry out thermal treatment in 3 hours under 60 ℃.Cooling immediately after the thermal treatment, make with respect to total solids become component contain 60 quality % hollow silica embodiment 3 be used to form the coating C of solar cell with antireflection film.
Then, use this to be used to form the coating C of solar cell, make the substrate C that solar cell is used antireflection film that has of embodiment 3 according to the method for embodiment 1 with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate C of antireflection film.Consequently, average transmittances is 84.2%.
Embodiment 4
The coating A that solar cell is used antireflection film that is used to form with embodiment 1, method according to embodiment 1, being applied to the surface that thickness is the blue or green sheet glass of 1.5mm (face) goes up and calcines, and then be applied on the back side of blue or green sheet glass and calcine, make formed antireflection film on two surfaces of blue or green sheet glass of embodiment 4 have the substrate D of solar cell with antireflection film.
Then, the method mensuration according to embodiment 1 has the transmitance of solar cell with the substrate D of antireflection film.Consequently, average transmittances is 85.3%.
Embodiment 5
The coating B that solar cell is used antireflection film that is used to form with embodiment 2, method according to embodiment 1, being applied to the surface that thickness is the blue or green sheet glass of 1.5mm (face) goes up and calcines, and then be applied on the back side of blue or green sheet glass and calcine, make formed antireflection film on two surfaces of blue or green sheet glass of embodiment 5 have the substrate E of solar cell with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate E of antireflection film.Consequently, average transmittances is 86.0%.
Embodiment 6
The coating C that solar cell is used antireflection film that is used to form with embodiment 3, method according to embodiment 1, being applied to the surface that thickness is the blue or green sheet glass of 1.5mm (face) goes up and calcines, and then be applied on the back side of blue or green sheet glass and calcine, make formed antireflection film on two surfaces of blue or green sheet glass of embodiment 6 have the substrate F of solar cell with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate F of antireflection film.Consequently, average transmittances is 86.3%.
Embodiment 7
Except the solar cell that is used to form with embodiment 1 is applied to the surface that thickness is the blank glass of 3.2mm (face) goes up with the coating A of antireflection film, have the substrate G of solar cell with antireflection film according to what the method for embodiment 1 was made embodiment 7.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate G of antireflection film.Consequently, average transmittances is 90.8%.
Embodiment 8
Except the solar cell that is used to form with embodiment 2 is applied to the surface that thickness is the blank glass of 3.2mm (face) goes up with the coating B of antireflection film, have the substrate H of solar cell with antireflection film according to what the method for embodiment 1 was made embodiment 8.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate H of antireflection film.Consequently, average transmittances is 91.8%.
Embodiment 9
Except the solar cell that is used to form with embodiment 3 is applied to the surface that thickness is the blank glass of 3.2mm (face) goes up with the coating C of antireflection film, have the substrate I of solar cell with antireflection film according to what the method for embodiment 1 was made embodiment 9.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate I of antireflection film.Consequently, average transmittances is 91.2%.
Embodiment 10
The coating A that solar cell is used antireflection film that is used to form with embodiment 1, method according to embodiment 1, the surface (face) that is applied to thickness and is the blank glass of 3.2mm is gone up and is calcined, and then be applied on the back side of blank glass and calcine, make formed antireflection film on two surfaces of blank glass of embodiment 10 have the substrate J of solar cell with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate J of antireflection film.Consequently, average transmittances is 91.7%.
Embodiment 11
The coating B that solar cell is used antireflection film that is used to form with embodiment 2, method according to embodiment 1, the surface (face) that is applied to thickness and is the blank glass of 3.2mm is gone up and is calcined, and then be applied on the back side of blank glass and calcine, make formed antireflection film on two surfaces of blank glass of embodiment 11 have the substrate K of solar cell with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate K of antireflection film.Consequently, average transmittances is 93.0%.
Embodiment 12
The coating C that solar cell is used antireflection film that is used to form with embodiment 3, method according to embodiment 1, the surface (face) that is applied to thickness and is the blank glass of 3.2mm is gone up and is calcined, and then be applied on the back side of blank glass and calcine, make formed antireflection film on two surfaces of blank glass of embodiment 12 have the substrate L of solar cell with antireflection film.
Then, measure this according to the method for embodiment 1 and have the transmitance of solar cell with the substrate L of antireflection film.Consequently, average transmittances is 94.1%.
Comparative example 1
Measuring thickness according to the method for embodiment 1 is the transmitance of the blue or green sheet glass of 1.5mm itself.Consequently, average transmittances is 81.8%.
Comparative example 2
Measuring thickness according to the method for embodiment 1 is the transmitance of the blank glass of 3.2mm itself.Consequently, average transmittances is 89.0%.
Comparative example 3
(making of coating)
Will be with the convert tetramethoxy-silicane (TMOS) of 1.19 mass parts of silicon-dioxide, with convert 3-methacryloxypropyl methyl dimethoxysilane (chemical industrial company of the SHIN-ETSU HANTOTAI system as silane coupling agent of 0.18 mass parts of silicon-dioxide, KBM-502), 79.58 the 2-propyl alcohol of mass parts, 1.94 the ethanol of mass parts, 2.76 the methyl alcohol of mass parts, 0.04 the methylethylketone of mass parts (MEK), 4.78 the water of mass parts, 8.33 the ethylene glycol of mass parts, 0.07 the organic silicon surfactant BYK346 of mass parts (PVC ッ Network ケ ミ one ジ ャ パ Application society system) mixes, then, the limit is stirred this mixed solution limit carry out thermal treatment in 3 hours under 60 ℃.Cooling immediately after the thermal treatment, the coating M of making comparative example 3.
Then, except using this coating M being coated with on the single side surface of thickness as the blank glass of 3.2mm, make the substrate M that has film of comparative example 3 according to the method for embodiment 1.
Then, measure the transmitance that this has the substrate M of film according to the method for embodiment 1.Consequently, average transmittances is 89.9%.
According to these results as can be known, embodiment 1～12 has solar cell with the substrate of antireflection film, compares with blue or green sheet glass, the blank glass of comparative example, the substrate M that has a film, and average transmittances improves more than 1.8%.
This has confirmed, by on base material, form antireflection film of the present invention, have reduce external light in the reflection on film surface, improve the effect of light absorption ratio of the photovoltaic device of solar cell.
Utilize possibility on the industry
The coating that is used to form solar cell usefulness antireflection film of the present invention, become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solid in the coating, the solid constituent that contains when being converted into silica is more than the 0.1 quality % and the organosilan below the 3.5 quality % or its hydrolysate with respect to the gross mass of above-mentioned coating, gross mass with respect to above-mentioned coating contains more than the 0.1 quality % and the silane coupler below the 0.8 quality %, gross mass with respect to above-mentioned coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, surplus is solvent and inevitable impurity, thereby be can be easily and the film thickness distribution that obtains at an easy rate in the face little, the reflecting properties aspect does not produce the coating of the antireflection film of inhomogeneous and deviation, therefore, by being applied to solar cell, help the high efficiency of solar power generation certainly needless to say, this effect is also big in the fields such as light receiving component such as cloche, and its industrial effect is very big.
Claims (5)
1. one kind is used to form the coating that solar cell is used antireflection film, it is characterized in that, become component to contain more than the 40 quality % and the hollow silica below the 65 quality % with respect to the total solids in the coating, the solids component that contains when being converted into silicon oxide is more than the 0.1 quality % and the organosilane below the 3.5 quality % or its hydrolysate with respect to the total mass of described coating, total mass with respect to described coating contains more than the 0.1 quality % and the silane coupling agent below the 0.8 quality %, total mass with respect to described coating contains more than the 0.01 quality % and the organic silicon surfactant below the 0.5 quality %, and surplus is solvent and unavoidable impurities.
2. a solar cell is with the manufacture method of antireflection film, it is characterized in that, use has the spraying plant of one or more two-fluid mixing nozzles, and the air supply pressure in described two-fluid mixing nozzle is more than the 0.1MPa and below the 1.0MPa, the feeding liquid amount is 10cm
3/ minute more than and 70cm
3/ minute below, the translational speed of described two-fluid mixing nozzle is more than 800m/ minute and under the condition below 1600m/ minute, the described solar cell that is used to form of claim 1 is applied to by on surface of any one or compound two kinds and the base material that forms in glass, the resin or two surfaces with the coating of antireflection film, then, more than 150 ℃ and the temperature lower calcination below 350 ℃.
3. a solar cell antireflection film is characterized in that, obtains by the manufacture method of the described solar cell of claim 2 with antireflection film.
4. a solar cell photovoltaic device is characterized in that, has the described solar cell antireflection film of claim 3.
5. a solar battery module is characterized in that, has the described solar cell photovoltaic device of claim 4.
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Application publication date: 20110921 |