CN103119725A - Glass-coated flexible polymeric substrates in photovoltaic cells - Google Patents

Glass-coated flexible polymeric substrates in photovoltaic cells Download PDF

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Publication number
CN103119725A
CN103119725A CN2011800434912A CN201180043491A CN103119725A CN 103119725 A CN103119725 A CN 103119725A CN 2011800434912 A CN2011800434912 A CN 2011800434912A CN 201180043491 A CN201180043491 A CN 201180043491A CN 103119725 A CN103119725 A CN 103119725A
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layer
glass
precursor
polymer
polymeric substrates
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S·布萨德
D·F·里尔登
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H01L31/03928—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • 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 present disclosure relates to a method of manufacturing of a glass coated flexible polymeric substrate. This invention also relates to a coated flexible polymeric substrate that is suitable for manufacturing flexible solar cells and electronic devices.

Description

The flexible polymer substrate of the vitreous coating in photovoltaic cell
Technical field
The present invention relates to make the method for the flexible substrates product of vitreous coating.The invention still further relates to the base material of coating, it is applicable to make flexible solar battery and other goods.
Background technology
Photovoltaic cell is made by deposit multilayer material in substrate.Described substrate can be rigidity (for example glass or silicon chip) or flexible (for example metal or polymer sheet).
Be most commonly used to make film Cu (In, Ga) Se 2(CIGS) base material of solar cell is soda-lime glass.Soda-lime glass helps the efficient of solar cell, and this is because the diffusion of alkali metal (being mainly sodium) from glass to cigs layer causes.Yet, the batch production of the CIGS on substrate of glass be expensive and glass usually too hard and can't be applicable to roller to the roller method.The disadvantage that the simple glass substrate is used for photovoltaic cell has promoted flexibility, tolerance is for generation of the high temperature, cheap of photosensitive layer and be applicable to roller to the exploration of the substrate of roller method.
Multiple material is carried out being used for as base material the test of flexible CIGS solar battery, comprised polymer (such as polyimides) and metal (such as molybdenum, aluminium and titanium foil).Substrate should tolerate up to the temperature of 800 ℃ and the air pressure of reduction.Metallic substrates also must and back contact between electric insulation with the production of the CIGS module that is conducive to integrated series.The thermal coefficient of expansion (CTE) of wishing described base material as much as possible near the CTE of electrical insulating material to avoid described insulating material from described substrate, hot breakage or layering to occur.
Also interesting exploitation is based on the solar cell of CZTS-Se, and described solar cell is similar to the CIGS solar cell, and different is to replace CIGS with CZTS-Se, and wherein " CZTS-Se " contained Cu 2ZnSn (S, Se) 4Whole may the combination, comprise Cu 2ZnSnS 4, Cu 2ZnSnSe 4And Cu 2ZnSnS xSe 4-x, 0≤x≤4 wherein.
Because polymer does not generally have thermal stability under higher than 450 ℃, so expectation applies metallic substrates, this is due to the temperature that can regularly reach in a large amount of application (comprising photovoltaic cell) higher than 450 ℃.
The known batch (-type) deposition process of using is with SiO xOr SiO 2Be deposited on bonding jumper, to form electric insulation layer on described metallic substrates.
Also the first coating metallizing substrate of known use subsilicate (randomly comprising alumina particles).Can be to silicone coated the second coating on subsilicate the first coating.
In another approach, stainless-steel sheet is contacted metal alkoxide, organoalkoxysilane, water and the thickener soln that is in organic solvent, such as alkoxy silane, carry out subsequently drying and calcining.
Disclose a kind of method of the substrate for the production of solar cell, wherein the first insulating barrier forms metallic plate (for example stainless-steel sheet) is upper.Oxidation is carried out on surface to the metallic plate that exposes by pore in described the first insulating barrier by described metallic plate is heated in air subsequently.Apply subsequently the second insulating barrier on described the first insulating barrier.
Disclose a kind of Coated Steels substrate that can be used as the substrate of flexible CIGS solar battery, the stainless steel strip that it comprises the aluminum oxide coating layer of sodium doping has deposited one deck molybdenum conductive layer on described alumina layer.
Disclose a kind of for form the method for aluminium oxide electric insulation layer on the ferrite stainless steel.The stainless steel substrates of described aluminum oxide coating layer is used for non-crystal silicon solar cell as substrate, and it is made by carry out PCVD (P-CVD) on sull.
In co-pending application serial no (CL4932), a kind of steel base is disclosed, it has glass coating and be equipped with one deck aluminium oxide between described glass and described steel layer.
Exist the demand to the production method of substrate, described substrate has the surface characteristic of pliability, glass of metal and the roller that can be used for making the CIGS battery to the roller method, need not inter coat between described glass coating and described metallic substrates.
Summary of the invention
In one aspect, the present invention is multi-layer product, comprises:
A) flexible polymer substrate; And
B) be set directly at the lip-deep glassy layer of at least a portion of described flexible polymer substrate, wherein be not equipped with the intermediate layer between the surface of described glassy layer and described flexible polymer substrate, wherein said glassy layer comprises SiO 2, Al 2O 3, Na 2O, B 2O 3And randomly comprise metal oxide.
In one aspect, the present invention is the method for the preparation of multi-layer product, comprises following steps:
1) with the glass precursor layer Direct precipitation settled at least a portion surface of the polymeric substrate layers of thickness 10nm to 1cm, wherein be not equipped with the intermediate layer between the surface of described glass precursor layer and described polymeric substrates, and wherein said glass precursor layer comprises: SiO 2Precursor, Al 2O 3Precursor, Na 2O precursor, B 2O 3Precursor, and randomly comprise metal oxide precursor, and
B) use light source to carry out Fast Heating less than 30 seconds to having about 10nm to the about glass precursor layer of 5 micron thickness, the heating of wherein said glass precursor layer causes the localized heating on described polymer surfaces, and wherein to the heating of described polymer surfaces at least lower than a period of time of approximately 30 seconds to approximately 250 ℃ to the about temperature of 400 ℃.
Embodiment
In one embodiment, the present invention is for deposition on the flexible substrates surface and/or forms the method for glassy layer.Can expect to give the glazed characteristic of class to overcome some shortcoming at least of using the simple glass substrate in photovoltaic cell for example to the surface of flexible material.
Flexible substrates of the present invention can be flexible polymeric substrates.Be applicable to polymeric substrates of the present invention and can comprise for example polyimide polymer and polyethylene terephthalate (PET) polymer.Be not that all polymer all are applicable to purposes of the present invention.Degrade under the high temperature that can use in the method for the invention such as the such polymer of PET.Yet, in one embodiment, but the present invention is the method for polymer of the thermal degradation of enforcement of the present invention that is applicable to for the preparation of these, thereby thereby described high temperature only local positioning in described polymer the surface and this localized heating can alleviate in fact high temperature process to the counter productive of described degradable polymer, this is to realize by the substantive thermal degradation in other zone of having been avoided described polymer.
In one embodiment, the present invention is the goods that comprise the polymer composite layer of vitreous coating.The polymer composite layer of vitreous coating can be used for electronic installation for example or as the assembly of photovoltaic cell.For example, the PET composite bed of vitreous coating can be used as the barrier layer of photovoltaic cell.The polyimides composite bed of vitreous coating can be used as the basalis of photovoltaic cell, is used for the deposition of film photovoltaic cell.For example, the substrate of vitreous coating of the present invention also can be used for printed substrate, transistor and is used as damp-proof layer.
Form the required processing temperature of glassy layer in view of the described glass precursor coating of roasting with on described flexible substrates, suitable substrate must be able to stand to surpass 250 ℃ and be up to the approximately processing temperature of 800 ℃.
This method can be used for the surface on passivation flexible substrates surface.Described passivation can protect described surface to avoid the chemistry infringement.Described glassy layer can be used as heat insulation layer and/or electric insulation layer plays a role, perhaps also can be used as the ion barrier layer and play a role, the harmful doping (600 ℃ under the prevention of ion migration by ESCA characterized) of impurity to CIGS when it can prevent at high temperature hot working of solar cell.
In the present invention, so-called passivation generally refers to prevent the adverse drug reactions at flexible base layer described in photovoltaic cell and described cigs layer.For example, passivation layer of the present invention acts on: (1) prevents that described cigs layer is subject to the ionic soil of stainless steel or other flexible substrates; And the irregularity place in the surface of the described flexible substrates of (2) polishing.
This method can or be carried out as continuous method with intermittence, for example carried out in the roller method at roller.
Polymeric substrates
In one embodiment, the present invention is the method for depositing glass layers on the flexible polymer substrate surface or glass precursor layer.Being applicable to implement polymeric substrates of the present invention is thermoplasticity or thermosetting polymer, can there be surpassing processing at the temperature of 250 ℃ the substance degraded of described polymer chain in it, or does not exist intention for the desired character of the polymer of glass/polymer multi-layer product and/or the remarkable infringement of required feature.For example: polyester polymers such as polyethylene terephthalate (PET) polymer may be fit to; And polyimide polymer can be used for enforcement of the present invention.May must only heat the surface of particular polymers to avoid the degraded of the polymer in described polymeric substrates other zone, wherein will contact described glassy layer or glass precursor layer.Randomly, the polymer of filling is applicable to enforcement of the present invention.Can be used for filler of the present invention and be in this area known and filler routine arbitrarily, and it can tolerate described processing conditions, particularly processing temperature used in the present invention.For example, glass and talcum can be the suitable filler in the flexible polymer substrate.In the present invention, the amount of available filler not should be the amount of the available characteristic of impairment flexible polymer substrate of the present invention, and those of ordinary skill can be learnt this amount by common experiment or by general knowledge.
The glass precursor layer
In one aspect of the invention, described substrate applies with the glass precursor layer, carries out subsequently the step of dry and the described glass precursor layer of roasting to form glassy layer on described flexible substrates.According to hereinafter describing, the thickness of described glassy layer can by apply before roasting-dry Multiple Cycle increases, or by apply-Multiple Cycle of drying-roasting increases.
Form described glassy layer by using the glass precursor composition that the surface of described flexible substrates is applied in whole or in part.Described precursor composition can comprise: (1) dissolves in the silicon of certain form of at least a solvent; (2) aluminium compound; (3) boron-containing compound; (4) sodium salt, and (5) sylvite randomly.
The silicon of soluble form can be for example tetrem acyloxy silane, four propionyloxy silane, two (pentanedione acidic group) two (acetate) silane, two (2-methoxy ethoxy) two (acetate) silane, two (pentanedione acidic group) two (ethyoxyl) silane, positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four isopropyl esters, or their mixture.
Aluminium compound for example can be: three (pentanedione acidic group) aluminium, first aluminium oxide, ethoxyquin aluminium, aluminium isopropoxide, normal propyl alcohol aluminium; or their mixture); also added trialkylboron acid esters (for example trimethylborate, triethyl borate, triproylborate, trimethoxyboroxine, or their mixture).
The precursor of sodium oxide molybdena can be for example sodium acetate, sodium propionate, sodium metasilicate, sodium alkoxide, Boratex, sodium tetraphenylborate, or their mixture.
Optional sylvite can be for example potassium acetate, potassium propionate, potassium methoxide, potassium ethoxide, potassium isopropoxide, or their mixture.
For forming described glass precursor composition, described soluble silicon can be dissolved in the solution of the silicon solution that dissolves with acquisition in solvent, described solvent such as: (1) C1-C10 alcohol (for example isomers of the isomers of the isomers of the isomers of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, n-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 1-amylalcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-hexanol, 1-heptanol, 1-heptanol, or their mixture); (2) acid (for example acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, or their mixture) and (3) water.With respect to silicon, can be incorporated into the water of 0 to 4 molar equivalent.Can use the solvent of minimum flow, notice that this amount should be fully also effectively for the solution that forms described component.
Described sodium salt can be dissolved in the identical C1-C10 alcohol that the described initial silicon solution of preparation uses and add described silicon solution.In certain embodiments, before being covered, described stainless steel-based primary coat filters described glass precursor preparation.In certain embodiments, the consisting of of the glass precursor in described preparation approximately 100 (Si) than 45 (B) than 26 (Na) elemental ratio than 3 (Al).
In one embodiment, in the n-butyl alcohol that described precursor composition can be by being dissolved in silica precursors (for example tetraethyl orthosilicate) minimum flow or the 1:1 mixture of n-butyl alcohol and acetic acid and stirred and prepare.Add the water of 2 molar equivalents and this solution is carried out the backflow of a hour in this solution.Alumina precursor (for example three (pentanedione acidic group) aluminium), boron oxide precursors (for example triethyl borate) and the sodium oxide molybdena precursor (for example sodium tetraphenylborate) that will be in n-butyl alcohol add.In case described precursor dissolving adds more solvent to obtain required concentration.
Described glassy layer optionally comprises the oxide of lithium, magnesium, potassium, calcium, barium, lead, germanium, tin, antimony, bismuth or any lanthanide series.Li 2O, MgO, BaO, K 2O, CaO, PbO, GeO 4, SnO 2, Sb 2O 3, Bi 2O 3Or the appropriate precursors of any oxide of lanthanide series metal all can comprise acetate separately, for example: potassium acetate, calcium acetate, lead acetate, acetic acid germanium, tin acetate, antimony acetate and bismuth acetate.Can use other oxide precursor, may be known as those of ordinary skill in the art.
Silicon alkoxide (for example tetraalkyl orthosilicate of silicon) and aluminium-alcohol salt (for example aluminium isopropoxide) also can be used for preparing described glass precursor composition.
Randomly, the borosilicate glass nano particle can be added described preparation.
The coating of described glass precursor composition can be undertaken by any known and/or conventional method to the deposition of described flexible substrates, comprises that rod is coated with, spraying, dip-coating, the coating of nick version or channel mould coating.Those of ordinary skill in the art should be appreciated that advantage and/or the shortcoming of any these painting methods commonly used, and can select suitable painting method according to the details of the machined parameters of considering.In one embodiment, the glass precursor layer can be set directly at least a portion surface of polymeric substrate layers of thickness 10nm to 1cm, the intermediate layer wherein is not set between the surface of described glass precursor layer and described polymeric substrates.The heating (for example lower than 30 seconds) that can carry out the utmost point short time to described glass precursor layer is with the direct polymer surfaces of this glassy layer of contact of heating effectively, and the method is defined as Fast Heating in this article.In the Fast Heating method of implementing in the present invention, described polymer surfaces reaches approximately 250 ℃ through heating to be continued lower than about time in 30 seconds to the about temperature of 400 ℃, perhaps continue the time lower than 1 second, perhaps continue the time (5000 microsecond) lower than 5 milliseconds, or lasting approximately 1 millisecond (1000 microsecond).In method of the present invention, the described substrate of glass of imagination repeatedly is exposed to Fast Heating.
Duration and number of times that described glassy layer is exposed to Fast Heating can depend on multiple processing conditions, comprise power that thermal source produces and under given condition group described glass in conjunction with the efficient of described polymeric substrates.All should avoid the destruction to described polymer under any condition group.
After described glass precursor composition is coated on described flexible substrates, generally in air, that this precursor is dry with desolventizing under 100 to 150 ℃.In certain embodiments, subsequently in air or oxygen containing gaseous environment at the glass precursor layer of 250 to 800 ℃ of described dryings of lower roasting so that described glass precursor layer is transformed into the roasting glassy layer.So-called " roasting " thus refer to the decomposition temperature that in the oxidizing gas environment described glass precursor layer of heating surpasses this precursor:
1) but remove for any organic aglucon that this glass precursor is dissolved among coating solution, and;
2) silicon, aluminium, boron and the sodium component of described solution is oxidized into separately oxidised form, and;
3) form thin dense glass film in described substrate.
Can expect by comprising that (1) deposits described glass precursor (coating) on described substrate surface and (2) carry out the thickness that dry additional cycles improves described roasting glassy layer before roasting.
(1) coating can repeat many times succeeded by (2) dry circulation, and this depends on desirable glassy layer thickness, and obtains the required number of repetition of this desired thickness.Can repeat the thickness that described coating/drying cycles obtains need by 2-5 time.
The thickness of described roasting glassy layer can be approximately 1nm to the thickness of several microns.In certain embodiments, the thickness of described glass roasting layer can be in about 10nm to the scope of number micron thickness.In some purposes-for example when using in photovoltaic cell-by its thickness reduction is reached about 10nm to the approximate number micron or approximately 25nm to approximately 10 microns or approximately 50nm to the about scope of 5 microns or lower than approximately 3 microns, thereby the pliability that improves described roasting glassy layer is desirable.Yet, can be depending on application, composition or other factors for flexible desired thickness.For example, can expect in some applications the pore in described glassy layer, and therefore can expect to reduce the thickness of described glassy layer to produce pore.In other is used, can improve described thickness so that best completely cutting off to be provided, therefore minimum pore is provided in this glassy layer.Under any circumstance, purpose of the present invention all is to provide pliability to glassy layer, makes thus normal processing can not produce fracture in glass.Even the fracture that only can just can observe by microscope is also disadvantageous.For avoiding the fracture in described glassy layer, the upper thickness limit of this glassy layer can reach approximately 5 microns, or reaches approximately 4 microns, or reaches approximately 3 microns.
Randomly, (1) coating, (2) dry step with (3) roasting can repeat 2 times or more times.So also can improve the gross thickness of described roasting glassy layer.In the middle of multiple, calcination steps helps to remove the carbon that may exist in this glass precursor component, and therefore multiple calcination steps may be preferred.
Can omit described drying steps in same optional situation, and at than the lower temperature of described calcination steps, this glass precursor layer be carried out preroast, and carry out roasting subsequently.The described glass precursor layer of preroast can be conducive to, for example: expel at faster speed solvent; The gelling of auxiliary described glass precursor layer; And/or other interaction between the component of auxiliary described glass precursor layer.Any combination of drying, preroast and calcination steps all can be repeatedly to obtain thickness desirable in final glassy layer or other characteristic.
In certain embodiments, add entry in described this precursor mixture of coating step forward direction.This has improved the viscosity of described glass precursor composition and helped to form the glassy layer of 50nm to 2 micron of thickness in primary coating and drying cycles.
Described calcination steps and drying steps all carry out guaranteeing the complete oxidation of this glass precursor usually in air.The existence of metal oxide in this glassy layer of elemental carbon, carbonate intermediate or reduction can reduce the puncture voltage of described insulating barrier.
After roasting, described glassy layer comprises usually: the silicon that surpasses 70 % by weight; Aluminium lower than 10 % by weight; The boron oxide of 5-15 % by weight; And lower than sodium and/or the potassium oxide of 10 % by weight.In one embodiment, described roasting glassy layer comprises: the about SiO of 81 % by weight 2, the about B of 13 % by weight 2O 3, approximately 1% to being up to the approximately Na of 4 % by weight 2O and the about Al of 2 % by weight 2O 3
In certain embodiments, described glass precursor composition is through selecting to provide and Mo and CIGS(or CZTS-Se) thermal linear expansion coefficient (CTE) of the glassy layer that is close of layer by layer CTE, thereby reduced Mo and CIGS(or CZTS-Se) pressure of layer is curling to reduce film.In certain embodiments, the CTE of borosilicate glass is approximately 3.25 * 10 -6/ ℃, thereby provide and the CTE(of Mo layer approximately 4.8 * 10 -6/ ℃) and the CTE(of cigs layer approximately 9 * 10 -6/ ℃) matched well.
One aspect of the invention is multi-layer product, comprise:
A) flexible polymer substrate;
B) be set directly at glassy layer at least a portion of described flexible polymer substrate, wherein said glassy layer comprises SiO 2, Al 2O 3, Na 2O, B 2O 3, and randomly comprising oxide, it is selected from Li 2O, BeO, BaO, MgO, K 2O, CaO, MnO, NiO, SrO, FeO, Fe 2O 3, CuO, Cu 2O, CoO, ZnO, PbO, GeO 4, SnO 2, Sb 2O 3, Bi 2O 3And any oxide of lanthanide series metal.
Described flexible polymer substrate and glassy layer are as described above.
This multi-layer product can be used as make electronic installation (such as, organic light emitting diode display is used, white organic LED is used, photovoltaic application) substrate.These multi-layer products also can be used for Medical Devices, such as cardiac valves.
In certain embodiments, described multi-layer product also comprises:
D) be arranged on conductive layer at least a portion of described glassy layer.
In certain embodiments, described multi-layer product also comprises:
E) be arranged on photosensitive layer on described conductive layer;
F) be arranged on CdS layer on described photosensitive layer; And
G) be arranged on transparent conductive oxide on described CdS layer.
These multi-layer products can be used for for example photovoltaic cell.
Suitable conductive layer comprises and is selected from following material: the metal of metal, doping oxide, metal oxide, organic conductor and their combination.Conductive metal layer can be deposited on described glassy layer by vapour deposition process or electroless coating layer method.Suitable metal comprises Mo, Ni, Cu, Ag, Au, Rh, Pd and Pt.Common 200nm to 1 micron thickness of described conductive metal layer.In one embodiment, described electric conducting material is the molybdenum of doping molybdenum oxide.
In certain embodiments, described multi-layer product comprises for example organic conductor of organic function layer, such as polyaniline and polythiophene.In these embodiments, after the described organic function layer of deposition, described multi-layer product usually is heated and is no more than 450 ℃ or 400 ℃ or 350 ℃ or 300 ℃ or 250 ℃ or 200 ℃ or 150 ℃ or 100 ℃.
Suitable photosensitive layer comprises CIS(cadmium selenide-indium), CIGS and CZTS-Se.
Can by gasification or sputter copper, indium and gallium (successively or simultaneously) randomly, subsequently film and the selenium steam that produces be reacted, thereby form described CIGS and CIS layer.The metal oxide particle suspension that alternatively, can use a variety of printing processes (comprising silk screen printing and ink jet printing) will be in ink is deposited on described conductive layer.This has produced porous membrane, in hot working, it is carried out densification and reduces to form CIGS or CIS layer subsequently.Above-described method is well known in the art and is conventional.In fact, can use any known or conventional method to form described CIGS or CIS layer.
The CZTS-Se film can prepare by several different methods, comprises thermal evaporation, sputter, mixing sputter, pulsed laser deposition, electron beam evaporation, photochemical precipitation and electrochemical deposition.The CZTS film also can be pyrogenically prepared by solution spray, and described solution comprises slaine and (is generally CuCl, ZnCl 2And SnCl 4), use thiocarbamide as the sulphur source.
For example, described CdS layer can deposit by chemical bath deposition.Can use other known and/or conventional method.
Suitable including transparent conducting oxide layer (such as doping zinc oxide or tin indium oxide) can be deposited on described CdS layer by sputter or pulse layer deposition.Can use is other known and/or conventional method for a person skilled in the art.
Example
Example 1:
Be coated on
Figure BDA00002899284000101
On the Na with 10% weight 2 The sodium aluminium borosilicate glass combination of O Thing
0.5M precursor formulation for [Si] prepares as follows:
Tetraethyl orthosilicate (Sigma Aldrich,〉99.0% purity with 2.4109g (11.57mmol)) be dissolved in the n-butyl alcohol of 10ml.Glacial acetic acid (the 1.0400g that adds 1.5 molar equivalents in this solution; 17.35mmol, EMD,〉99.7% purity) and 1 (0.02g) nitric acid.Described solution 2h subsequently refluxes under 118 ℃.After backflow is completed; at room temperature add sodium propionate (the Sigma Aldrich of 0.2873g (2.99mmol) in this solution by following interpolation order; 99% purity), three (pentanedione acidic group) aluminium (Sigma Aldrich of 0.1179g (0.36mmol); 99% purity) and the triethyl borate (Sigma Aldrich, 99% purity) of 0.5054g (3.46mmol).Stir subsequently described solution until clarify, and add n-butyl alcohol until reach the cumulative volume of 25.00ml.
With 50.8 micron thickness
Figure BDA00002899284000102
(DuPont) film cutting is slit into a certain size, and is cleared up by using the washed with methanol surface, and/or carries out the argon plasma cleaning (A.G.Services PE-PECVD System1000) of 30s time with following condition:
Power=24.3W
Pressure=100.0mTorr
Choke pressure=200.0mTorr
Argon flow amount=10.0sccm
Use the PTFE filter of 0.45 micron to filter described glass precursor preparation.
At room temperature, in clean room environment (100 grades),
Figure BDA00002899284000103
Use the filtered glass precursor preparation of 0.1ml to apply carrying out bar type through the polyimides substrate of cleaning with the #40 post on electronic constant speed coating machine.Described sample through applying is dry 30s at room temperature subsequently, under 150 ℃ dry 2 minutes subsequently.
Repeat under the same conditions the coating of coating and dry circulation until obtain required thickness.
Subsequently with the ramp rate roasting of 10 ℃/s final the layer 2 minutes to 400 ℃.
Characterize the integrality of this vitreous coating by ESCA, thereby measure the glass composition on top coating surface.
Example 2:
Be coated on 50.8um30 % by weight TiO 2 Has 10% weight on the polyimide film of filling The Na of amount 2 The sodium composition of aluminum boron silicate glass of O
0.5M precursor formulation for [Si] prepares as follows:
Tetraethyl orthosilicate (Sigma Aldrich,〉99.0% purity with 2.4109g (11.57mmol)) be dissolved in the n-butyl alcohol of 10ml.Glacial acetic acid (the 1.0400g that adds 1.5 molar equivalents in this solution; 17.35mmol, EMD,〉99.7% purity) and 1 (0.02g) nitric acid.Described solution 2h subsequently refluxes under 118 ℃.After backflow is completed; at room temperature add sodium propionate (the Sigma Aldrich of 0.2873g (2.99mmol) in this solution by following interpolation order; 99% purity), three (pentanedione acidic group) aluminium (Sigma Aldrich of 0.1179g (0.36mmol); 99% purity) and the triethyl borate (Sigma Aldrich, 99% purity) of 0.5054g (3.46mmol).Stir subsequently described solution until clarify, and add n-butyl alcohol until reach the cumulative volume of 25.00ml.
30 % by weight TiO with 50.8 microns 2Polyimides (DuPont) film cutting of filling is slit into a certain size, and cleared up by using the washed with methanol surface, and/or carried out the argon plasma cleaning (A.G.Services PE-PECVD System1000) of 30s time with following condition:
Power=24.3W
Pressure=100.0mTorr
Choke pressure=200.0mTorr
Argon flow amount=10.0sccm
Use the PTFE filter of 0.45 micron to filter described glass precursor preparation.
At room temperature, in clean room environment (100 grades),
Figure BDA00002899284000111
Use the filtered glass precursor preparation of 0.1ml to apply carrying out bar type through the polyimides substrate of cleaning with the #40 post on electronic constant speed coating machine.Described sample through applying is dry 30s at room temperature subsequently, under 150 ℃ dry 2 minutes subsequently.
Repeat under the same conditions the coating of coating and dry circulation until obtain required thickness.
Subsequently with the ramp rate roasting of 10 ℃/s final the layer 2 minutes to 400 ℃.
Example 3:
Be coated on 10% weight that has on the polyimide film that 50.8um30 % by weight talcum fills The Na of amount 2 The sodium composition of aluminum boron silicate glass of O
0.5M precursor formulation for [Si] prepares as follows:
Tetraethyl orthosilicate (Sigma Aldrich,〉99.0% purity with 2.4109g (11.57mmol)) be dissolved in the n-butyl alcohol of 10ml.Glacial acetic acid (the 1.0400g that adds 1.5 molar equivalents in this solution; 17.35mmol, EMD,〉99.7% purity) and 1 (0.02g) nitric acid.Described solution 2h subsequently refluxes under 118 ℃.After backflow is completed; at room temperature add sodium propionate (the Sigma Aldrich of 0.2873g (2.99mmol) in this solution by following interpolation order; 99% purity), three (pentanedione acidic group) aluminium (Sigma Aldrich of 0.1179g (0.36mmol); 99% purity) and the triethyl borate (Sigma Aldrich, 99% purity) of 0.5054g (3.46mmol).Stir subsequently described solution until clarify, and add n-butyl alcohol until reach the cumulative volume of 25.00ml.
Polyimides (DuPont) film cutting that the 30 % by weight talcums of 50.8 microns are filled is slit into a certain size, and cleared up by using the washed with methanol surface, and/or carried out the argon plasma cleaning (A.G.Services PE-PECVD System1000) of 30s time with following condition:
Power=24.3W
Pressure=100.0mTorr
Choke pressure=200.0mTorr
Argon flow amount=10.0sccm
Use the PTFE filter of 0.45 micron to filter described glass precursor preparation.
At room temperature, in clean room environment (100 grades),
Figure BDA00002899284000121
Use the filtered glass precursor preparation of 0.1ml to apply carrying out bar type through the polyimides substrate of cleaning with the #40 post on electronic constant speed coating machine.Described sample through applying is dry 30s at room temperature subsequently, under 150 ℃ dry 2 minutes subsequently.
Repeat under the same conditions the coating of coating and dry circulation until obtain required thickness.
Subsequently with the ramp rate roasting of 10 ℃/s final the layer 2 minutes to 400 ℃.
Example 4:
Be coated on
Figure BDA00002899284000122
On 10% weight Na 2 The sodium composition of aluminum boron silicate glass of O
0.5M precursor formulation for [Si] prepares as follows:
Tetraethyl orthosilicate (Sigma Aldrich,〉99.0% purity with 2.4109g (11.57mmol)) be dissolved in the n-butyl alcohol of 10ml.Glacial acetic acid (the 1.0400g that adds 1.5 molar equivalents in this solution; 17.35mmol, EMD,〉99.7% purity) and 1 (0.02g) nitric acid.Described solution 2h subsequently refluxes under 118 ℃.After backflow is completed; at room temperature add sodium propionate (the Sigma Aldrich of 0.2873g (2.99mmol) in this solution by following interpolation order; 99% purity), three (pentanedione acidic group) aluminium (Sigma Aldrich of 0.1179g (0.36mmol); 99% purity) and the triethyl borate (Sigma Aldrich, 99% purity) of 0.5054g (3.46mmol).Stir subsequently described solution until clarify, and add n-butyl alcohol until reach the cumulative volume of 25.00ml.
With 50.8 micron thickness
Figure BDA00002899284000131
(DuPont) film cutting is slit into a certain size, and is cleared up by using the washed with methanol surface, and/or carries out the argon plasma cleaning (A.G.Services PE-PECVD System1000) of 30s time with following condition:
Power=24.3W
Pressure=100.0mTorr
Choke pressure=200.0mTorr
Argon flow amount=10.0sccm.
Use the PTFE filter of 0.45 micron to filter described glass precursor preparation.
At room temperature, in clean room environment (100 grades),
Figure BDA00002899284000132
Use the filtered glass precursor preparation of 0.1ml to apply carrying out bar type through the polyimides substrate of cleaning with the #40 post on electronic constant speed coating machine.Described sample through applying is dry 30s at room temperature subsequently, under 150 ℃ dry 2 minutes subsequently.
Use subsequently PulseForge3300 equipment (by Exploitation) with sample being exposed under the pulse length of 1000 microseconds between the wide wave spectrum between 51% and 100% (between 200nm and 1000nm) of four kinds of different relative dosages, thereby processing this glass film and do not damage the integrality of coated substrate in described polyimides substrate.Described film through applying is exposed to peak power〉100kW/cm 2The pulse of lower 1000 microseconds, it is enough to form described glass in described polyimides substrate.To measure the chemical composition of described coating, the sodium aluminium borosilicate glass on the top surface that has confirmed to expose forms by this final coating of esca analysis.

Claims (10)

1. multi-layer product comprises:
A) flexible polymer basalis; And
B) be set directly at the lip-deep glassy layer of at least a portion of described flexible polymer basalis, wherein between the surface of described glassy layer and described flexible polymer substrate, the intermediate layer be not set, wherein said glassy layer comprises SiO 2, Al 2O 3, Na 2O, B 2O 3And randomly comprise metal oxide.
2. goods according to claim 1, wherein said polymeric substrates is polyimide polymer or polyester polymers.
3. goods according to claim 1, wherein said polymeric substrates comprises filler.
4. goods according to claim 3, wherein said polymeric substrates is polyimides.
5. goods according to claim 4, wherein said filler is glass or talcum.
6. goods according to claim 5, wherein said filler is talcum.
7. prepare the method for multi-layer product, comprise the following steps:
1) with set glass precursor layer Direct precipitation at least a portion surface of the polymeric substrate layers of thickness 10nm to 1cm, the intermediate layer wherein is not set, and wherein said glass precursor layer comprises between the surface of described glass precursor layer and described polymeric substrates: SiO 2Precursor, Al 2O 3Precursor, Na 2O precursor, B 2O 3Precursor, and randomly comprise metal oxide precursor, and
B) use light source to carry out Fast Heating lower than 30 seconds to having about 10nm to the about glass precursor layer of 5 micron thickness, the heating of wherein said glass precursor layer causes the localized heating on described polymer surfaces, and wherein to the heating of described polymer surfaces at least lower than a period of time of approximately 30 seconds to approximately 250 ℃ to the about temperature of 400 ℃.
8. method according to claim 7, wherein said polymeric substrates is polyimide polymer.
9. method according to claim 8 is wherein to the time of described polymer surfaces heating at least about 1000 microseconds.
10. the goods of method according to claim 7 preparation.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110922623A (en) * 2019-12-19 2020-03-27 浙江道明光电科技有限公司 Colorless transparent polyimide composite film and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2852641T3 (en) 2012-05-22 2019-01-31 Dsm Ip Assets B.V. Composition and process for making a porous inorganic oxide coating
CA2878704A1 (en) 2012-08-09 2014-02-13 Dsm Ip Assets B.V. Roll coating process and apparatus
CN103296092B (en) * 2013-06-18 2015-11-18 天津理工大学 A kind of CIGS solar cell device and preparation method thereof
CN103311322B (en) * 2013-06-18 2015-11-18 天津理工大学 A kind of CIGS solar cell device and preparation method thereof
WO2017098053A1 (en) 2015-12-11 2017-06-15 Dsm Ip Assets B.V. System and method for optical measurements on a transparent sheet
JP7276775B2 (en) 2017-04-18 2023-05-18 コベストロ （ネザーランズ） ビー．ブイ． Coatings and coating formulations

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017340A (en) * 1975-08-04 1977-04-12 General Electric Company Semiconductor element having a polymeric protective coating and glass coating overlay
US5419781A (en) * 1981-11-04 1995-05-30 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Flexible photovoltaic device
US5439849A (en) * 1994-02-02 1995-08-08 At&T Corp. Encapsulation techniques which include forming a thin glass layer onto a polymer layer
CN1322009A (en) * 2000-05-02 2001-11-14 三星电子株式会社 Spin coating glass composition and method for forming silica layer in production of semiconductor
CN1355858A (en) * 1999-04-14 2002-06-26 联合讯号公司 Low dielectric mano-porous material obtainable from polymer decomposition
CN1622225A (en) * 2003-10-30 2005-06-01 日本派欧尼株式会社 Material for forming insulation film and film-forming method with the use of the material
CN101125324A (en) * 2006-08-17 2008-02-20 株式会社半导体能源研究所 Film forming method, discharging droplet method and droplet discharging device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5498583A (en) * 1978-01-20 1979-08-03 Sanyo Electric Co Ltd Coating method of metallic film
GB2430547A (en) * 2005-09-20 2007-03-28 Seiko Epson Corp A method of producing a substrate having areas of different hydrophilicity and/or oleophilicity on the same surface

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017340A (en) * 1975-08-04 1977-04-12 General Electric Company Semiconductor element having a polymeric protective coating and glass coating overlay
US5419781A (en) * 1981-11-04 1995-05-30 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Flexible photovoltaic device
US5439849A (en) * 1994-02-02 1995-08-08 At&T Corp. Encapsulation techniques which include forming a thin glass layer onto a polymer layer
CN1355858A (en) * 1999-04-14 2002-06-26 联合讯号公司 Low dielectric mano-porous material obtainable from polymer decomposition
CN1322009A (en) * 2000-05-02 2001-11-14 三星电子株式会社 Spin coating glass composition and method for forming silica layer in production of semiconductor
CN1622225A (en) * 2003-10-30 2005-06-01 日本派欧尼株式会社 Material for forming insulation film and film-forming method with the use of the material
CN101125324A (en) * 2006-08-17 2008-02-20 株式会社半导体能源研究所 Film forming method, discharging droplet method and droplet discharging device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110922623A (en) * 2019-12-19 2020-03-27 浙江道明光电科技有限公司 Colorless transparent polyimide composite film and preparation method thereof
WO2021120496A1 (en) * 2019-12-19 2021-06-24 浙江道明光电科技有限公司 Colorless and transparent polyimide composite film and preparation method therefor

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