WO2012037242A2 - Substrats polymères flexibles enrobés de verre pour cellules photovoltaïques - Google Patents

Substrats polymères flexibles enrobés de verre pour cellules photovoltaïques Download PDF

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WO2012037242A2
WO2012037242A2 PCT/US2011/051580 US2011051580W WO2012037242A2 WO 2012037242 A2 WO2012037242 A2 WO 2012037242A2 US 2011051580 W US2011051580 W US 2011051580W WO 2012037242 A2 WO2012037242 A2 WO 2012037242A2
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layer
glass
substrate
metal
glass layer
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PCT/US2011/051580
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WO2012037242A3 (fr
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Salah Boussaad
Damien Francis Reardon
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E. I. Du Pont De Nemours And Company
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Publication of WO2012037242A3 publication Critical patent/WO2012037242A3/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/02—Coating with enamels or vitreous layers by wet methods
    • 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
    • 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

Definitions

  • the present disclosure relates to a method of manufacturing a metal oxide and glass coated metal product.
  • This invention also relates to a coated metallic substrate material that is suitable for manufacturing flexible solar cells and other articles in which a passivated stainless steel surface is desirable.
  • Photovoltaic cells are made by depositing various layers of materials on a substrate.
  • the substrate can be rigid (e.g., glass or a silicon wafer) or flexible (e.g., a metal or polymer sheet).
  • the most common substrate material used in the manufacture of thin-film Cu(ln,Ga)Se 2 (CIGS) solar cells is soda lime glass. Soda lime glass contributes to the efficiency of the solar cell, due to the diffusion of an alkali metal (primarily sodium) from the glass into the CIGS layer.
  • an alkali metal primarily sodium
  • substrate materials for flexible CIGS solar cells including polymers such as polyimide and metals such as molybdenum, aluminum and titanium foils.
  • the substrate should be tolerant of temperatures up to 800 °C and reducing atmospheres.
  • a metallic substrate must also be electrically insulated from the back contact to facilitate production of CIGS modules with integrated series
  • CTE coefficient of thermal expansion
  • CZTS-Se CZTS-Se based solar cells
  • Cu 2 ZnSn(S,Se) 4 including Cu 2 ZnSnS 4 , Cu 2 ZnSnSe 4 , and
  • coated metal substrates have been desirable since temperatures of above 450°C are routinely achieved in many applications, including photovoltaic cells.
  • a metallic base with a first coat of an alkali silicate, optionally containing alumina particles.
  • a second coat of silicone can be applied onto the first coat of an alkali silicate.
  • a stainless steel plate is contacted with a solution of a metal alkoxide, an organoalkoxysilane, water, and thickeners such as alkoxy silane in an organic solvent, then dried and calcined.
  • a method for producing a substrate for solar batteries has also been disclosed in which a first insulating layer is formed on a metal plate (e.g., a stainless steel plate). Then the surface of the metal plate exposed by pinholes in the first insulating layer is oxidized by heating the metal plate in air. A second insulating layer is then applied over the first insulating layer.
  • a metal plate e.g., a stainless steel plate
  • a coated steel substrate useful as a substrate for flexible CIGS solar cells comprises a stainless steel strip coated with a sodium-doped alumina layer onto which an electrically conducting layer of molybdenum has been deposited.
  • a process for forming an electrically insulating layer of aluminum oxide on ferritic stainless steel has been disclosed.
  • the alumina-coated stainless steel sheet was used as a substrate for an amorphous silicon solar battery manufactured by plasma chemical vapor deposition (P-CVD) on the oxide film.
  • P-CVD plasma chemical vapor deposition
  • this invention is a process comprising the steps: a) depositing a glass precursor directly on to at least a portion of a surface of a flexible substrate, wherein there are no intervening layers between the glass precursor and the substrate surface; and
  • the glass precursor comprises SiO 2 , AI 2 O 3 , Na 2 O, and B2O3, and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO 2 , Sb 2 O3, Bi 2 O3, an oxide of any lanthanide metal, or mixtures of any of these.
  • the present invention is a process comprising the steps of:
  • the present invention is a multilayer article
  • a multilayer composite comprising a flexible metal layer having deposited directly on a surface thereof a glass layer, wherein there are no intervening layers disposed between the glass layer and the surface of the flexible metal layer, and wherein the glass layer comprises SiO 2 , AI2O3, Na 2 O, and B 2 O 3 , and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 , an oxide of any lanthanide metal, or mixtures of any of these.
  • this invention is a process comprising the steps: a) depositing a glass precursor directly on to at least a portion of a surface of a flexible polymeric substrate, wherein there are no intervening layers between the glass precursor and the polymeric substrate surface; and b) heating the glass precursor to form a glass layer on the surface of the metal substrate, wherein the glass layer comprises SiO 2 , AI 2 O 3 , Na 2 O, and B 2 O 3 , and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 , an oxide of any lanthanide metal, or mixtures of any of these.
  • the present invention is a multi-layer article comprising:
  • a glass layer disposed directly on at least a portion of a surface of the flexible polymeric substrate, wherein there are no intervening layers disposed between the glass layer and the surface of the flexible polymeric substrate, and wherein the glass layer comprises SiO 2 , AI 2 O 3 , Na 2 O, and B 2 O 3 , and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 , an oxide of any lanthanide metal, or mixtures of any of these.
  • this invention is a process comprising the steps: a) depositing a glass precursor directly on to at least a portion of a surface of a flexible metal substrate, wherein there are no intervening layers between the glass precursor and the metal substrate surface; and
  • the glass layer comprises S1O2, AI2O3, Na2O, and B2O3, and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 , an oxide of any lanthanide metal, or mixtures of any of these and wherein the sodium component is present in an amount of from about 1 to about 25% by weight of the glass layer.
  • this invention is a multi-layer article comprising: a) a flexible metal substrate comprising 1 to 10 wt% aluminum; and b) a glass layer disposed directly on at least a portion of a surface of the metal substrate, wherein there are no intervening layers disposed between the glass layer and the surface of the metal substrate, and wherein the glass layer comprises SiO 2 , AI 2 O 3 , Na 2 O, and B 2 O 3 , and optionally an oxide selected from the group consisting of Li 2 O, BeO, MgO, BaO, K 2 O, CaO, MnO, NiO, SrO, FeO, Fe 2 O 3 , CuO, Cu 2 O, CoO, ZnO, PbO, GeO 4 , SnO2, Sb2O 3 , Bi 2 O 3 , an oxide of any lanthanide metal, or mixtures of any of these, and wherein the sodium component of the glass layer is present in an amount of from about 1 to about 25% by weight of the glass layer.
  • the present invention is a process comprising the steps:
  • the present invention is a multi-layer article
  • the present invention is a process for depositing and/or forming a glass layer on the surface of a flexible substrate. It can be desirable to impart glass-like properties to the surface of flexible materials in order to overcome at least some disadvantages of using common glass substrates in, for example, photovoltaic cells.
  • a flexible substrate of the present invention can be a flexible metal substrate or a polymeric substrate.
  • Flexible metal substrates suitable for inclusion in the present invention can include stainless steel, aluminum, titanium, and molybdenum, nickel, vanadium, chromium, silver and gold, for example. Flexibility in a metal substrate can be dependent on the intrinsic properties of the specific metal, as well as on the bulk properties such as thickness. Extrinsic conditions, such as temperature for example, can affect flexibility. For the purposes of the present invention, flexibility can be loosely described as the extent to which the substrate will allow utilization of roll-to-roll processes.
  • a flexible substrate of the present invention can be a flexible polymeric substrate.
  • Polymeric substrates suitable for use in the present invention can include polyimide polymers and polyethyleneterephthalate (PET) polymers, for example. All polymers are not suitable for use herein. Polymers such as PET can degrade at the high temperatures used in the process of the present invention.
  • the present invention is a process to make such heat-degradable polymers suitable for use in the practice of the present invention, whereby the high temperature is localized only at the surface of the polymer and whereby such localization of heating can substantially reduce the negative effect of high temperature processing on the degradable polymer by avoiding substantial thermal degradation in other regions of the polymer.
  • the present invention is an article comprising a glass-coated polymer composite layer.
  • Glass-coated polymer composite layers can be useful in electronic devices or as a component of a photovoltaic cell, for example.
  • a glass-coated PET composite layer can be useful as a barrier layer in a photovoltaic cell.
  • a glass-coated polyimide composite layer can be useful as a substrate layer in a photovoltaic cell for deposition of thin-film photovoltaic cells.
  • a suitable substrate must be able to withstand processing temperatures of greater than 250°C up to about 800°C.
  • One aspect of this invention is a process comprising:
  • the glass precursor comprises S1O2, AI2O3, Na2O, and B2O3, and optionally an oxide selected from the group consisting of MgO, K 2 O, CaO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 or any oxide of a lanthanide metal
  • the passivation may protect the surface from chemical attack.
  • the glass layer may serve as a thermal and/or electrical insulating layer, or also as an ion barrier, preventing detrimental doping of CIGS from iron, chromium, vanadium, nickel, titanium, phosphorus, manganese, molybdenum, niobium (or columbium) upon thermal processing of solar cells at elevated temperatures (ion migration prevention at 600 °C has been characterized by ESCA).
  • An additional desirable property the glass passivation layer offers is leveling of the stainless steel surface to minimize shunting of the solar cell (planarization Ra ⁇ 20nm can be achieved and have been measured).
  • passivation in the present invention, it is meant that the stainless steel is prevented from undesirable interaction with the CIGS layer in a photovoltaic cell.
  • a passivating layer of the present invention acts to: (1 ) prevent ion contamination of the CIGS layer by stainless steel or other flexible substrate; (2) smooth irregularities in the surface of the stainless steel or other flexible substrate; and (3) provide electrical insulation of the CIGS layer from the stainless steel layer to enable monolithic stacking of a photovoltaic cell .
  • This process can be conducted batch-wise or as a continuous process, e.g., in a roll-to-roll process.
  • Suitable stainless steel substrates can be in the form of sheets, foils or other shapes. Sheets and foils are preferred for roll-to-roll processes.
  • Suitable stainless steel typically comprises: 13 - 22 wt% chromium; 1 .0 - 10 wt% aluminum; less than 2.1 wt % manganese; less than 1 .1 wt% silicon; less than 0.13 wt% carbon; less than 10.6 wt% nickel; less than 3.6 wt% copper; less than 2 wt % titanium; less than 0.6 wt%
  • molybdenum less than 0.15 wt% nitrogen; less than 0.05 wt%
  • the stainless steel comprises: about 13 wt% chromium; 3.0 - 3.95 wt% aluminum; less than 1 .4 wt% titanium; about 0.35 wt% manganese; about 0.3 wt% silicon; and about 0.025 wt% carbon, wherein the balance is iron.
  • the stainless steel comprises: about 22 wt% chromium and about 5.8 wt% aluminum, wherein the balance is iron.
  • the present invention is a process for depositing a glass layer or a glass precursor layer on the surface of a flexible metal substrate other than stainless steel.
  • Suitable other metals for the purposes of the present invention include, for example: aluminum, titanium, and molybdenum, nickel, vanadium, chromium, silver and gold Polymer Substrates
  • the present invention is a process for depositing a glass layer or a glass precursor layer on the surface of a flexible polymer substrate.
  • a polymer substrate suitable for the practice of the present invention is a thermoplastic or thermoset polymer that is capable of being processed at temperatures above 250°C without substantial degradation to the polymer chain, or significant deterioration of the desired and/or required properties of the polymer for the intended use of the glass/polymer multilayered article. For example,
  • PET polyethyleneterephthallate
  • polyimide polymers can be useful in the practice of the present invention. It can be necessary or desirable to heat only the surface of certain polymers, that is, only where the polymer surface will come into contact with the glass layer or glass precursor layer, in order to avoid potential degradation of the polymer in other regions of the polymeric substrate.
  • the substrate is coated with a glass precursor layer, followed by steps of drying and firing the glass precursor layer to form a glass layer on the stainless steel substrate.
  • the thickness of the glass layer can be increased by carrying out multiple cycles of coating-and-drying before firing, or by carrying out several cycles of coating-drying-and-firing.
  • the glass layer is formed by coating the surface of the stainless steel substrate, in whole or in part, with a glass precursor composition.
  • the precursor composition can comprise: (1 ) a form of silicon that is soluble in at least one solvent; (2) an aluminum compound; (3) a boron- containing compound; (4) a sodium salt and, optionally (5) a potassium salt.
  • a soluble form of silicon can be, for example, silicon tetraacetate, silicon tetrapropionate, bis(acetylacetonato) bis(acetato) silicon, bis(2- methoxyethoxy) bis (acetato) silicon, bis(acetylacetonato) bis(ethoxy) silicon, tetramethylorthosilicate, tetraethylorthosilicate,
  • An aluminum compound can be, for example: tris(acetylacetonato) aluminum, aluminum methoxide, aluminum ethoxide, aluminum
  • isopropoxide, aluminum n-propoxide, or mixtures thereof) is added as well as a trialkylborate (for example, trimethylborate, triethylborate,
  • tripropylborate trimethoxyboroxine, or mixtures thereof.
  • a precursor for sodium oxide can be, for example, sodium acetate, sodium propionate, sodium silicate, sodium alkoxides, sodium borate, sodium tetraphenyl borate, or mixtures thereof.
  • a sodium source is included in the glass precursor layer in order that the glass layer functions as a sodium transport layer, to provide a source of sodium to an adjacent layer in an electronic device such as a photovoltaic cell and improve the efficiency of the device.
  • the doping with sodium can be accomplished by doping the glass precursor layer with sufficient sodium to provide from about 0.01 atomic% to about 5 atomic% sodium to the conductive layer of a photovoltaic cell.
  • the sodium source can be ionic or covalent. Migration of sodium from the glass layer to the semi-conductive layer can provide the level of sodium required in the semi-conductive layer to exhibit improved efficiency relative to a cell wherein sodium is not present in the semi-conductive layer at the same level as described herein.
  • the sodium source can be, for example, any salt of sodium that can be dissolved or made soluble or dispersible in the glass precursor composition of the present invention.
  • the optional potassium salt can be, for example, potassium acetate, potassium propionate, potassium methoxide, potassium ethoxide, potassium isopropoxide, or mixtures thereof.
  • the soluble silicon can be dissolved in a solvent such as, for example: (1 ) a C1 -C10 alcohol (for example methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol, isomers of 1 -butanol, 1 -pentanol, 2-pentanol, 3-pentanol, isomers of 1 - pentanol, 1 -hexanol, 2-hexanol, 3-hexanol, isomers of 1 -hexanol, 1 - heptanol, isomers of 1 -heptanol, or mixtures thereof ); (2) an acid (for example, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, or mixtures thereof) and (3) water to obtain a solution of dissolved silicon solution.
  • Water can be included in an amount of from 0 to 4 mole
  • the sodium salt can be dissolved in the same C1 -C10 alcohol used to prepare the initial silicon solution, and added to the silicon solution .
  • the glass precursor formulation is filtered prior to coating the stainless steel substrate.
  • the composition of the glass precursors in the formulation is in an element ratio of about 100 (Si) to 45 (B) to 26 (Na) to 3 (Al).
  • the precursor composition can be prepared by dissolving a silicon oxide precursor (for example, tetraethylorthosilicate) in a minimum amount of 1 -butanol, or a 1 :1 mixture of 1 -butanol and acetic acid, and stirring. To this solution, two mole equivalents of water are added and the solution is refluxed for one hour. An aluminum oxide precursor (for example, tris(acetylacetonato)aluminum), a boron oxide precursor (for example, triethyl borate) and a sodium oxide precursor (for example, sodium tetraphenylborate) in 1 -butanol, are added. Once the precursors are dissolved, more solvent is added to obtain the desired concentration.
  • a silicon oxide precursor for example, tetraethylorthosilicate
  • the glass layer can optionally include an oxide of lithium, magnesium, potassium, calcium, barium, lead, germanium, tin, antimony, bismuth or any lanthanide.
  • Suitable precursors for Li 2 O, MgO, BaO, K 2 O, CaO, PbO, GeO 4 , SnO2, Sb2O3, B12O3 or any oxide of a lanthanide metal can include the respective acetates, for example: potassium acetate, calcium acetate, lead acetate, germanium acetate, tin acetate, antimony acetate, and bismuth acetate.
  • Other oxide precursors can be used, as may be known to one of ordinary skill in the art.
  • Silicon alkoxides for example, a silicon tetraalkylorthosilicate
  • aluminum alkoxides for example, aluminum isopropoxide
  • borosilicate glass nanoparticles can be added to the formulation.
  • Depositing a coating of the glass precursor composition onto the stainless steel substrate can be carried out by any known and/or conventional means, including bar-coating, spray-coating, dip-coating, microgravure coating, or slot-die coating.
  • any known and/or conventional means including bar-coating, spray-coating, dip-coating, microgravure coating, or slot-die coating.
  • One of ordinary skill in the art would appreciate the benefits and/or disadvantages of any of these conventional coating means, and could choose an appropriate coating method based on the particulars of the process parameters under consideration.
  • the precursor After coating the glass precursor composition onto the stainless steel substrate, the precursor is typically dried in air at 100 to 150 °C to remove solvent. In some embodiments, the dried glass precursor layer is then fired in air or an oxygen-containing atmosphere at 250 to 800 °C to convert the glass precursor layer to a fired glass layer.
  • firing it is meant that the glass precursor layer is heated above the decomposition temperature of the precursors in an oxidizing atmosphere to:
  • the cycle of (1 ) coating followed by (2) drying can be repeated numerous times, depending on the thickness of the glass layer that is desirable, and the number of repetitions that are needed to obtain the desired thickness. Typically the desired thickness can be obtained with 2- 5 repetitions of the coating/drying cycle.
  • the thickness of the fired glass layer can be from about 10 nm to several micrometers in thickness. In certain embodiments, the thickness of the glass fired layer can be in the range of from about 1 nm to several microns in thickness. In some uses -- for example when used in a photovoltaic cell - it can be desirable to increase the flexibility of the fired glass layer by reducing its thickness to within the range of from about 10 nm to about several microns, or from about 25 nm to about 10
  • the desired thickness for flexibility can depend on the application, the composition, or other factors. For example, in some applications pinholes in the glass layer can be desirable and it can therefore be desirable to reduce the thickness of the glass layer to allow pinholes. In other applications the thickness can be increased to provide optimum insulation, therefore, minimum pinholes in the glass layer.
  • the purpose of the present invention is to provide flexibility to a glass layer whereby normal handling does not produce cracks in the glass. Cracks, even if observable only with a microscope, are undesirable. To avoid cracking in the glass layer, an upper thickness limit for the glass layer may be reached at about 5 micrometers, or at about 4 micrometers, or at about 3 micrometers.
  • the steps of (1 ) coating, (2) drying, and (3) firing can be repeated 2 or more times. This can also increase the total thickness of the fired glass layer. Multiple intermediate firing steps facilitate removal of any carbon that might be present in the glass precursor components, and therefore multiple firing steps can be preferred. Also optionally, the drying step can be skipped and the glass precursor layer can be pre-fired at lower temperature than the firing step, and then subsequently fired. It can be advantageous to pre-fire the glass precursor layer to, for example: drive off solvent at a faster rate; facilitate gellation of the glass precursor layer; and/or to facilitate other interactions among the components of the glass precursor layer. Any combination of drying, pre-firing and firing steps can be repeated multiple times to get the thickness or other properties desirable in the final glass layer.
  • water is added to the precursor mixture prior to the coating step. This increases the viscosity of the glass precursor composition and facilitates the formation of glass layers of 50 nm to 2 microns thickness in one coating and drying cycle.
  • Both the firing step(s) and drying step(s) are typically conducted in air to ensure complete oxidation of the glass precursors.
  • the presence of elemental carbon, carbonate intermediates or reduced metal oxides in the glass layer may lower the breakdown voltage of the insulating layer.
  • the glass layer can comprise: greater than 70 wt% silica; less than 10 wt% alumina; 5-15 wt% of a boron oxide; and less than 10 wt% of oxides of sodium and/or potassium.
  • the fired glass layer comprises: about 81 wt% SiO 2 , about 13 wt% B 2 O 3 , from about 1 wt% up to about 4 wt% Na2O, and about 2 wt% AI2O3.
  • the glass layer can comprise the sodium component in an amount greater than about 4% by weight of the glass layer.
  • the sodium component can be present in an amount of from about 4% to about 25% by weight of the glass layer, or from about 4% to about 18% by weight of the glass layer, or from about 4% to about 16% by weight of the glass layer.
  • the glass precursor compositions are selected to provide coefficients of linear thermal expansion (CTE) of the glass layers to be close to those of the Mo and CIGS (or CZTS-Se) layers to reduce stress on the Mo and CIGS (or CZTS-Se) layers and to reduce film curling.
  • CTE of the borosilicate glass is about 3.25 x 10 "6 /°C to provide a good match to the CTE of the Mo layer (about 4.8 x 10 "6 /°C) and the CIGS layer (about 9 x 10 "6 /°C).
  • One aspect of this invention is a multi-layer article comprising: a) a stainless steel substrate comprising 1 to 10 wt% aluminum;
  • a glass layer disposed directly on at least a portion of the stainless steel, wherein the glass layer comprises S1O2, AI2O3, Na2O, B2O3, and optionally an oxide selected from the group consisting of LiO, MgO, K 2 O, BaO, CaO, PbO, GeO 4 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 and any oxide of a lanthanide metal.
  • the stainless steel substrate and glass layer are as described above.
  • This multilayer article can be used as the substrate for the manufacture of electronic devices, such as for example, organic light emitting diode display applications, white light organic light emitting diode applications, photovoltaic applications. Such multilayer articles can also be used in medical devices such as heart valves.
  • the multilayer article further comprises: d) a conductive layer disposed on at least a portion of the glass layer.
  • the multilayer article further comprises: e) a photoactive layer disposed on the conductive layer;
  • Such multilayer articles can be used in photovoltaic cells, for example.
  • Suitable conductive layers comprise materials selected from the group consisting of metals, oxide-doped metals, metal oxides, organic conductors, and combinations thereof.
  • a conductive metal layer can be deposited onto the glass layer through a vapor deposition process or electroless plating. Suitable metals include Mo, Ni, Cu, Ag, Au, Rh, Pd and Pt.
  • the conductive metal layer is typically 200 nm -1 micron thick. In one embodiment, the conductive material is molybdenum oxide-doped molybdenum.
  • the multilayer article comprises organic functional layers, e.g., organic conductors such as polyaniline and polythiophene.
  • the multilayer article is generally not heated above 450 °C, or 400 °C, or 350 °C, or 300 °C, or 250 °C, or 200 °C, or 150 °C, or 100 °C after the organic functional layer has been deposited.
  • Suitable photoactive layers include CIS (cadmium-indium-selenide),
  • the CIGS and CIS layers can be formed by evaporating or sputtering copper, indium and optionally gallium sequentially or
  • a suspension of metal oxide particles in an ink can be deposited on the conductive layer using a wide variety of printing methods, including screen printing and ink jet printing. This produces a porous film, which is then densified and reduced in a thermal process to form the CIGS or CIS layer.
  • printing methods including screen printing and ink jet printing.
  • the processes described hereinabove are known and conventional in the art. In fact, any known or conventional process can be used to form the CIGS or CIS layers.
  • CZTS-Se thin films can be made by several methods, including thermal evaporation, sputtering, hybrid sputtering, pulsed laser deposition, electron beam evaporation, photochemical deposition, and
  • CZTS thin-films can also be made by the spray pyrolysis of a solution containing metal salts, typically CuCI, ZnC ⁇ , and SnCI 4 , using thiourea as the sulfur source.
  • metal salts typically CuCI, ZnC ⁇ , and SnCI 4
  • the CdS layer can be deposited by chemical bath deposition, for example. Other means that are known and/or conventional can be used.
  • a suitable transparent conductive oxide layer such as doped zinc oxide or indium tin oxide, can be deposited onto the CdS layer by sputtering or pulsed layer deposition, for example. Other methods that are known and/or are conventional to one of ordinary skill in the art can be used.
  • a 50.8 micrometer thick stainless steel foil (Ohmaloy® 30, 2-3 wt% aluminum, ATI Allegheny Ludlum) was annealed at 1000 °C in air for 15 hr to provide a coating of alumina on the surface of the stainless steel foil. The foil was then diced to size and argon plasma-cleaned (A.G. Services PE-PECVD System 1000) for 30 sec under the following conditions:
  • Tetraethylorthosilicate (3.9042 g, 18.74 mmol) was dissolved in 1 -butanol (5.00 ml) and 5 ml of acetic acid containing 0.6725 ml of deionized water. The solution was refluxed for 1 h. To this solution, was added triethylborate (0.5247g, 3.59 mmol) and tris(acetylacetonato) aluminum (0.1768 g, 0.55 mmol).
  • a sodium tetraphenyl borate (1 .6553g; 4.84 mmol) solution in 1 -butanol (5 ml) was prepared and mixed with the silicon, aluminum, boron precursor 1 -butanol solution. .
  • the solution was stirred and 1 -butanol was added until a total volume of 25.00 ml was achieved.
  • the glass precursor composition was filtered through a 2 micron filter prior to coating the stainless steel substrate.
  • the substrates were rod-coated using a #20 bar on a Cheminstrument® motorized drawdown coater at room temperature in a clean room environment (class 100).
  • the coated substrate was then dried at room temperature for 30s and subsequently at 150 °C for 2 min to form a dried glass precursor layer on the annealed stainless steel substrate. This procedure was used one or more times in each of the examples described below.
  • the coated substrates were fired to 500 °C for 2 min at a ramp rate of 8 °C/s using a modified Leyboldt L560 vacuum chamber outfitted with cooled quartz lamp heaters above and below the coated substrate, with an air bleed of 20 seem (total pressure 1 mTorr). Out-gassing was monitored using a residual gas analyzer. This procedure was used one or more times in each of the examples described below.
  • Breakdown voltage was measured with a Vitrek 944i dielectric analyzer (San Diego, CA). The sample was sandwiched between 2 electrodes, a fixed stainless steel rod as cathode (6.35 mm diameter and 12.7 mm long) and a vertically sliding stainless steel rod as anode (6.35 mm diameter and 100 mm long). The mass of the sliding electrode (32.2 g) produced enough pressure so the anode and cathode form good electrical contact with the sample. The voltage was ramped at 100 V/s to 250 V and kept constant for 30 sec to determine the breakdown voltage and the sustained time. The thickness was measured using a digital linear drop gauge from ONO SOKKI, model EG-225. Dielectric strength can be calculated as the breakdown voltage per unit of thickness.
  • the filtered glass precursor composition described above (0.1 ml) was rod-coated onto an annealed, plasma-cleaned stainless steel substrate and dried, as described above.
  • the drawdown coating and drying cycle was repeated five times.
  • the substrate was then fired, as described above.
  • Breakdown voltage was found to be 520 - 600 V DC at 10 randomly selected locations.
  • the filtered glass precursor composition (0.1 ml) was rod-coated onto an annealed, plasma-cleaned stainless steel substrate and dried, as described above.
  • This layer was then fired as described above.
  • the drawdown coating and drying cycle was repeated under the same conditions five times.
  • the coated substrate was fired a second time, and then a 200 nm Mo layer was deposited on the fired glass layer via sputter vapor deposition.
  • the filtered glass precursor composition (0.1 ml) was rod-coated onto an annealed, plasma-cleaned stainless steel substrate and dried, as described above.
  • This layer was then fired as described above.
  • a 0.5M precursor formulation with respect to [Si] was prepared in the following manner:
  • a 50.8 micrometer thick stainless steel foil (430 ferritic stainless steel, from ATI) was diced to size and cleaned by rinsing the surface with methanol.
  • the glass precursor formulation was filtered using a 0.45 micron PTFE filter.
  • the cleaned stainless steel substrate was rod-coated with a #40 bar on a Cheminstrument® motorized drawdown coater with 0.1 ml of filtered glass precursor formulation at room temperature in a clean room environment (class 100).
  • the coated sample was then dried at room temperature for 30s, then at 150°C for 2 minutes.
  • the final layer was then fired to 500°C for 2 minutes at a ramp rate of 10°C/s.
  • Example 5 SODIUM ALUMINOBOROSILICATE GLASS COMPOSITION HAVING 12% WEIGHT NA ? O COATED ON STAINLESS STEEL 430
  • a 0.5M precursor formulation with respect to [Si] was prepared in the following manner:
  • a 50.8 micrometer thick metal stainless steel foil 430 foil was diced to size and argon plasma cleaned (A.G. Services PE-PECVD System 1000) under the following conditions for a time of 30s:
  • the glass precursor formulation was filtered using a 0.45 micron PTFE filter.
  • the cleaned metal foil substrate was rod-coated with a #40 bar on a
  • Cheminstrument® motorized drawdown coater with 0.1 ml of filtered glass precursor formulation at room temperature in a clean room environment (class 100). The coated sample was then dried at room temperature for 30s, then at 150°C for 2 minutes.
  • the layer was then fired to 500°C for 2 minutes at a ramp rate of 10°C/s.
  • a 500 nm Mo coating was deposited via sputter vapour deposition.
  • a 1 .7um Cu(ln 0 . 7 Gao.3)Se2 coating was then deposited via an evaporation process.
  • a 70nm CdS coating was the subsequently deposited via a wet bath deposition process.
  • a 120nm aluminium zinc oxide layer was then deposited by sputtering
  • a 0.5M precursor formulation with respect to [Si] was prepared in the following manner: 2.3466g (1 1 .26 mmol) of tetraethylorthosilicate (Sigma Aldrich, >99.0% purity) was dissolved in 10ml of 1 -butanol. To this solution, was added 1 .5 mole equivalents of glacial acetic acid (1 .01 OOg; 16.89 mmol, EMD, >99.7% purity) and 1 drop (0.02g) of nitric acid. The solution was then refluxed at 1 18°C for 2h.
  • a 50.8 micrometer thick metal stainless steel foil 430 foil was diced to size and cleaned by rinsing the surface with methanol and by argon plasma treatment (A.G. Services PE-PECVD System 1000) under the following conditions for a time of 30s:
  • the glass precursor formulation was filtered using a 0.45 micron PTFE filter.
  • the cleaned metal foil substrate was rod-coated with a #40 bar on a
  • Cheminstrument® motorized drawdown coater with 0.1 ml of filtered glass precursor formulation at room temperature in a clean room environment (class 100). The coated sample was then dried at room temperature for 30s, then at 150°C for 2 minutes.
  • the layer was then fired to 500°C for 2 minutes at a ramp rate of 10°C/s.
  • the drawdown coating, drying and firing cycle was repeated under the same conditions until the desired thickness was obtained.

Abstract

La présente invention concerne un procédé de fabrication d'un matériau enrobé de verre se prêtant à la fabrication de cellules solaires et autres dispositifs électroniques flexibles. L'invention concerne en outre des articles comprenant lesdites cellules solaires flexibles.
PCT/US2011/051580 2010-09-14 2011-09-14 Substrats polymères flexibles enrobés de verre pour cellules photovoltaïques WO2012037242A2 (fr)

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CN103378201A (zh) * 2012-04-16 2013-10-30 财团法人工业技术研究院 柔性基板、复合层在太阳能电池的应用、及太阳能电池
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WO2014138393A1 (fr) * 2013-03-06 2014-09-12 Covalent Coating Technologies, LLC Fusion de verre/céramique biocompatible à un substrat métallique
US9421303B2 (en) 2013-03-06 2016-08-23 Covalent Coating Technologies, LLC Fusion of biocompatible glass/ceramic to metal substrate
US10109761B2 (en) 2014-05-23 2018-10-23 Flisom Ag Fabricating thin-film optoelectronic devices with modified surface
US10431709B2 (en) 2014-05-23 2019-10-01 Flisom Ag Fabricating thin-film optoelectronic devices with modified surface
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US10651324B2 (en) 2016-02-11 2020-05-12 Flisom Ag Self-assembly patterning for fabricating thin-film devices
US10658532B2 (en) 2016-02-11 2020-05-19 Flisom Ag Fabricating thin-film optoelectronic devices with added rubidium and/or cesium
US10971640B2 (en) 2016-02-11 2021-04-06 Flisom Ag Self-assembly patterning for fabricating thin-film devices
US11257966B2 (en) 2016-02-11 2022-02-22 Flisom Ag Fabricating thin-film optoelectronic devices with added rubidium and/or cesium
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