EP2628188A1 - Module solaire à couche mince ayant une structure de vitre feuilletée - Google Patents

Module solaire à couche mince ayant une structure de vitre feuilletée

Info

Publication number
EP2628188A1
EP2628188A1 EP11779596.3A EP11779596A EP2628188A1 EP 2628188 A1 EP2628188 A1 EP 2628188A1 EP 11779596 A EP11779596 A EP 11779596A EP 2628188 A1 EP2628188 A1 EP 2628188A1
Authority
EP
European Patent Office
Prior art keywords
layer
thin
film solar
solar module
adhesive layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11779596.3A
Other languages
German (de)
English (en)
Inventor
Matthias DÖCH
Walter Stetter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Priority to EP11779596.3A priority Critical patent/EP2628188A1/fr
Publication of EP2628188A1 publication Critical patent/EP2628188A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0869—Acids or derivatives thereof
    • C09D123/0876—Neutralised polymers, i.e. ionomers
    • 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • H01L31/06—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 characterised by potential barriers
    • H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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 invention relates, according to its type, to a thin-film solar module with a composite disk structure.
  • Photovoltaic layer systems for the direct conversion of solar radiation into electrical energy are well known.
  • the materials and the arrangement of the layers are coordinated so that incident light radiation is converted directly into electrical current by one or more semiconductive layers with the highest possible radiation yield.
  • Photovoltaic layer systems are also referred to as "solar cells”.
  • the term "thin-film solar cells ⁇ " refers photovoltaic layer systems with thicknesses of only a few microns, which support substrates need to provide sufficient mechanical strength.
  • ⁇ based polycrystalline chalcopyrite semiconductor In terms of efficiency to thin film solar cells have proved ⁇ based polycrystalline chalcopyrite semiconductor to be advantageous, whereby in particular ⁇ sondere copper-indium-diselenide (CuInSe 2 or CIS) Due to its angepass- to the spectrum of sunlight th bandgap by a particularly high Absorpti ⁇ onskostoryen distinguished.
  • CuInSe 2 or CIS copper-indium-diselenide Due to its angepass- to the spectrum of sunlight th bandgap by a particularly high Absorpti ⁇ onskostoryen distinguished.
  • Carriers known substrates for thin film solar cells contained th inorganic glass, polymers, or metal alloys, and may be designed as rigid plates, or flexible films, depending on the layer thickness and Materialei ⁇ properties. Because of the widely available carrier ⁇ substrates and a simple monolithic integration of large assemblies can be manufactured cost of thin film solar cells. Since only voltage levels of less than 1 volt are usually achievable with individual solar cells, many solar cells are usually connected in series in a solar module in order to obtain a technically useful output voltage in this way. Thin-film solar modules offer the particular advantage that the thin-film solar cells can be serially connected in integrated form during layer production.
  • the solar modules must be permanently ge ⁇ protects against environmental influences.
  • the adhesion-promoting polymer films contain, for example, polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyethylene (PE), polyethylene acryl copolymer or polyacrylamide (PA).
  • PVB polyvinyl butyral
  • EVA ethylene vinyl acetate
  • PE polyethylene
  • PA polyacryl copolymer
  • Adhesion-promoting polymer films with io ⁇ African polymers are th example, from the Druckschrif- US 5,476,553 and WO 2009/149000 known.
  • the object of the present invention is to develop conventional thin film solar modules of the type in question ⁇ the type in an advantageous manner, in particular aging and weather-related Lei ⁇ tion losses of solar modules to be reduced at comparatively low ⁇ production costs.
  • a thin-film solar module with a composite disk structure is shown.
  • the thin-film solar module has a plurality of thin-film solar cells connected in series for photovoltaic power generation on, which are preferably interconnected in an integrated form.
  • the thin film solar module comprises two through an adhesive layer (encapsulant) is fixedly connected ⁇ interconnected substrates.
  • Each Solarzel ⁇ le has a disposed between the two substrates layer structure comprising a first electrode layer, a second electrode layer and at least one is arranged between the two electrode layers semiconductor layer.
  • each layer may comprise one or more individual layers.
  • a hetero-junction or pn-junction that is to say a sequence of layers of different conductivity type, is formed in each case.
  • the semiconductor layer is doped with a dopant, typically metal ions.
  • the semiconductor layer consists of a chalcopyrite compound, which is in particular an I-III-VI semiconductor from the group copper indium / gallium Dischwefei / diselenide
  • the doping is preferably carried out with sodium, potassium ⁇ around and / or lithium, wherein the dopant in the semiconductor layer is present ionic.
  • the sodium, potassium or lithium doping leads to an intrinsic doping of the copper indium / gallium Dischwefei / Diselenids
  • the two substrates interconnecting adhesive layer comprising the dopant used for the Dotie ⁇ tion of the semiconductor layer (typically metal ions) in an amount such that diffusion of the dopant of the semiconductor layer is suppressed in the adhesive layer.
  • a diffusion of the charged dopant from the semiconductor layer into the adhesive layer can be at least vermin ⁇ changed when the dopant in the adhesive layer at least in a certain minimum concentrate is included ion.
  • the long-term stability of the solar module can be improved and a performance penalty to be counteracted in the semiconductor layer due to occurring defects ⁇ Tenden reduced by aging Dotierstoffkonzentrat ion.
  • the out-diffusion of the charged dopant from the semiconductor layer is always accompanied by a diffusion ei ⁇ nes charged particle the same charge type, so that ultimately takes place an exchange between ions of the same charge at di f fus ionsVorgang.
  • Substrate bonding adhesive layer of ei ⁇ nem material that consists of a compound or at least this includes, which contains the dopant used for doping the semiconductor layer ionically bound.
  • the ions of the dopant of the adhesive layer are thus suitably used as a diffusion source for the ions of the species of the semiconductor layer for Availability checked ⁇ supply.
  • an adhesion-promoting polymer layer in particular an ionic polymer (ionomer)
  • wel ⁇ ches easy to handle and is inexpensive can be used in industrial scale production.
  • a set ⁇ ions can be chemically performed in a simple manner, so that the concentration of the dopant in the adhesive layer is easily and reliably adjusted.
  • the ionomer has relatively long non-ionic alkylene chains. Due to these alkylene chains, the adhesive layer advantageously has a relatively low electrical conductivity despite the ionic portions of the polymer, so that the electrically insulating property of the adhesive layer is not or only slightly impaired by the ionic property of the ionomer.
  • the two substrates together linking adhesive ⁇ layer preferably contains ionomers, ie organic polyme ⁇ re functional with ionic groups.
  • the adhesive layer contains preferably copolymers and / or block copolymers of formula AB, wherein A is linear or branched non-polar hydrocarbon groups and B hydrocarbon ⁇ groups with sodium-bound acid groups.
  • non-polar hydrocarbon groups include saturated and unsaturated hydrocarbon groups ⁇ material having no polar functional groups.
  • sodium-bound acid groups includes organic acid groups, the acidic protons are replaced partially or totally by sodium ions. The replacement of the acidic protons can be carried out, for example, by reaction with sodium hydroxide solution.
  • 20% to 90% of the acidic protons are replaced by the dopant ions, in particular sodium ions, whereby advantageously a particularly high stability of the semiconductor layer can be achieved.
  • less than 5% of the acidic protons (but more than 0%) are replaced by dopant ions, in particular sodium ions, which advantageously results in particularly high adhesion the adhesive layer on the two substrates can be achieved. This applies in particular to glassy substrates in which hydrogen bonds can form between the acidic protons of the adhesive layer and Si atoms of the substrates.
  • a relative proportion of the acidic protons, which are replaced by the dopant ions, in particular sodium ions in a range from 0.1% to less than 5%, in particular 1% to 4%, in particular 2% to 4%, in particular 3% to 4%.
  • the above percentages indicate the relative proportion of substituted acidic protons, based on the total amount of acidic protons before substitution. The percentages thus correspond to a degree of substitution of the material of the adhesive layer.
  • the groups A and B can occur in the copolymer both alternately -ABABA and non-alternating, for example in the sequence -AABABBB- or -AAAAABBBB-.
  • the adhesive layer preferably contains other thermal moplastische polymers such as polyolefins, polyethylene, Po ⁇ lypropylen, polyacrylates, ethyl acrylate, methyl acrylate, polyvinyl lyvinylalkohol, polyvinyl acetate, polyvinyl acetals and / or polyamide.
  • the adhesive layer preferably contains 5 to 30% by weight (percent by weight) of copolymers of the formula AB.
  • R 2 -COONa, -CH 2 -COONa, S0 3 Na, or -H 2 CSNa, and
  • R 3 H, CH 3 , CH 2 -CH 3 or phenyl
  • n and m correspond to numbers> 5, preferably> 10, particularly preferably> 25 and can assume the same or different values. Within the scope of the polymer molecule weight distribution, averaged, not complete values of n and m are also possible.
  • the copolymers of the invention can be prepared, for example, by copolymerization of ethylene and methacrylic acid. Advantageous it may be if the adhesive layer contains copolymers in which as radicals R 2 exclusively -H 2 CSNa are included.
  • the copolymers of the formula A-B contain the constituent B preferably in an amount of 5 to 30 wt .-% of the component B, particularly preferably in an amount of 10 to 20 wt .-%.
  • the charged dopant may, for example, be adsorbed on at least one surface facing the semiconductor layer (alternatively on both surfaces) of the adhesive layer.
  • Ki ⁇ NEN the adsorbed ions of a reduction in the concentration of the dopant into the semiconductor layer are particularly effective against.
  • An adhesive film for bonding the two substrates by melting with temperature increase can be particularly simple and inexpensive provided with adsorbed Dotierstoffionen in industrial mass production. It suffices, for example, to immerse the adhesive film in a corresponding immersion bath with a solution containing the dopant. Alternatively, it would also be conceivable to spray the adhesive film with this solution.
  • the term “adsorption” is understood to mean the adhesion of the dopant to the surfaces of the adhesive film, regardless of the nature of the binding of the dopant to the surfaces.
  • binding mechanisms should be included, which are known in the context of "chemical adsorption” or “physical adsorption” in the art.
  • General suspended the concentra ⁇ on the dopant, which contained in the adhesive layer for inhibiting the diffusion of dopant from the semiconductor layer must be on the concentration of the dopant in the semiconductor layer.
  • a mass occupancy in a sodium ion-doped chalcopyrite semiconductor of the group copper indium / gallium disulphide / diselenide (Cu (In, Ga) (S, Se) 2 ) is in the range of 200-1000 ng / cm 2 .
  • the material of the adhesive layer is in a range of 0.1 to 4 wt%, more preferably in a range of 0.5 to 2 wt%, and even more preferably in a range of 1 to 2 wt%.
  • the metal ions may, for example, be contained in a range of more than 1.5% by weight to 2% by weight, in particular 1.6% by weight to 2% by weight, in the adhesive layer.
  • the percentages here refer to the total weight of the adhesive layer contained in the
  • the adhesive layer is connected ionically and / or covalently to the adjacent layers or layers contacting the adhesive layer.
  • a covalent bond between the adhesive layer and contacting these layers can be preferably achieved so that the adhesive layer contains a compound on ⁇ comprises containing inorganic hydride compounds with the Mate rials the may form the adhesive layer contacting the adjacent layers and.
  • the adhesive layer may contain, for example, alkylsilanes or alkylalans in a suitable amount for this purpose. This compound can for example be added to the material of the adhesive layer. Alternatively, a layer consisting of this compound can be arranged in each case between the adhesive layer and the adjacent layers or the layers contacting the adhesive layer.
  • the adhesive layer has a water content of less than 0.1% or is completely free of water.
  • the long-term stability of the thin-film solar module can be further improved by inhibiting the diffusion of metal ions from the semiconductor layer by reducing the amount Moegli ⁇ cher exchange partner (hydrogen ions).
  • Prior art ionomer films used as an adhesive layer have a certain amount of zinc for lowering the moisture content, as is known, for example, from WO 02/103809 A1.
  • As experiments of the registration ⁇ rin have shown a so-called Dry-heat aging test in Surprisingly, the efficiency of Cu (In, Ga) (S, Se) 2 _ thin film solar cells with adhesive layers having a zinc content of 0 , 7 wt .-% at a temperature of 85 ° C significantly lowered.
  • the Dichtma ⁇ TERIAL is formed advantageous in that it (for example by lithe Zeo-) water chemically (eg calcium carbonate CaO) and / or physically may bind.
  • a significant advantage of such a sealing material results from the fact that it serves as a sink for water molecules and thus can attract and bind water in the edge region between the two substrates, so as to lower the water content in the thin-film solar module.
  • the first electrode layer is formed in the form of a transparent front electrode layer and the second electrode layer is formed as an opaque back electrode layer.
  • Zvi ⁇ a rule, arranged on a ask ⁇ faces of the front electrode layer side of the back electrode layer ⁇ sub strate and the back electrode layer, a material for the doping, in particular metal ions, disposed impermeable barriers ⁇ layer.
  • the long-term stability of the thin-film solar module can be further improved.
  • the invention further extends to a method for producing a thin-film solar module. The method comprises a step in which two substrates with a layer structure arranged between the two substrates to be provided.
  • the layer structure comprises a first electrode layer, a second electrode layer and at least one semiconductor layer arranged between the two electrode layers, wherein the semiconductor layer forms a pn junction and is doped with a dopant.
  • the method includes a further step, in which the two substrates are bonded with an adhesive layer under Einwir ⁇ effect of heat, vacuum and / or pressure.
  • the adhesive layer used has the dopant of the semiconductor layer in an amount such that diffusion of the dopant of the semiconductor layer in the adhesive layer ⁇ is prevented.
  • connection of the thin-film solar module takes place, for example, with known lamination processes, for example with autoclave processes or vacuum processes, so that no further details need to be given here
  • the invention extends to the use of an adhesive layer in a process as described thin-film solar module, wherein the adhesive layer comprises the information contained in the half- ⁇ conductor layer of the thin film solar module Do ⁇ animal material in an amount such that the Diffu ⁇ sion of the dopant from the doped Semiconductor layer is prevented in the adhesive layer.
  • the invention extends to the use of an adhesive layer having a sodium content of from 0.1 to 4% by weight in a thin-film solar module with a sodium-doped semiconductor layer, in particular a sodium-doped Cu (In, Ga) ( S, Se) 2 ⁇ layer. Due to the sodium content of the adhesive layer, the diffusion of Nat ⁇ criterion is suppressed from the sodium-doped semiconductor layer in the adhesive layer.
  • the invention also extends to the use of an adhesive layer in a process as described Dünn Anlagenso ⁇ larmodul which ionomers, in particular copolymers of research mel AB, where A is non-polar hydrocarbon groups and B is hydrocarbon groups with sodium-bonded organic acid groups.
  • the copolymers of formula AB can Be ⁇ stand part B, in particular in an amount of 5 to 30 weight percent, in particular 10 to 20 weight percent, hold ⁇ ent.
  • a relative proportion of the acidic protons of the ionomers substituted by the dopant may be more preferably less than 5% (but more than 0%).
  • Fig. Larzelle 1 is a schematic cross sectional view of an example of the exporting ⁇ approximately Dünn Anlagenso- according to the invention.
  • FIG. 2 is a schematic cross-sectional view of an example of exporting ⁇ approximately Dünn Anlagenso ⁇ larmoduls invention with two series-connected thin-film solar cells.
  • FIG. 1 illustrates a thin-film solar module, designated overall by the reference numeral 1.
  • the thin film solar module ⁇ 1 comprises a plurality of interconnected solar cells in an integrated form in series 11, wherein in figure for the sake of simplicity, only a single thin-film solar cell 11 is shown.
  • the thin film solar module 1 one of the so-called substrate configuration corresponding structure, ie it has an electrically insulating first substrate 2 having applied thereto a layer structure 3 of PH ⁇ NEN layers, the layer structure 3 on a light-incident-side surface 4 of the first Substrate 2 is arranged.
  • the first substrate 2 consists here beispielswei ⁇ se of glass with a relatively low Lichtehr understand ⁇ speed, while equally other electrically insulating materials with desired strength and inert behavior compared to the process steps performed can be set sets.
  • the layer structure 3 comprises a rear electrode layer 5 which is arranged on the surface 4 of the first substrate 2 and consists, for example, of an opaque metal such as molybdenum (Mo) and can be applied to the first substrate 2, for example by vapor deposition or magnetic field-assisted cathode sputtering.
  • the back ⁇ electrode layer 5 has a layer thickness of 300 nm to 600 nm, which is for example 500 nm.
  • a photovoltaically active semiconducting ⁇ ter- or absorber layer 6 is deposited, consisting of a metal-doped ion semiconductor whose band gap is preferably able to absorb the greatest possible proportion of the sunlight.
  • the absorber layer 6 consists, for example, of a p-type chalcopyrite semiconductor, for example a compound of the group Cu (In, Ga) (S, Se) 2 , in particular sodium (Na) -doped
  • the absorber layer 6 has, for example, a layer thickness which is in the range of 1-5 ⁇ and is for example about 2 ⁇ .
  • a barrier ⁇ layer which acts as a diffusion barrier for serving as a dopant metal ions of the absorber layer provided be, which is not shown in detail in Figure 1.
  • the bar ⁇ centering layer contains, for example silicon nitride.
  • a buffer layer 7 is separated off, which here miumsulfid example of a single ply cadmium (CdS) and a single layer of intrinsic zinc oxide (i-ZnO) is made, which is not closer Darge in Figure 1 ⁇ situated on the absorber layer.
  • a front electrode layer 8 is applied, for example, by vapor deposition.
  • the front electrode layer 8 is ⁇ ⁇ ral Scheme transparent to radiation in the visible Spekt ( "window electrode”) / so that the irradiating sunlight is attenuated only slightly.
  • the transparent front electrode layer 8 is based beispielswei ⁇ se on a doped metal oxide, such as n-conductive, aluminum (Al) -doped zinc oxide (ZnO).
  • TCO Transparent Conductive Oxide
  • a heterojunction ⁇ gear ie, sequence of layers of the opposite conductivity type
  • the buffer layer 7 can bring about an electronic matching between the semiconductive material of the absorber layer 6 and the material of the front electrode layer 8.
  • the layer thickness of the front electrode layer 8 is for example about 500 nm.
  • the layer structure 3 is provided with a material transparent to sunlight second substrate 10 is, for example ⁇ from extra-white glass with a low iron content be, wherein both other electrically insulating materials with the desired strength and inert behavior can be used in relation to the process steps carried out.
  • the second substrate 10 serves to Ver ⁇ sealing of the layer structure 3.
  • the first substrate 2 and the second substrate 10 are connected by the adhesive layer 9 to each other.
  • the adhesive layer ⁇ 9 is here, for example a thermoplastic adhesive layer which is plastically deformable by heating and on cooling the two substrates firmly connects with each other 2 and 10.
  • the adhesive layer 9 has the same metal ions as the absorber layer 6, which are used there as a dopant.
  • the adhesive layer 9 for example, holds a certain An ⁇ part in an ionic polymer, here for example, polyethylene-co-methacrylic acid in which the hydrogen ions to ⁇ least in part by serving as a dopant Me ⁇ tallionen the absorber layer 6, here for example Sodium ions were exchanged.
  • a semiconductor of the group copper indium / gallium Dischwefel / diselenide (Cu (In, Ga) (S, Se) 2 ) ⁇ comprehensive Absorber layer 6 is the relative proportion of the sodium ions contained in the adhesive layer 9 with respect to the entire material of the adhesive layer 9 in a range of 1 wt .-% to 2 wt .-%.
  • the relative proportion of the sodium ions contained in the adhesive layer 9, based on the total amount of acidic protons before replacement by sodium ions be less than 5% (but more than 0%), on the one hand a particularly high Haf ⁇ tion of the two Substrates 2, 10 and on the other hand to achieve a sufficient in practice inhibition of the outdiffusion of sodium ions from the absorber layer 6.
  • polyethylene-co-methacrylic acid has the advantage that the acid has long non-ionic ethylene chains, so that the electrically insulating intrinsic shank of the adhesive layer 9 is only slightly affected by the ionomer.
  • the adhesive layer 9 could be formed, for example, by an adhesive sheet which is drawn through a saline bath prior to deposition in the layered structure 3 and fused to form the adhesive layer 9 to adsorb sodium ions to the surfaces thereof.
  • the adhesive layer 9 could be formed, for example, by an adhesive sheet which is drawn through a saline bath prior to deposition in the layered structure 3 and fused to form the adhesive layer 9 to adsorb sodium ions to the surfaces thereof.
  • the adhesive layer 9 could be formed, for example, by an adhesive sheet which is drawn through a saline bath prior to deposition in the layered structure 3 and fused to form the adhesive layer 9 to adsorb sodium ions to the surfaces thereof.
  • the adhesive layer 9 could be formed, for example, by an adhesive sheet which is drawn through a saline bath prior to deposition in the layered structure 3 and fused to form the adhesive layer 9 to adsorb sodium ions to the surfaces thereof.
  • the adhesive layer 9 contains a certain amount ei ⁇ ner compound which causes the material of the adhesive layer 9 can be received with the materials of the adjacent layers, here the second substrate 10 and the front ⁇ electrode layer 8, covalent bonds.
  • ei ⁇ ner compound which causes the material of the adhesive layer 9 can be received with the materials of the adjacent layers, here the second substrate 10 and the front ⁇ electrode layer 8, covalent bonds.
  • 9 ei ⁇ ne compound is admixed with the material of the adhesive layer
  • the inorganic hydride can form compounds with the materials of adjacent layers, for example, alkylsilanes or Alklyalane.
  • a layer consisting of this compound is respectively arranged between the adhesive layer 9 and the front electrode layer 8 or the second substrate 10.
  • a further improvement in the long-term stability of the thin-film solar module 1 can be achieved by inhibiting the access of water molecules to the absorber layer 6.
  • a circumferential edge gap between the two substrates 2 and 10 with a serving as a barrier to water sealing material here for example polyisobutylene (PIB)
  • PIB polyisobutylene
  • the sealing material is additionally provided with at least one Ver ⁇ bond to bind water molecules chemically and / or PHY sikalisch.
  • the thin film solar module 1 can be manufactured simply and inexpensively in industrial Se ⁇ rien production, wherein the different layers of the layer structure 3 on the first substrate 2 is deposited and using a suitable patterning technology such as laser write ⁇ and mechanical processing, for example by lifting or scratching, textured become.
  • a suitable patterning technology such as laser write ⁇ and mechanical processing, for example by lifting or scratching, textured become.
  • Structuring typically comprises three structuring steps for each solar cell, which need not be discussed in more detail here.
  • FIG. 2 shows two thin-film solar cells 11.1 and 11.2 of a thin-film solar module 1, which are connected in series.
  • the subdivision into the individual thin-film solar cells 11.1 and 11.2 takes place by means of cuts 12 using a suitable structuring technology, such as laser writing and mechanical processing, for example by lifting or scribing.
  • the individual solar cells 11.1 and 11.2 are connected in series via a layer region 13 of the back electrode layer 5.
  • An inventive thin film solar module 1 comprises at ⁇ play, 100 series-connected thin-film solar cell and an open circuit voltage of 56 volts.
  • both the resulting positive (+) and the resulting negative voltage connection (-) of the thin-film solar module 1 are guided over the back electrode ⁇ layer 5 and contacted there electrically.
  • the present invention provides a thin film solar module whose long-term stability is improved, with age-related, irreversible power losses can be counteracted due to a degradation of the absorber layer 6.
  • This can be achieved, on the one hand, in that migration of mobile ions from the absorber layer 6 is at least largely prevented by saturating the adhesive layer 9 with the mobile ions, so that it does not act as a sink for the mobile ions.
  • one may be counteracted by induced in the thin film solar module 1 before ⁇ handenes water, hydrolysis of the absorber layer 6 against. This avoids that hydrolysis products in the structuring trenches lead to unfavorable electrical resistances. In addition, it can be prevented that moisture increases the electrical parallel resistance of the solar cells.
  • sodium-doped Cu (In, Ga) (S, Se) 2 thin film solar modules _ significantly lowered by the indicated measures the usual losses in efficiency. As shown in Table 1, were sodium-doped
  • the sodium and zinc contents of the adhesive layers were determined by X-ray fluorescence analysis.
  • a sodium or zinc content of 0 wt .-% in Table 1 means a level of the fluorescence analysis in the X-ray detectable amount of ⁇ 100 ppm, bezo ⁇ gene on the weight of the adhesive layer.
  • film 2 having a sodium content of 0% by weight and a zinc content of 0% by weight after the dry heat aging test showed a loss relative to the efficiency of the thin film solar module of 10%.
  • Film 3 with a zinc content of 0.7% by weight showed a loss of 40%.

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Abstract

L'invention concerne un module solaire à couche mince (1) comprenant une pluralité de cellules solaires à couche mince (11) branchées en série pour produire de l'énergie photovoltaïque. Le module comprend deux substrats (2, 10) reliés l'un à l'autre par une couche d'adhésif (9). Chaque cellule solaire présente un empilement de couches, disposé entre les deux substrats, lequel empilement de couches comprend une première couche d'électrode (5), une deuxième couche d'électrode (8) et une couche semi-conductrice (6) disposée entre les deux couches d'électrode. La couche semi-conductrice forme selon l'invention une jonction PN, et elle est dopée avec un agent dopant. A cet effet, il importe que la couche d'adhésif contienne l'agent dopant en une quantité telle qu'elle empêche une diffusion de l'agent dopant de la couche semi-conductrice dans la couche d'adhésif.
EP11779596.3A 2010-10-12 2011-10-11 Module solaire à couche mince ayant une structure de vitre feuilletée Withdrawn EP2628188A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11779596.3A EP2628188A1 (fr) 2010-10-12 2011-10-11 Module solaire à couche mince ayant une structure de vitre feuilletée

Applications Claiming Priority (3)

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EP10187214 2010-10-12
EP11779596.3A EP2628188A1 (fr) 2010-10-12 2011-10-11 Module solaire à couche mince ayant une structure de vitre feuilletée
PCT/EP2011/067700 WO2012049157A1 (fr) 2010-10-12 2011-10-11 Module solaire à couche mince ayant une structure de vitre feuilletée

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EP2628188A1 true EP2628188A1 (fr) 2013-08-21

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US (1) US20130255745A1 (fr)
EP (1) EP2628188A1 (fr)
JP (1) JP2013542603A (fr)
KR (1) KR101531452B1 (fr)
CN (1) CN103155175A (fr)
EA (1) EA201390523A1 (fr)
WO (1) WO2012049157A1 (fr)

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CN108878584A (zh) * 2018-06-21 2018-11-23 汉能新材料科技有限公司 太阳能电池及其制备方法
CN108767038A (zh) * 2018-06-21 2018-11-06 汉能新材料科技有限公司 太阳能电池及其制备方法
EP3597389A1 (fr) * 2018-07-18 2020-01-22 PARAT Beteiligungs GmbH Procédé de fabrication d'un composant de surface et composant avec un ensemble de cellules solaires
US10931229B2 (en) * 2018-12-13 2021-02-23 Industrial Technology Research Institute Solar cell testing system and testing method thereof

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WO2004032189A2 (fr) * 2002-09-30 2004-04-15 Miasolé Appareil et procede de fabrication conçus pour produire a grande echelle de cellules solaires a film mince
CN100530701C (zh) * 2002-09-30 2009-08-19 米亚索尔公司 薄膜太阳能电池大规模生产的制造装置与方法
JP5054326B2 (ja) * 2006-05-01 2012-10-24 昭和シェル石油株式会社 Ｃｉｓ系薄膜太陽電池モジュールの改良された耐久性試験方法
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WO2012049157A1 (fr) 2012-04-19
EA201390523A1 (ru) 2013-08-30
US20130255745A1 (en) 2013-10-03
KR20130101083A (ko) 2013-09-12
CN103155175A (zh) 2013-06-12
KR101531452B1 (ko) 2015-06-24
JP2013542603A (ja) 2013-11-21

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