US20030175557A1 - Transparent substrate comprising an antireflection coating - Google Patents

Transparent substrate comprising an antireflection coating Download PDF

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Publication number
US20030175557A1
US20030175557A1 US10/296,410 US29641003A US2003175557A1 US 20030175557 A1 US20030175557 A1 US 20030175557A1 US 29641003 A US29641003 A US 29641003A US 2003175557 A1 US2003175557 A1 US 2003175557A1
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substrate
index
layer
oxide
glass
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Charles Anderson
Ulf Blieske
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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Assigned to SAINT-GOBAIN GLASS FRANCE reassignment SAINT-GOBAIN GLASS FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BLIESKE, ULF, ANDERSON, CHARLES
Publication of US20030175557A1 publication Critical patent/US20030175557A1/en
Priority to US12/496,966 priority Critical patent/US7833629B2/en
Priority to US12/893,024 priority patent/US8372513B2/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • 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
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10091—Properties of the bulk of a glass sheet thermally hardened
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/10201—Dielectric coatings
    • 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
    • B32B17/1077—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 polyurethane
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
    • F24S80/50—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings
    • F24S80/52—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings characterised by the material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G02B1/116—Multilayers including electrically conducting layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • 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
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick

Definitions

  • the invention relates to a transparent, especially glass, substrate provided on at least one of its faces with an antireflection coating.
  • Antireflection coatings usually consist, in the simplest cases, of a thin interferential layer whose refractive index is between that of the substrate and that of air or, in the more complex cases, of a film comprising multiple thin layers (in general, an alternation of layers based on a dielectric having a high refractive index and a dielectric having a low refractive index).
  • a first solution has consisted in using extra-clear glass, having a very low content of iron oxide(s).
  • extra-clear glass having a very low content of iron oxide(s).
  • Such is, for example, the glass sold by Saint-Gobain Vitrage in the “DIAMANT” range.
  • Another solution has consisted in providing the glass, on the outside, with an antireflection coating consisting of a monolayer of porous silicon oxide, the porosity of the material making it possible to lower the refractive index thereof.
  • an antireflection coating consisting of a monolayer of porous silicon oxide, the porosity of the material making it possible to lower the refractive index thereof.
  • the performance of this monolayer coating is not very high. Furthermore, its durability, especially with regard to moisture, is insufficient.
  • the object of the invention is therefore to develop a novel antireflection coating which is capable of further increasing the transmission through the transparent substrate carrying it (and of further reducing the reflection therefrom), within a broad wavelength band, especially both in the visible and in the infrared.
  • the object of the invention is to develop a novel antireflection coating suitable for solar cells.
  • the object of the invention is to develop such coatings which are furthermore capable of undergoing heat treatments, especially if the carrier substrate is made of glass which, in its final application, must be annealed or toughened.
  • the object of the invention is to develop such coatings which are sufficiently durable for outdoor use.
  • the subject of the invention is primarily a transparent substrate, especially made of glass, having on at least one of its faces an antireflection coating (A) comprising multiple thin layers of a dielectric having alternately high and low refractive indexes. It comprises, in succession:
  • a high-index first layer 1 having a refractive index n 1 , of between 1.8 and 2.3 and a geometrical thickness e 1 of between 5 and 50 nm;
  • a low-index second layer 2 having a refractive index n 2 of between 1.30 and 1.70 and a geometrical thickness e 2 of between 5 and 50 nm;
  • a high-index third layer 3 having a refractive index n 3 of between 1.80 and 2.30 and a geometrical thickness e 3 of at least 100 nm or at least 120 nm;
  • a low-index fourth layer 4 having a refractive index n 4 of between 1.30 and 1.70 and a geometrical thickness e 4 of at least 80 nm or at least 90 nm.
  • the term “layer” is understood to mean either a single layer, or a superposition of layers in which each of the layers respects the refractive index indicated and in which the sum of their geometrical thicknesses also remains the value indicated for the layer in question.
  • the layers are made of a dielectric, especially of the oxide or nitride type, as will be explained in detail below.
  • a dielectric especially of the oxide or nitride type
  • the invention applies preferably to glass substrates, but it may also apply to transparent substrates based on a polymer, for example polycarbonate.
  • the invention therefore relates to an antireflection film of the four-layer type. This is a good compromise since the number of layers is large enough for their interferential interaction to allow a significant antireflection effect to be achieved. However, this number remains sufficiently reasonable for it to be possible to manufacture the product on a large scale, on an industrial line, on large substrates, for example using a vacuum deposition technique of the sputtering type (magnetically enhanced).
  • the thickness and refractive index criteria used in the invention make it possible to obtain a broadband antireflection effect with a substantial increase in the transmission of the carrier substrate, not only in the visible range but also beyond it, especially in the infrared and more particularly in the near infrared. This is high-performance antireflection over a wavelength range extending at least between 400 and 1100 nm.
  • the thickness of the low-index last layer has been increased: its preferred thickness is greater than the ⁇ /4 value normally used (taking ⁇ as the centre of the visible spectrum);
  • the thickness of the high-index penultimate (third) layer is relatively large.
  • the inventors have thus discovered that they could use materials whose index is around 2, such as tin oxide SnO 2 or silicon nitride Si 3 N 4 (which include within this formula, silicon nitrides which may contain other elements in a minor amount compared with silicon, such as a metal of the Al type, or boron, the indicated stoichiometry of the nitrogen with respect to the silicon therefore not being limiting, but merely for ease of writing.
  • the oxygen stoichiometry of the metal or silicon oxides mentioned in the present text are especially compared with TiO 2 , these materials have the advantage of having very much higher deposition rates when the deposition technique called sputtering is used. Within this moderate range of indices, there is also a greater choice of materials that can be deposited by sputtering. This provides more flexibility in industrial manufacture and a greater possibility of adjusting the properties of the multilayer film.
  • the inventors have thus selected thicknesses for the layers of the multilayer film which are different from the thicknesses usually chosen for conventional antireflection coatings intended to reduce reflection only in the visible. In the present invention, this selection has been made so as to antireflect the substrate not only in the visible but also in part of the infrared.
  • n 1 , and/or n 3 are advantageously between 1.85 and 2.15, especially between 1.90 and 2.10 or between 2.0 and 2.1,
  • e 1 is advantageously between 10 and 30 nm, especially between 15 and 25 nm,
  • e 3 is advantageously between 100 and 180 nm, especially between 130 and 170 nm or between 140 and 160 nm;
  • n 2 and/or n 4 are advantageously between 1.35 and 1.55 or alternatively between 1.40 and 1.50,
  • e 2 is advantageously between 15 and 45 nm, especially between 20 and 40 nm, and is preferably less than or equal to 35 nm,
  • e 4 is advantageously greater than or equal to 90 nm and is especially less than or equal to 120 or 110 nm, e 4 preferably being chosen between 95 and 115 nm.
  • the high-index first layer 1 and the low-index second layer 2 with a single layer 5 having a refractive index e 5 called “intermediate”, especially one between 1.60 and 1.90, preferably between 1.70 and 1.80.
  • This layer preferably has a geometrical thickness e 5 of between 40 and 120 nm (preferably 60 to 100 nm or 65 to 85 nm).
  • this thickness is instead generally chosen to be above 120 nm.
  • This intermediate-index layer has an optical effect similar to that of a high-index layer/low-index layer sequence when this is the first sequence, of the two layers closest to the carrier substrate of the multilayer film. It has the advantage of reducing the overall number of layers in the multilayer film. It is preferably based on a mixture between, on the one hand, silicon oxide and, on the other hand, at least one metal oxide chosen from tin oxide, zinc oxide and titanium oxide. It may also be based on silicon oxynitride or oxycarbide and/or based on aluminium oxynitride.
  • the most appropriate materials for constituting the first and/or the third layer are based on one or more metal oxides chosen from zinc oxide ZnO, tin oxide SnO 2 and zirconium oxide ZrO 2 . It may especially be a mixed Zn/Sn oxide, of the zinc stannate type. It may also be based on one or more nitrides chosen from silicon nitride Si 3 N 4 and/or aluminium nitride AlN.
  • a nitride layer for one or other of the high-index layers makes it possible to add a functionality to the multilayer film, namely the ability to better withstand heat treatments without its optical properties being appreciably impaired.
  • it is a functionality which is important in the case of any glass which has to form part of solar cells, since such glass must in general undergo a high-temperature heat treatment, of the toughening type, in which the glass must be heated between 500 and 700° C. It then becomes advantageous to be able to deposit the thin layers before the heat treatment without this causing any problem, since it is simpler from the industrial standpoint for the deposition to be carried out before any heat treatment. It is thus possible to have a single configuration of multilayer antireflection film, whether or not the carrier glass is intended to undergo a heat treatment.
  • the first and/or the third layer may in fact consist of several superposed high-index layers.
  • This may most particularly be a bilayer of the SnO 2 /Si 3 N 4 or Si 3 N 4 /SnO 2 type.
  • the advantage of this is the following: Si 3 N 4 tends to be deposited a little less easily and slightly more slowly than a conventional metal oxide such as SnO 2 , ZnO or ZrO 2 by reactive sputtering.
  • the third layer which is the thickest and the most important for protecting the multilayer film from any deterioration resulting from a heat treatment
  • the most appropriate materials for constituting the second and/or the fourth layer are based on silicon oxide, silicon oxynitride and/or silicon oxycarbide or else based on a silicon-aluminium mixed oxide.
  • Such a mixed oxide tends to have a better durability, especially chemical durability, than pure SiO 2 (an example of this is given in the Patent EP-791 562).
  • the respective proportions of the two oxides may be adjusted in order to obtain the expected improvement in durability without excessively increasing the refractive index of the layer.
  • the glass chosen for the coated substrate of the multilayer film according to the invention, or for the other substrates with which it is associated in order to form glazing may in particular be, for example, extra clear of the “Diamant” type (a glass with a low content of iron oxides in particular) or it may be a standard silica-soda-lime clear glass of the “Planilux” type (both types of glass are sold by Saint-Gobain Vitrage).
  • SiAlO corresponds here to an aluminium-silicon mixed oxide, without prejudging their respective amounts in the material
  • Substrates of the glass type, especially extra-clear glass, having this type of multilayer film may thus achieve transmission values integrated between 400 and 1100 nm of at least 90%, especially for thicknesses of between 2 mm and 8 mm.
  • the subject of the invention is also the substrates coated according to the invention as the external substrates for solar cells of the Si or CIS type.
  • this type of product is commercially available in the form of solar cells mounted in series and placed between two transparent rigid substrates of the glass type.
  • the cells are held between the substrates by a polymer material (or several polymer materials).
  • the solar cells may be placed between the two substrates and then the hollow space between the substrates is filled with a cast polymer capable of curing, most particularly a polyurethane-based polymer coming from the reaction of an aliphatic isocyanate prepolymer and a polyether polyol.
  • the polymer may be cured hot (at 30 to 50° C.) and possibly with a slight overpressure, for example in an autoclave.
  • Other polymers may be used, such as ethylene-vinyl acetate EVA, and other arrangements are possible (for example, one or more sheets of thermoplastic polymer may be laminated between the two glass panels of the cells).
  • the subject of the invention is therefore also the said modules.
  • the efficiency of the solar modules can be increased by at least 1, 1.5 or 2% (expressed in terms of integrated current density) over modules which use the same substrate but do not have the coating.
  • solar modules are not sold to the square metre, but by the delivered electric power (approximately, it may be estimated that one square metre of solar cell can deliver about 130 watts), each additional per cent of efficiency increases the electrical performance, and therefore the cost, of a solar module of given dimensions.
  • the subject of the invention is also the process for manufacturing glass substrates with an antireflection coating (A) according to the invention.
  • One process consists in depositing all the layers, in succession, by a vacuum technique, especially by magnetically enhanced sputtering or by plasma-enhanced sputtering.
  • a vacuum technique especially by magnetically enhanced sputtering or by plasma-enhanced sputtering.
  • SiO 2 or Si 3 N 4 it is possible to start with a silicon target which is lightly doped with a metal, such as aluminium, in order to make it sufficiently conductive.
  • FIG. 1 a substrate provided with a three-layer or four-layer antireflection film A according to the invention
  • FIGS. 2, 3, 4 , 6 graphs showing the transmission spectrum for the coated substrates according to the invention and the efficiency of the solar cells using them, compared with a reference cell;
  • FIG. 5 a solar module incorporating the substrate according to FIG. 1.
  • FIG. 1 which is highly schematic, shows, in cross section, a glass substrate 6 surmounted by an antireflection film (A) consisting of four layers 1 , 2 , 3 , 4 or three layers 5 , 3 , 4 .
  • A antireflection film
  • This example uses a 4 mm thick substrate 6 made of extra-clear glass, from the aforementioned DIAMANT range. It uses the three-layer antireflection film.
  • the multilayer film was the following: Refractive index Thickness (nm) SiON (5) 1.75 76 Si 3 N 4 (3) 2.05 145 SiO 2 (4) 1.47 105
  • Example 2 relates to a four-layer antireflection film, and is the result of modelling.
  • the multilayer antireflection film used was the following: Refractive index Thickness (mn) SnO 2 (1) 1.95-2.05 19 SiO 2 (2) 1.47 29 SnO 2 (3) 1.95-2.05 150 SiO 2 (4) 1.47 100
  • the SnO 2 may be replaced, in the case of layer ( 1 ) and/or layer ( 3 ), with Si 3N 4 .
  • Example 2a was produced, this time experimentally, on a 4 mm extra-clear glass from the aforementioned DIAMANT range.
  • FIG. 5 shows highly schematically a solar module 10 according to the invention.
  • the module 10 was formed in the following manner: the glass panel 6 provided with the antireflection coating (A) was combined with a glass panel 8 called the “internal” glass panel.
  • This glass panel 8 was made of toughened glass 4 mm in thickness and of the extra-clear (“Planidur DIAMANT”) type.
  • the solar cells 9 were placed between the two glass panels and then a polyurethane-based curable polymer 7 in accordance with the teaching of the aforementioned Patent EP 0 739 042 was poured into the inter-glass space.
  • Each solar cell 9 consisted, in a known manner, of silicon wafers forming a p-n junction and printed front and rear electrical contacts.
  • the silicon solar cells could be replaced with solar cells using other semiconductors (such as CIS, CdTe, a-Si, GaAs, GalnP).
  • FIG. 2 shows the results of the cell using Example 1:
  • the curve with the triangles shows the degree of conversion of the solar energy into electrical energy (EQE, standing for External Quantum Efficiency) as a function of the wavelength;
  • the curve with circles represents the transmission T through the external glass panel 6 of the solar module
  • the curve with squares represents the “Air Mass 1.5” integrated short-circuit current, taking into account the standard solar spectrum according to the ASTM E892-87 standard.
  • FIG. 3 shows the modelling results obtained with the solar module using Example 2.
  • FIG. 6 shows the results obtained with the solar module using the coating actually produced according to Example 2a:
  • curve C 2 corresponds to the transmission T through the external glass panel when it is made only of a standard silica-soda-lime glass 4 mm in thickness, from the Planilux range sold by Saint-Gobain Glass (for comparison);
  • curve C 3 corresponds to the transmission T when the external glass panel is made of a glass 4 mm in thickness from the “DIAMANT” range (for comparison);
  • curve C 4 corresponds to an external glass panel according to Example 2a, the glass once it had been provided with the antireflection coating having been subjected, before being mounted, to a toughening operation, followed by a moisture resistance test known as a damp-heat test, which consists in leaving the coated glass for 1000 hours at 85° C. in a chamber whose atmosphere has a controlled relative humidity of 85% (IEC 61215 standard);
  • curve CS corresponds to an external glass panel again according to Example 2a, but this time the coated glass was subjected, prior to mounting, to a chemical resistance test known as a neutral salt-fog or NSF test, according to the EN ISO 6988 standard.
  • This test consists in subjecting the glass to 20 cycles consisting of 8 hours at 40° C. and 100% relative humidity in an atmosphere containing 0.67% by volume of SO 2 , followed by 16 hours at 23° C. ⁇ 1° C. in an atmosphere having a relative humidity of 75%;
  • curve C 6 (with squares) represents the integrated short-circuit current, with the same conventions as in FIG. 2.
  • FIG. 4 shows, with the same conventions, the results obtained with the cell using the extra-clear glass without the antireflection coating, by way of comparison.
  • Example 1 show that the antireflection coating (A) according to the invention is capable of undergoing heat treatments of the toughening type.
  • the experimental results of Example 2a confirm the modelling results of Example 2, with integrated current densities significantly higher than with glass without an antireflection coating. It has also been verified that these good results are obtained even when the coated glass has undergone a toughening treatment and/or water-resistance and chemical-resistance tests: the stability of the coating according to the invention is thus proved.
  • the four-layer coatings have a slightly higher performance than the three-layer coatings, but take a little longer to manufacture.
  • the present invention is an improvement of the invention described in Patent FR-2 800 998 which relates to antireflection coatings suitable for optimizing the antireflection effect at non-normal incidence in the visible (especially aimed at applications for vehicle windscreens).
  • the coatings according to the present invention have thicknesses selected for a particular application to solar modules, especially with a thicker third layer (the thickness generally being at least 120 nm and not at most 120 nm).

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ES2344588T3 (es) 2010-09-01
EP1297362B1 (fr) 2010-04-21
EP1297362A1 (fr) 2003-04-02
WO2001094989A1 (fr) 2001-12-13
EP2267491B1 (fr) 2012-11-14
FR2810118A1 (fr) 2001-12-14
EP2267491A3 (fr) 2011-04-13
US7833629B2 (en) 2010-11-16
FR2810118B1 (fr) 2005-01-21
JP2003536097A (ja) 2003-12-02
US20110017272A1 (en) 2011-01-27
DE60141903D1 (de) 2010-06-02
ATE465427T1 (de) 2010-05-15
EP2267491A2 (fr) 2010-12-29
PT2267491E (pt) 2013-02-21
PT1297362E (pt) 2010-06-08
US8372513B2 (en) 2013-02-12
JP4824254B2 (ja) 2011-11-30
ES2398436T3 (es) 2013-03-19
US20100000591A1 (en) 2010-01-07

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