Classifications

• • 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
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/02—Pretreatment of the material to be coated
  • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
  • C23C16/029—Graded interfaces
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
  • C23C16/401—Oxides containing silicon
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
  • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• • 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
  • C03C2217/90—Other aspects of coatings
  • C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/152—Deposition methods from the vapour phase by cvd

Definitions

• the present invention relates to transparent conductive layers, in particular based on oxides, of great interest on glass substrate.
• ITO indium tin oxide
• SnO 2 F layers of fluorine-doped tin oxide.
• Such layers constitute electrodes in certain applications: flat lamps, electroluminescent glazing, electrochromic glazing, liquid crystal display screen, plasma screen, photovoltaic glazing, heated glasses.
• these transparent conductive layers do not have to be activated by a power-up.
• these transparent conductive layers are generally associated with an underlayer to improve the optical properties of a layer or a stack of transparent conductive layers on a glass substrate.
• EP 611 733 by PPG proposes a mixed gradient layer of silicon oxide and tin oxide to avoid the iridescence effects induced by the transparent conductive oxide layer.
• tin doped with fluorine proposes a variant of this underlayer for improving the color properties of a conductive transparent layer of fluorine-doped tin oxide.
• the precursors mentioned in this patent are on the other hand unusable on an industrial scale.
• SAINT-GOBAIN also has a know-how in this field: the patent FR 2,736,632 thus proposes a mixed sub-layer with a reverse index gradient of silicon oxide and tin oxide as anti-backing layer.
• a characterization test of this phenomenon consists of subjecting the glass and its electrode during for example 10 minutes to the joint action of fields electric of the order of 200 V for example, on both sides of the glass, and temperatures of 200 0 C. The action of an electric field at these temperatures induced for the duration of the test a total of electrical charges displaced from 1 to 8 mC / cm 2 according to the electrical resistivity values of the glass at the test temperature.
• delaminations are also observed in the case of curved glasses. These delaminations are undetectable by a man who is not of the profession if the glasses thus coated are not traversed by an electric current. On the other hand, in the case of applications where the glass thus coated is traversed by an electric current, as is the case for a heating glass for example, then the presence of these delaminations removes the functionality.
• the inventors have developed an underlayer connecting a glass substrate to a transparent conductive oxide layer considerably improving the adhesion of the latter, in particular under conditions of placing in the electric field of the assembly and relatively high temperatures, greater than 100, or even 150 0 C, or especially when the glass is formed (curved and / or tempered).
• the subject of the invention is therefore a transparent glass substrate, associated with a transparent electroconductive layer capable of constituting a photovoltaic cell electrode and composed of a doped oxide, characterized by the interposition, between the glass substrate and the transparent electroconductive layer, a mixed layer of one or more first nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s) having good adhesion properties with the glass, and one or more several second nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s) likely (s) to constitute, optionally in the doped state, a transparent electroconductive layer.
• a transparent electroconductive layer capable of constituting a photovoltaic cell electrode and composed of a doped oxide
• the invention makes it possible to obtain stackings of layers adapted for photovoltaic cells whose mechanical strength on a glass substrate is not affected in the presence of an electric field and at high temperature. This considerable improvement can be obtained for large areas of glass (PLF - full width float), because deposition processes compatible with such dimensions are available for the layers concerned.
• the transparent electroconductive layer of the substrate of the invention is not only able to constitute a photovoltaic cell electrode, but also a coating having excellent adhesion to tempered and / or curved glass.
• a low-emissive coating is mentioned, in particular on the face of a glazing turned towards the interior of a building in order to reflect and conserve the ambient heat.
• the mixed underlayer may not be a barrier for the migration of alkali from the glass to the transparent conductive layer. It is advantageously sparse to allow passage to alkaline glass and itself conductive.
• the transparent substrate of the invention has improved optical properties compared to transparent electroconductive layers on glass substrate: reduced iridescence, more uniform reflection coloration.
• said mixed layer has a composition gradient in the direction of a decreasing proportion of the first nitride (s) or oxynit (s), or oxide (s) or oxycarbide (s) at increasing distance from the glass substrate; said mixed layer has a compositional gradient in the direction of an increasing proportion of the first nitride (s) or oxynit (s), or oxide (s) or oxycarbide (s) at increasing distance from the glass substrate.
• the substrate of the invention is characterized in that its mechanical strength is not affected within 24 hours after a treatment of at least 10 minutes, preferably 20 minutes, with an electric field of at least 100 V , preferably 200 V on either side of the substrate, and a temperature of at least 200 0 C, inducing a displacement of electric charges of at least 2 mC / cm 2 , preferably 8 mC / cm 2 of after the electrical resistivity values of the glass substrate at the test temperature.
• mechanical strength it is meant that the stack or part of the stack does not delaminate.
• the stack of said mixed layer to said transparent electroconductive layer has a blur of at most 30%
• said mixed layer has at its interface with said transparent electroconductive layer a surface consisting of randomly oriented rods of lengths of 10 to 50 nm, of diameters of 5 to 20 nm, forming a roughness rms of 10 to 50 nm, and causing an increase in the blurring of the complete stack by 5 to 10% with respect to the same stack of said mixed layer to said transparent electroconductive layer where the first named has a smooth surface - in the photovoltaic application, a high blur is sought - - a light transmission (transmission in the visible weighted by the sensitivity curve of the human eye - ISO 9050 standard) of at least 75%, preferably 80%,
• R D a square resistor, defined as the electrical resistance measured across two linear electrodes, parallel, of the same length L, and distant from this length L, these two electrodes being in electrical contact along their entire length with the face electroconductive substrate, between 5 and 1000 ⁇ ,
• the stack of said mixed layer to said transparent electroconductive layer has a blur of less than 5%, preferably less than 1%;
• the said first nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s) are chosen from nitrides or oxynitrides, or oxides or oxycarbides of Si, Al and Ti, in particular SiO 2 , TiO 2 and Al 2 O 3 ;
• the one or more second nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s) are chosen from nitrides or oxynitrides, or oxides or oxycarbides of Sn, Zn and In, in particular SnO 2; , ZnO and InO;
• said transparent electroconductive layer is composed of an oxide doped with Sn, Zn or In, such as SnO 2 : F, SnO 2 : Sb, ZnO: Al, ZnO: Ga, InO: Sn or ZnO: In
• ⁇ is electrically conductive, and non-insulating, and in particular has a resistance per square at most equal to 100,000 ⁇ , preferably 10,000 ⁇ ; at a molar ratio F / Sn at least equal to 0.01, preferably 0.05.
• the thickness of said mixed layer is between 20 and 500 nm, preferably between 50 and 300 nm;
• the face of said mixed layer located on the side of the glass substrate consists exclusively of a thickness of 2 to 20 nm, of one or more first nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s), which promotes the adhesion of the mixed layer to the glass;
• the face of said mixed layer situated on the side opposite to that of the glass substrate consists exclusively of a thickness of 2 to 20 nm of one or more second nitride (s) or oxynitride (s), or oxide ( s) or oxycarbide (s), which promotes the adhesion of the mixed layer to its coating of similar composition, such as said transparent electroconductive layer.
• said transparent electroconductive layer composed of a doped oxide is connected to said mixed layer with the interposition of a layer of the same undoped oxide, the cumulative thickness of the two layers undoped oxide and doped oxide being between 700 and 2000 nm, and the ratio of the thicknesses of the two layers being between 1: 4 and 4: 1.
• the doped oxide layer may be coated with a layer of plasma-supported CVD-deposited microcrystalline silicon (PECVD) to form a photovoltaic cell.
• PECVD plasma-supported CVD-deposited microcrystalline silicon
• the two undoped oxide and doped oxide layers advantageously have an RMS roughness of 20-40 nm. Indeed silicon absorbs relatively little light. The roughness of the underlying layers makes them scattering and thus lengthens the path of light in the active silicon layer, ensuring a sufficient number of electron-hole pairs within it, and effective light trapping.
• said transparent electroconductive layer with a thickness of between 300 and 600 nm, composed of a doped oxide is formed directly on said mixed layer.
• the doped oxide layer may be covered with a cadmium-tellurium layer to form a photovoltaic cell.
• said transparent electroconductive layer composed of a doped oxide is coated with a protective layer vis-à-vis the deposition of constituent coatings of a photovoltaic cell, including deposition by PECVD a layer such as silicon, or a layer increasing the quantum efficiency of the photovoltaic cell, such as zinc oxide or titanium oxide.
• one of the faces of the substrate - in particular the glass face opposite to that carrying said mixed layer - is coated by a stack providing a feature of the anti-reflective or hydrophobic or photocatalytic type.
• said mixed layer may comprise grains of one or more first nitride (s) or oxynitride (s) or oxide (s) or oxycarbide (s), mixed with grains of one or more second nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s).
• An example is a mixed layer comprising SiO 2 grains mixed with SnO 2 grains.
• the continuous gradient of composition means a regular decrease in the proportion of SiO 2 grains compared to those of SnO 2, for example in the entire thickness of the mixed layer at increasing distance from the glass substrate.
• This regular decay does not exclude a decrease in steps or steps, or the presence of two separate zones and nested one in the other (like pieces of a puzzle) with exclusive contents in one only one or more of said first (s) or second (s) nitride (s) or oxynitride (s) or oxide (s) or oxycarbide (s).
• Said mixed layer may also comprise, additionally or alternatively, mixed grains of one or more first nitride (s) or oxynitride (s) or oxide (s) or oxycarbide (s), and of one or more second (s) nitride (s) or oxynitride (s) or oxide (s) or oxycarbide (s).
• An example is a mixed layer comprising the elements Si, Sn, Al and O.
• the sizes of said grains determined by transmission electron microscopy observation are between 10 and 80 nm, preferably 20 and 50 nm.
• the subject of the invention is also a method of manufacturing a substrate in which said mixed layer is obtained by vapor phase chemical deposition resulting from contacting precursors of said first and second nitride (s). (s) or oxynitride (s) or oxide (s) or oxycarbide (s) with the substrate in the presence of at least one fluorine compound, such as tetrafluoromethane (CF4), octafluoropropane (C3F8), hexafluoroethane (C2F6), hydrogen fluoride (HF), difluoro-chloromethane (CHCIF 2 ), difluorochloroethane (CH 3 CCIF 2 ), trifluoromethane (CHF 3 ), dichlorodifluoromethane (CF) 2 Cl 2 ), trifluoro-chloromethane (CF 3 Cl), trifluoromethylmethane (CF 3 Br), trifluoroacetic acid (TFA, CF 3 CO
• the fluorine compound accelerates the deposition of the first nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s), in particular SiO 2, relative to that of the second (s) - such as SnO 2 .
• said mixed layer is obtained by implementing a chemical vapor deposition (CVD for Chemical Vapor Plasma assisted deposition (PE CVD for Plasma Enhanced CVD), especially plasma at atmospheric pressure (AP PECVD for Atmospheric Pressure PECVD); the temperature of the substrate is then advantageously at most equal to 300 ° C.
• CVD chemical vapor deposition
• PECVD Plasma Vapor Plasma assisted deposition
• AP PECVD atmospheric pressure
• Atmospheric Pressure PECVD Atmospheric Pressure
• said mixed layer is obtained at a substrate temperature of at least 500 ° C., preferably at least 600 ° C., and particularly preferably at least 650 ° C.
• said mixed layer is obtained in the presence of auxiliary agents for controlling the relative deposition rates of said first and second nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s).
• auxiliary agents for controlling the relative deposition rates of said first and second nitride (s) or oxynitride (s), or oxide (s) or oxycarbide (s).
• This invention advantageously uses fluorine not only to accelerate the deposition rate of SiO 2 relative to that of SnO 2 during the formation of the mixed layer, but also to dope the underlayer and make it itself conductive.
• the electrical conduction of the sub-layer contributes to improving the mechanical strength of the stack, in particular under the effect of an electric field.
• the invention also has the following objects: a photovoltaic cell comprising a substrate described above; a tempered and / or curved glass with a radius of curvature at most equal to 2000 mm, preferably at most equal to 500 mm and particularly preferably at most equal to 300 mm, comprising a substrate according to the invention; the mechanical strength of the layers deposited on this glass is excellent; a shaped heating glass comprising a substrate as previously described; a plasma screen (PDP for Plasma Display Panel) comprising a substrate according to the invention; a flat lamp electrode comprising such a substrate.
• PDP Plasma Display Panel
• Example 1 Deposition of SiOSn doped with fluorine in a static thermal reactor CVD
• Substrate 4 mm glass, dimensions 10 x 20 cm 2
• Example 2 Deposition of SiOSn doped with fluorine / SnO 2 undoped / SnO? doped with fluorine, realized in dynamics in a thermal CVD reactor at atmospheric pressure
• Substrate extra-clear glass of 4 mm, dimensions 100 x 60 cm 2
• MBTCI 0.3 mol / min
• TEOS 0.36 mol / min
• O 2 13% vol.
• TFA 0.19 mol / min
• Example 3 Deposition of Si-O-Sn carried out dynamically in a reactor of
• Substrate Planilux Saint-Gobain glass of 4 mm
• a 78% light transmission layer with a square resistance of 10 ohms and a blur of 4% are obtained.
• Example 4 Deposition of Ti-O-Sn carried out dynamically in a reactor of
• Substrate Planilux Saint-Gobain glass 4 mm
• the order of arrival of the precursors involves a glass / TiO 2 / Ti-O-stack
• the resulting layer is 10 ohms squared, 80% light transmission, 1.5% blur.
• Plasma power 2 W / cm 2 with impulse type power supply.
• the discharge regime is homogeneous.
• the deposited layer is amorphous SiOSn type, and has a gradient such that the concentration of tin is higher on the surface.
• the deposition rate of this layer is equal to 200 nm / min.
• the holding in the photovoltaic test is equal to 4 (the layer is the test but eventually delaminate either after 24 hours or very weakly before 24 hours).
• photovoltaic test is meant a treatment of 10 minutes by an electric field of 200 V on either side of the substrate, and a temperature of 200 C: the delamination or not of the layer is observed within 24 hours after treatment .

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• 2008
  • 2008-01-14 KR KR1020097014702A patent/KR101456560B1/ko not_active IP Right Cessation
  • 2008-01-14 AU AU2008214505A patent/AU2008214505B2/en not_active Ceased
  • 2008-01-14 JP JP2009545213A patent/JP5475461B2/ja not_active Expired - Fee Related
  • 2008-01-14 EP EP08761934A patent/EP2114839A2/fr not_active Withdrawn
  • 2008-01-14 US US12/523,174 patent/US8470434B2/en not_active Expired - Fee Related
  • 2008-01-14 RU RU2009131040/03A patent/RU2462424C2/ru not_active IP Right Cessation
  • 2008-01-14 BR BRPI0806628-0A patent/BRPI0806628A2/pt not_active IP Right Cessation
  • 2008-01-14 MX MX2009007526A patent/MX2009007526A/es active IP Right Grant
  • 2008-01-14 WO PCT/FR2008/050063 patent/WO2008099115A2/fr active Application Filing

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