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
  • C03C17/3429—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
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
  • C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
  • C03C17/3678—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in 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
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
  • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
  • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
  • H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
  • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
  • H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
• • 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
  • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
  • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
• • 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
  • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less

Definitions

• the present invention relates to transparent conductive layers, in particular based on oxides, of great interest on glass substrate. These transparent layers are generally called TCO for "Transparent Conductive Oxide”.
• ITO indium tin oxide
• SnO 2 F layers doped with fluorine-doped tin oxide, or zinc-doped tin oxide oxide layers.
• These materials are generally deposited chemically, for example by chemical vapor deposition (“CVD”), optionally enhanced by plasma (“PECVD”) or physically, such as by vacuum deposition by cathodic sputtering, possibly assisted. by magnetic field (“magnetron sputtering").
• CVD chemical vapor deposition
• PECVD plasma
• magnetic field magnetic field
• the TCO-based electrode coating must be deposited at a relatively large physical thickness, of the order of a few hundred nanometers, which is expensive in view of the prices of these materials when deposited in thin layers.
• TCOs are deposited hot.
• the deposition process requires a heat input, it further increases the cost of manufacture.
• TCO-based electrode coatings Another major drawback of TCO-based electrode coatings lies in the fact that for a chosen material, its physical thickness is always a compromise between the electrical conduction finally obtained and the transparency finally obtained because the greater the physical thickness, the greater the conductivity will be strong but more transparency will be weak and vice versa, the greater the physical thickness is weak, the higher the transparency, but the lower the conductivity.
• TCO thermoelectric cell
• LCD screen LCD screen
• plasma screen photovoltaic cell
• heated glasses glazing low emissive.
• the present invention therefore aims at overcoming the drawbacks of the preceding techniques by proposing a TCO solution whose optical and electrical conduction properties are not affected by the heat treatment phases, and are even improved by the latter.
• the subject of the invention is therefore a glass transparent substrate, associated with a stack of thin layers forming an electrode, the stack comprising an alkaline barrier sublayer, an electroconductive layer, said electroconductive layer being coated with an overcoat layer.
• protection against oxidation is characterized in that the stack comprises a metal blocking layer capable of oxidizing during a heat treatment.
• this blocking layer Thanks to the presence of this blocking layer, it is possible to obtain, by a cold deposition process, identical performances to those obtained by hot deposition and the performances obtained after heat treatment are improved compared to to those obtained before heat treatment.
• the metal blocking layer is based on titanium, chromium, nickel, niobium, zinc, tin, used alone or as a mixture,
• the thickness of the metal blocking layer is between 0.5 and 20 nm, preferably between 0.5 and 10 nm,
• the metal blocking layer is located below the electroconductive layer,
• the metal blocking layer is located above the electroconductive layer,
• the blocking layer is located above and below the electroconductive layer, the materials forming each of the blocking layers being identical,
• the blocking layer is situated above and below the electroconductive layer, the materials forming each of the blocking layers being different, the barrier sub-layer is based on a dielectric material, the dielectric material is based on nitrides, oxides or oxynitrides of silicon, or nitrides, oxides or aluminum oxy nitrides, or nitrides, oxides or oxynitrides of titanium, nitrides, oxides or oxynitrides of zirconium, used alone or as a mixture, the thickness of the barrier sub-layer is between 3 and 250 nm preferably between 10 and 200 nm and substantially close to 20 to 25 nm, the overcoat of protection against oxidation is identical to the alkali barrier sub-layer the electroconductive layer is based on doped Sn, Zn, Ti or In oxide such as SnO 2 : F, SnO 2 : Sb, ZnO: Al, ZnO: Ga, InO: Sn, ZnO: In or TiO
• 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 achieved for large glass surfaces (PLF - full width float), since deposition methods compatible with such dimensions are available for the relevant layers.
• the resistivity of the electrode is improved after undergoing heat treatment.
• the transparent electroconductive layer of the substrate of the invention is not only able to constitute a photovoltaic cell electrode.
• the transparent substrate of the invention has improved optical properties compared to transparent electroconductive layers on glass substrate: reduced iridescence, more uniform reflection coloration, increased transmission.
• An element capable of collecting light will be described below.
• the transparent substrate with a glass function may for example be entirely of glass containing alkalis such as a soda-lime glass. It may also be a thermoplastic polymer such as a polyurethane or a polycarbonate or a polymethylmethacrylate.
• the entire glass-function substrate is made of material (x) having the best possible transparency and having preferably a linear absorption of less than 0.01 mm 1 in the part of the spectrum useful for the application (solar module), generally the spectrum ranging from 380 to 1200 nm.
• the substrate can have a total thickness ranging from 0.5 to 10 mm when used as a protective plate of a photovoltaic cell of various chalcopyrite technologies (CIS, CIGS, CIGSe2), or belonging to silicon-based technology , the latter may be amorphous or microcrystalline, or belonging to the technology using cadmium telluride (CdTe).
• CIS chalcopyrite technologies
• CIGS CIGSe2
• CdTe cadmium telluride
• the substrate When the substrate is used as a protective plate, it may be advantageous to subject the plate to a heat treatment (of the quenching type for example) when it is made of glass.
• A defines the front face of the substrate directed towards the light rays (this is the external face), and B the rear face of the substrate directed towards the rest of the solar module layers (it is acts of the internal face).
• the B side of the substrate is coated with a stack of thin layers according to the methods of the invention.
• At least one surface portion of the substrate is coated with an alkali barrier layer.
• This alkaline barrier layer is based on a dielectric material, this dielectric material being based on nitrides, oxides or oxynitrides of silicon, or nitrides, oxides or oxynitrides of aluminum, based on zirconium nitrides, oxides or oxynitrides, used alone or as a mixture.
• the thickness of the barrier layer is between 3 and 200 nm, preferably between 10 and 100 nm and substantially close to 20 to 25 nm.
• This alkali barrier layer for example, based on silicon nitride, may not be stoichiometric. It can be sub-stoichiometric in nature, and even superstoichiometrically. The presence of this barrier layer on the B side of the substrate makes it possible to avoid or even block the diffusion of Na from the glass towards the upper active layers.
• an electroconductive TCO layer is deposited for "Transparent Conductive Oxide". It may be chosen from the following materials: doped tin oxide, in particular fluorine or antimony (the precursors that can be used in the case of CVD deposition may be organo-metallic or tin halides associated with a fluorine precursor of the hydrofluoric acid or trifluoroacetic acid type), doped zinc oxide, in particular with aluminum (the precursors that can be used, in the case of CVD deposition, may be organometallic or zinc and aluminum halides), or doped indium oxide, in particular with tin (the precursors that can be used in the case of CVD deposition can be organo-metallic or tin and indium halides).
• the TCO layer for example ZnO may also be deposited by sputtering from metal or ceramic target.
• This conductive layer must be as transparent as possible, and have a high transmission of light in all wavelengths corresponding to the absorption spectrum of the material constituting the functional layer, so as not to reduce the efficiency of the module unnecessarily. solar.
• the thickness of this electroconductive layer is between 50 and 1500 nm, preferably between 200 and 800 nm, and substantially close to 500 nm.
• the conductive layer has a square resistance of at most 40 ohms / square, in particular at most 30 ohms / square.
• the electroconductive layer is then covered with an oxidation protection layer similar to the alkali migration protection layer.
• an oxidation protection layer similar to the alkali migration protection layer.
• it may not be stoichiometric.
• the metal blocking layer will be based on titanium, nickel, chromium, niobium, used alone or in mixture.
• This blocking layer according to an alternative embodiment of the invention is located below the electroconductive layer and in contact with the alkali barrier layer, or according to another embodiment of the invention located above the electroconductive layer and therefore in contact with the protective layer against oxidation, or according to another embodiment located above and below the electroconductive layer.
• the blocking layers located above and below will be made of an identical material, or different.
• the thickness of this metal blocking layer is between 0.5 and 20 nm, preferably between 0.5 and 10 nm.
• the stack of thin layers thus formed and producing an electrode is covered with a functional layer based on absorbent agent for energy conversion between light rays and electrical energy.
• chalcopyrite absorbent agent based on, for example, CIS, CIGS or CIGSe2 or based on silicon-based absorbent agent, for example a thin layer, based on amorphous silicon or silicon. micro crystalline, or is an absorbent agent based on cadmium telluride.
• the functional layer is covered with a conductive, possibly transparent layer of
• TCO classically or non-transparent type such as molybdenum metal material or metal oxide.
• this electrode layer is based on ITO (indium tin oxide) or metal (silver, copper, aluminum, molybdenum), fluorine doped tin oxide or doped zinc oxide.
• the set of thin layers is trapped between two substrates via a lamination interlayer for example PU, PVB or EVA to form the solar cell.
• the square resistance can be improved after quenching only if the barrier layers to oxidation and alkali are thick. In this case, there is a high risk that delamination of the layers will occur (problem of adhesion to the substrate), this delamination is visible visually. Examples of embodiments according to the invention are given below.
• the resistivity is decreased after quenching singularly compared to the examples of the prior art. It is noted that this improvement in electrical properties is not at the expense of mechanical properties (no delamination problem), the thickness of the alkali barrier layers and protection against oxidation is significantly lower than those used in the art prior.
• Another advantage of the invention is that the light transmission is singularly improved after quenching.
• Si3N4 Ti: Rcarred before Rcarré after TL before TL after
• Si3N4 Ti Thickness in nm Rcarred before Rcarred after TL before TL after
• ZnO Ti: 15: 2: 500: 2: 25 tempering quenching (ohms) quenching quenching
• Example 1 State of the Art: Encapsulation of AZO in Si3N4 to Withstand Quenching
• Example 3 showing that the addition of the blocking layer below the electroconductive layer makes it possible to reduce the thickness of Si3N4 less up to 25 nm without increasing Rsq
• this example shows that, unlike the lower Si3N4, the thickness of the higher Si3N4 can be reduced without affecting the Rsq at 25 nm, which also shows that a blocking layer positioned above the electroconductive layer is not not necessarily necessary

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• General Chemical & Material Sciences (AREA)
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• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
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• 2007
  • 2007-10-25 FR FR0758571A patent/FR2922886B1/fr not_active Expired - Fee Related
• 2008
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