Classifications

• • 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
• • 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
• • 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
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • 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
• • 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

Definitions

• the invention relates to the field of substrates for photovoltaic cells. It relates more specifically substrates for photovoltaic cells comprising at least one float glass sheet provided on one side with at least one electrode.
• a thin-film photovoltaic material typically CdTe or Cu (In, Ga) Se2 (CIGS)
• CdTe or Cu (In, Ga) Se2 CdTe
• CGS In, Ga
• the material with photovoltaic properties, and generally the electrode are deposited in a thin layer by deposition processes such as evaporation, sputtering, chemical vapor deposition (CVD) or sublimation (CSS) on the glass sheet.
• CVD chemical vapor deposition
• SCS sublimation
• the latter must generally be heated at high temperature, either during the deposition or after the deposition (annealing treatment, selenization, etc.), and therefore undergoes temperatures of the order of 500 ° C. or more.
• These treatments make it possible, for example, to improve the crystallinity of the layers and therefore their electronic conduction or photovoltaic properties.
• Glasses of higher thermal resistance have been proposed, but have a high production cost, for example because of the use of raw materials expensive (barium or strontium carriers for example), or particularly high melting temperatures. In addition, some of these glasses are not suitable for forming glass float.
• the object of the invention is to obviate these drawbacks, by proposing a glass composition having improved thermal resistance making it compatible with the processes used in the manufacture of cells based on thin-film photovoltaic materials, particularly CdTe or Cu (In, Ga) Se2 (CIGS), further allowing to produce a glass float and under very favorable economic conditions.
• an object of the invention is a photovoltaic cell substrate comprising at least one float glass sheet provided on one side with at least one electrode, characterized in that said glass has a chemical composition comprising the following constituents, in a weight content varying within the limits defined below:
• compositions surprisingly make it possible to impart high thermal resistances to glass substrates, characterized in particular by lower annealing temperatures of at least 30 ° C. higher than those of standard glass.
• the sum of the weight contents of SiO 2 , Al 2 O 3 , CaO, MgO, Na 2 ⁇ 0, K 2 O is preferably at least 95%, especially 98%.
• the content of SrO, BaO, B 2 O 3 and / or ZrO 2 is advantageously zero so as not to penalize the cost of the glass sheet.
• the content of antimony and arsenic oxides is also advantageously zero because these oxides are not compatible with the float process.
• the other constituents of the composition may be impurities originating from the raw materials (in particular iron oxide) or due to the degradation of the refractories of the melting furnace or of the refining agents (in particular SO 3 ).
• Silica (S10 2 ) is the main formative element of glass. In too low levels, the hydrolytic resistance of the glass, especially in basic medium, would be reduced too much. On the other hand, contents above 70% lead to an increase in the viscosity of the highly detrimental glass.
• the SiO 2 content is preferably at most 66%, especially 65.5% and even 65% and / or at least 61%, especially 62%, or even 62.5% or 63%.
• Alumina (Al 2 O 3) makes it possible to increase the hydrolytic resistance of the glass and to reduce its refractive index, this latter advantage being particularly significant when the substrate is intended to constitute the front-face substrate of the photovoltaic cell.
• the content of Al 2 O 3 is preferably at most 11.5%, especially 11%, even 10% and / or at least 8%, especially 8.5% or 9%.
• the addition of lime (CaO) has the advantage of reducing the high temperature viscosity of the glass, and thus of facilitating its melting and refining, while increasing the lower annealing temperature, and therefore the thermal stability.
• the increase in temperature liquidus and the refractive index attributable to this oxide lead however to limit its content.
• the CaO content is preferably at most 9.5%, especially 9% and / or at least 7%, especially 7.5% or 8%.
• Magnesia (MgO) is useful for improving the chemical durability of glass and decreasing its viscosity. High levels, however, lead to increased risks of devitrification.
• the MgO content is preferably at most 5%, especially 4.5% or 4% and / or at least 3%.
• Soda (Na 2 ⁇ 0) is useful for reducing the viscosity at high temperature and liquidus temperature. Too high levels, however, lead to degrade the hydrolytic strength of the glass and its thermal stability, while increasing the cost.
• the Na 2 O content is preferably at most 15%, in particular 14.5% or even 14% and / or at least 11%, especially 12% or even 12.5% or 13%.
• Potash (K 2 O) has the same advantages and disadvantages. Its content is preferably at most 4%, especially 3%. It may be zero in some embodiments.
• compositions comprise the following components, in one
• the melting of the glass may be carried out in continuous furnaces, heated with electrodes and / or using burners, aerated and / or immersed and / or arranged in the vault of the oven so that the flame impact the raw materials or the glass bath.
• the raw materials are generally pulverulent and include natural materials (sand, feldspars, limestone, dolomite, nepheline syenite altogether or artificial (sodium or potassium carbonate, sodium sulphate ).
• the raw materials are charged and then undergo fusion reactions in the physical sense of the term and various chemical reactions leading to obtaining a glass bath.
• the molten glass is then fed to a forming step during which the glass sheet will take shape.
• the forming is carried out in a known manner by floating, that is to say by pouring the molten glass (at a viscosity of the order of 3000 Poises) on a bath of molten tin.
• the obtained glass ribbon is then carefully annealed in order to eliminate any thermal stresses within it, before being cut to the desired dimensions.
• the thickness of the glass sheet is typically between 2 and 6 mm, especially between 2.5 and 4 mm.
• the electrode is preferably in the form of a thin layer deposited on the substrate (generally on the entire face of the substrate), directly in contact with the substrate or in contact with at least one underlayer. It may be a transparent and electroconductive thin layer, for example based on tin oxide (doped with fluorine or antimony), zinc oxide (doped with aluminum or gallium) , or based on tin oxide and indium (ITO). It can still be a thin metal layer, for example molybdenum. Transparent layers are generally used when the substrate is intended to form the front face substrate of the photovoltaic cell, as explained in more detail later in the text. The term "front face" is understood to mean the face traversed first by solar radiation.
• the electrode in the form of a thin layer may be deposited on the substrate by various deposition methods, such as chemical vapor deposition (CVD) or sputtering deposition, in particular assisted by a magnetic field (magnetron process).
• CVD chemical vapor deposition
• sputtering deposition in particular assisted by a magnetic field (magnetron process).
• halide or organometallic precursors are vaporized and transported by a carrier gas to the surface of the hot glass, where they decompose under the effect of heat to form the thin layer.
• the advantage of the CVD process is that it can be implemented in the process of forming the glass sheet by floating. It is thus possible to deposit the layer when the glass sheet is on the tin bath, at the exit of the tin bath, or in the lehr, that is to say when the glass sheet is annealed to eliminate mechanical stress.
• the CVD process is particularly suitable for depositing fluorine or antimony doped tin oxide layers.
• the sputtering process
• Another object of the invention is a semiconductor device comprising at least one substrate according to the invention and at least one thin layer of a material with photovoltaic properties deposited on said at least one substrate.
• the material with photovoltaic properties is preferably chosen from compounds of the CdTe type or Cu (In, Ga) Se2 (CIGS).
• (In, Ga) we mean that the material can comprise In and / or Ga, according to any possible combinations of contents: Ini_ x Ga x , x being able to take any value of 0 to 1. In particular, x can be zero (material of type CIS).
• the material with photovoltaic properties may also be in amorphous or polycrystalline silicon.
• the photovoltaic material is deposited on the semiconductor device, above the electrode, and generally in contact therewith.
• Different deposition techniques are possible, among which examples that may be mentioned are evaporation, sputtering, chemical vapor deposition (CVD), electrolytic deposition or else sublimation (CSS).
• evaporation evaporation, sputtering, chemical vapor deposition (CVD), electrolytic deposition or else sublimation (CSS).
• CVD chemical vapor deposition
• SCS sublimation
• CIGS-type layers mention may be made of sputtering or electroplating processes (followed by a selenization step) or coevaporation.
• An additional electrode may be deposited on (and in particular in contact with) the layer of photovoltaic material. It may be a transparent and electroconductive thin layer, for example based on tin oxide (doped with fluorine or antimony), zinc oxide (doped with aluminum or gallium) , or based on tin oxide and indium (ITO). It may still be a metal layer, for example gold or nickel alloy and aluminum.
• the transparent layers are generally used when the substrate is intended to form the rear-face substrate of the photovoltaic cell, as explained in more detail later in the text. Buffer layers can also be interposed between the layer of photovoltaic material and the additional electrode. In the case of CIGS type materials, it may for example be a layer of CdS.
• Another object of the invention is a photovoltaic cell comprising a semiconductor device according to the invention.
• An object of the invention is finally a photovoltaic module comprising a plurality of photovoltaic cells according to the invention.
• the substrate according to the invention may be the front or rear face substrate of the photovoltaic cell.
• the CIGS layer is generally deposited on the rear-face substrate (provided with its electrode, typically made of molybdenum). It is therefore the backside substrate which then has a glass sheet having the advantageous chemical composition described above.
• the photovoltaic material is often deposited on the front-face substrate, so that the aforementioned chemical composition is used for the glass sheet of the front-face substrate.
• the photovoltaic cell is formed by joining the substrates of the front face and rear face, for example by means of a lamination interlayer of thermosetting plastic material, for example PVB, PU or EVA.
• the photovoltaic cell according to the invention comprises, as a front-face substrate, the substrate according to the invention, the chemical composition of the glass sheet of said substrate further comprising iron oxide in a weight content. not more than 0,02%, in particular 0,015%. In this case, it is important that the optical transmission of the glass is as high as possible.
• the glass sheet does not include preferably no agent absorbing visible or infrared radiation (especially for a wavelength between 380 and 1000 nm) other than iron oxide (whose presence is unavoidable).
• the composition of the glass preferably does not contain agents chosen from the following agents, or any of the following agents: transition element oxides such as CoO, CuO, Cr 2 O 3, MnO 2 , oxides of rare earths such as Ce0 2 , La 2 O 3, d 2 O 3, or elemental coloring agents such as Se, Ag, Cu, Au.
• transition element oxides such as CoO, CuO, Cr 2 O 3, MnO 2
• oxides of rare earths such as Ce0 2 , La 2 O 3, d 2 O 3, or elemental coloring agents such as Se, Ag, Cu, Au.
• elemental coloring agents such as Se, Ag, Cu, Au.
• the redox (defined as the ratio between the ferrous iron content expressed as FeO and the total iron content expressed as Fe 2 O 3) is preferably at most 0 , 2, especially 0.1.
• the glass sheet is preferably such that its energy transmission (T E ) calculated according to the ISO 9050: 2003 standard is greater than or equal to 90%, in particular 90.5%, even 91% and even 91.5%, for a 3.2 mm thick.
• the front face substrate may be provided, on the face opposite to that carrying the electrode, with an antireflection coating, for example porous silica or comprising a stack of thin layers alternating high and low refractive index layers.
• a substrate according to the invention is typically used provided with a doped ITO and / or SnO 2 electrode, a CdTe photovoltaic material, an additional electrode made of gold or a nickel alloy and aluminum.
• the backside substrate is preferably of standard silico-soda-lime glass.
• the photovoltaic cell according to the invention comprises, as rear-face substrate, the substrate according to the invention, the chemical composition of the glass sheet of said substrate further comprising iron oxide in a weight content. at least 0.05%, in particular ranging from 0.08 to 2%, especially from 0.08 to 0.2%.
• a substrate according to the invention is typically used provided with a molybdenum electrode, a CIGS photovoltaic material, an additional doped ZnO electrode. High levels of iron oxide (from 0.5% to 2%) can in this case correct the aesthetic appearance due to the presence of molybdenum.
• the front face substrate is preferably made of extra-clear glass of standard soda-lime-calcium composition.
• Table 1 illustrates certain compositions according to the invention (Examples 1 to 6) and a standard composition (Comparative Example C1).
• T2 the temperature at which the glass has a viscosity of 100 Poises
• the temperature at which the glass has a viscosity of 3162 Poises called T3.5 and expressed in ° C
• the forming margin called ⁇ and expressed corresponding to the difference between the temperature T3, the liquidus temperature.
• compositions provide glasses having lower annealing temperatures of about 30 ° C higher than that of standard glass. This results in better mechanical behavior, and glass sheets less able to deform during the manufacturing steps of solar cells. These glass compositions are floatable under good conditions, as evidenced by the positive forming margins.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Electromagnetism (AREA)
• General Physics & Mathematics (AREA)
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• Condensed Matter Physics & Semiconductors (AREA)
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• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Glass Compositions (AREA)
• Photovoltaic Devices (AREA)

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• 2011
  • 2011-03-15 FR FR1152093A patent/FR2972724B1/fr active Active
• 2012
  • 2012-03-14 WO PCT/FR2012/050528 patent/WO2012123677A1/fr active Application Filing
  • 2012-03-14 EA EA201391307A patent/EA024931B1/ru not_active IP Right Cessation
  • 2012-03-14 KR KR1020137024027A patent/KR20140021559A/ko not_active Application Discontinuation
  • 2012-03-14 US US13/984,859 patent/US20130313671A1/en not_active Abandoned
  • 2012-03-14 JP JP2013558485A patent/JP6023098B2/ja not_active Expired - Fee Related
  • 2012-03-14 CN CN2012800130432A patent/CN103402936A/zh active Pending
  • 2012-03-14 EP EP12714772.6A patent/EP2686278A1/de not_active Withdrawn

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