US20140311573A1 - Solar Cell With Selectively Doped Conductive Oxide Layer And Method Of Making The Same - Google Patents

Solar Cell With Selectively Doped Conductive Oxide Layer And Method Of Making The Same Download PDF

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Publication number
US20140311573A1
US20140311573A1 US14/200,443 US201414200443A US2014311573A1 US 20140311573 A1 US20140311573 A1 US 20140311573A1 US 201414200443 A US201414200443 A US 201414200443A US 2014311573 A1 US2014311573 A1 US 2014311573A1
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Prior art keywords
coating
dopant
layer
precursor material
oxide layer
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US14/200,443
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Inventor
James W. McCamy
Peter Tausch
Gary J. Nelis
Ashtosh Ganjoo
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Vitro SAB de CV
Vitro Flat Glass LLC
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PPG Industries Ohio Inc
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Priority to US14/200,443 priority Critical patent/US20140311573A1/en
Priority to TW103108818A priority patent/TWI529955B/zh
Assigned to PPG INDUSTRIES OHIO, INC. reassignment PPG INDUSTRIES OHIO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GANJOO, ASHTOSH, MCCAMY, JAMES W., NELIS, GARY J., TAUSCH, PETER
Publication of US20140311573A1 publication Critical patent/US20140311573A1/en
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE ADDRESS PREVIOUSLY RECORDED AT REEL: 040473 FRAME: 0455. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: PPG INDUSTRIES OHIO, INC.
Priority to US15/905,123 priority patent/US11031514B2/en
Assigned to VITRO FLAT GLASS LLC reassignment VITRO FLAT GLASS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VITRO, S.A.B. DE C.V.
Abandoned legal-status Critical Current

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    • 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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
    • 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
    • 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
    • C03C17/3482—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 silicon, hydrogenated silicon or a silicide
    • 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
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • 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
    • C03C17/3636—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 one layer at least containing silicon, hydrogenated silicon or a silicide
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    • 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
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    • 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
    • C03C17/3649—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 made of metals other than silver
    • 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
    • C03C17/3655—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 containing at least one conducting layer
    • 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
    • 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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • 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
    • C23C16/44—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 method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • H01L31/18—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
    • C03C2217/91—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
    • 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

Definitions

  • This invention relates generally to solar cells, e.g., photovoltaic (PV) cells, and, more particularly, to a solar cell having a selectively doped transparent conductive oxide layer and a method of making the same.
  • PV photovoltaic
  • a solar cell or photovoltaic (PV) cell is an electronic device that directly converts sunlight into electricity. Light shining on the solar cell produces both a current and a voltage to generate electric power.
  • photons from sunlight hit the solar cell and are adsorbed by a semiconducting material. Electrons are knocked loose from their atoms, causing an electric potential difference. Current flows through the material to cancel the potential difference. Due to the special composition of solar cells, the electrons are only allowed to move in a single direction.
  • a conventional amorphous silicon thin film solar cell typically includes a glass substrate (cover plate) over which is provided an underlayer, a transparent conductive oxide (TCO) contact layer, and an amorphous silicon thin film active layer having a p-n junction.
  • a rear metallic layer acts as a reflector and back contact.
  • the TCO layer preferably has an irregular surface to increase light scattering.
  • light scattering or “haze” is used to trap light in the active region of the cell. The more light that is trapped in the cell, the higher the efficiency that can be obtained. However, the haze cannot be so great as to adversely impact upon the transparency of light through the TCO layer. Therefore, light trapping is an important issue when trying to improve the efficiency of solar cells and is particularly important in thin film cell design.
  • the TCO layer is highly transparent to permit the maximum amount of solar radiation to pass to the silicon layer.
  • the more photons that arrive at the semiconductor material the higher the efficiency of the cell.
  • the TCO layer should be highly conductive to allow the easy transfer of electrons in the cell. This conductivity can be enhanced by the addition of a dopant material to the TCO material.
  • the TCO layer is an important factor in solar cell performance.
  • the TCO material should preferably have a high conductivity (i.e., low sheet resistance), a high transparency in the desired region of the electromagnetic spectrum, and should have high haze to promote light scattering.
  • conductivity is dependant upon the dopant concentration and the thickness of the TCO layer.
  • increasing the dopant concentration or the thickness of the TCO layer generally decreases the transparency of the TCO layer.
  • surface roughness (light scattering) generally increases with coating thickness.
  • increasing the coating thickness generally decreases the transmission (particularly visible light transmission) through the coating.
  • the affect and interaction of each of these factors must be weighed when selecting a TCO layer for a solar cell.
  • TCO layer in which the conductivity, light transmission, and light scattering could more easily be selected. It would also be desirable to provide a method of providing a TCO layer for a solar cell in which these factors could be controlled more easily. It would also be desirable to provide a solar cell having such a TCO layer.
  • a solar cell comprises a first substrate having a first surface and a second surface.
  • a first conductive layer is provided over at least a portion of the second surface, wherein the first conductive layer comprises a transparent conductive oxide layer incorporating a dopant material. The dopant material is selectively distributed in the conductive layer.
  • a semiconductor layer is provided over the transparent first conductive layer.
  • a second conductive layer is provided over at least a portion of the semiconductor layer.
  • a method of making a coated substrate having a transparent conductive oxide layer with a dopant selectively distributed in the layer comprises selectively supplying an oxide precursor material and a dopant precursor material to each coating cell of a multi-cell chemical vapor deposition coater, wherein the amount of dopant material supplied is selected to vary the dopant content versus coating depth in the resultant coating.
  • a chemical vapor deposition system comprises at least one coater having a plurality of coating cells, wherein the coating cells are connected to one or more coating supply sources comprising at least one oxide precursor material and at least one dopant material.
  • the coating cells are individually connected to respective coating supply sources comprising at least one oxide precursor material and at least one dopant material.
  • a method of making a coated substrate having a coating layer with a dopant selectively distributed in the coating layer comprises: supplying a coating precursor material to coating cells of a multi-cell chemical vapor deposition coater; supplying a dopant precursor material to coating cells of a multi-cell chemical vapor deposition coater; controlling the supply of at least one of the coating precursor material and the dopant precursor material to define a coating composition having a selected ratio of the dopant precursor material to the coating precursor material at the coating cells; and depositing the coating composition onto a substrate to form a doped coating layer.
  • the ratio of the dopant precursor material to the coating precursor material is selected to define a desired dopant content versus coating depth profile of a resultant doped coating.
  • FIG. 1 is a side, sectional view (not to scale) of a solar cell incorporating features of the invention
  • FIG. 2 is a side, prospective view of a chemical vapor deposition (CVD) coating system (not to scale) incorporating features of the invention;
  • CVD chemical vapor deposition
  • FIG. 3 is a graph of TFA flow (lb/hr) versus cell number for Example 1;
  • FIG. 4 is a graph of F/Sn ratio versus coating depth for Example 1;
  • FIG. 5 is a graph of TFA flow (lb/hr) versus cell number for Example 2;
  • FIG. 6 is a graph of F/Sn ratio versus coating depth for Example 2.
  • FIG. 7 is a graph of TFA flow (lb/hr) versus cell number for Example 3.
  • FIG. 8 is a graph of F/Sn ratio versus coating depth for Example 3.
  • FIG. 9 is a graph of TFA flow (lb/hr) versus cell number for Example 4.
  • FIG. 10 is a graph of F/Sn ratio versus coating depth for Example 4.
  • FIG. 11 is a graph of fluorine and tin content versus coating depth for Example 5.
  • FIG. 12 is a graph of F/Sn ratio versus coating depth for Example 5.
  • FIG. 13 is a graph of tin, oxygen, and fluorine content versus coating depth for Sample 1 of Example 6;
  • FIG. 14 is a graph of tin, oxygen, and fluorine content versus coating depth for Sample 2 of Example 6;
  • FIG. 15 is a graph of tin, oxygen, and fluorine content versus coating depth for Sample 3 of Example 6;
  • FIG. 16 is a graph of percent haze versus coating thickness for Example 6.
  • FIG. 17 is a graph of sheet resistance versus coating thickness for Example 6
  • FIG. 18 is a graph of haze versus wavelength for Example 6.
  • each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • all ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein.
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and the like.
  • the terms “formed over”, “deposited over”, “provided over”, or “located over” mean formed, deposited, provided, or located on a surface but not necessarily in direct contact with the surface.
  • a coating layer “formed over” a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate.
  • the terms “polymer” or “polymeric” include oligomers, homopolymers, copolymers, and terpolymers, e.g., polymers formed from two or more types of monomers or polymers.
  • visible region refers to electromagnetic radiation having a wavelength in the range of 380 nm to 760 nm.
  • infrared region or “infrared radiation” refer to electromagnetic radiation having a wavelength in the range of greater than 760 nm to 100,000 nm.
  • ultraviolet region or “ultraviolet radiation” mean electromagnetic energy having a wavelength in the range of 200 nm to less than 380 nm.
  • microwave region or “microwave radiation” refer to electromagnetic radiation having a frequency in the range of 300 megahertz to 300 gigahertz.
  • the refractive index values are those for a reference wavelength of 550 nanometers (nm).
  • the term “film” refers to a region of a coating having a desired or selected composition.
  • a “layer” comprises one or more “films”.
  • a “coating” or “coating stack” is comprised of one or more “layers”.
  • the solar cell 10 includes a first (outer) substrate 12 having a first (outer) major surface 14 and a second (inner) major surface 16 .
  • outer is meant the surface facing the incident radiation, e.g., sunlight.
  • An optional undercoating 18 may be located over the second surface 16 .
  • a first conductive layer 20 (for example a TCO layer) is located over the second surface 16 (such as on the undercoating 18 , if present).
  • a semiconductor layer 22 is located over the TCO layer 20 .
  • a second conductive layer 24 is located over the semiconductor layer 22 .
  • the second conductive layer 24 can be a metal layer or a metal-containing layer.
  • An optional second (inner) substrate 26 is located over the second conductive layer 24 .
  • the first substrate 12 can include any desired material having any desired characteristics.
  • the first substrate 12 can be transparent or translucent to visible light.
  • transparent is meant having a visible light transmittance of greater than 0% up to 100%.
  • the first substrate 12 can be translucent.
  • translucent is meant allowing electromagnetic energy (e.g., visible light) to pass through but diffusing this energy such that objects on the side opposite the viewer are not clearly visible.
  • suitable materials include, but are not limited to, plastic substrates (such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethylmethacrylates, polypropylmethacrylates, and the like; polyurethanes; polycarbonates; polyalkylterephthalates, such as polyethyleneterephthalate (PET), polypropyleneterephthalates, polybutyleneterephthalates, and the like; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); glass substrates; or mixtures or combinations of any of the above.
  • plastic substrates such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethylmethacrylates, polypropylmethacrylates, and the like; polyurethanes; polycarbonates; polyalkylterephthalates, such as polyethyleneterephthalate (PET
  • the first substrate 12 can include conventional soda-lime-silicate glass, borosilicate glass, or leaded glass.
  • the glass can be clear glass.
  • clear glass is meant non-tinted or non-colored glass.
  • the glass can be tinted or otherwise colored glass.
  • the glass can be annealed or heat-treated glass.
  • heat treated means tempered or at least partially tempered.
  • the glass can be of any type, such as conventional float glass, and can be of any composition having any optical properties, e.g., any value of visible transmission, ultraviolet transmission, infrared transmission, and/or total solar energy transmission.
  • float glass glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath, such as molten tin.
  • molten metal bath such as molten tin.
  • the bottom side of the glass, i.e., the side that was in contact with the molten tin bath, conventionally is referred to as the “tin side” and the top side of the glass conventionally is referred to as the “air side”.
  • the tin side of the glass can have small amounts of tin incorporated into the glass surface.
  • the first substrate 12 can be of any desired dimensions, e.g., length, width, shape, or thickness.
  • the first substrate 12 can be planar, curved, or have both planar and curved portions.
  • the first substrate 12 can have a thickness in the range of 0.5 mm to 10 mm, such as 1 mm to 5 mm, such as 2 mm to 4 mm, such as 3 mm to 4 mm.
  • the first substrate 12 can have a high visible light transmission at a reference wavelength of 550 nanometers (nm) and a reference thickness of 2 mm.
  • high visible light transmission is meant visible light transmission at 550 nm of greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equal to 90%, such as greater than or equal to 91%, such as greater than or equal to 92%, such as greater than or equal to 93%.
  • the optional undercoating 18 can be a single layer or a multilayer coating having a first layer and a second layer over the first layer.
  • the undercoating 18 can provide a barrier between the first substrate 12 and the overlying coating layers.
  • Silica is known to provide good barrier properties, particularly as a barrier to sodium ion diffusion out of a glass substrate.
  • the undercoating 18 can be a mixture of two or more oxides, such as selected from oxides of silicon, titanium, aluminum, tin, zirconium, phosphorous. The oxides can be present in any desired proportions.
  • the second layer of the undercoating 18 if present, can be a homogeneous coating. Alternatively, the second layer can be a gradient coating with the relative proportions of at least two of the constituents of the coating varying through the coating thickness.
  • the TCO layer 20 comprises at least one conductive oxide layer, such as a doped oxide layer.
  • the TCO layer 20 can include one or more oxide materials, such as but not limited to, one or more oxides of one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials, such as zinc stannate.
  • the TCO layer 20 can also include one or more dopant materials, such as but not limited to, F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, and/or Sb.
  • the TCO layer 20 can have a thickness greater than 200 nm, such as greater than 250 nm, such as greater than 350 nm, such as greater than 380 nm, such as greater than 400 nm, such as greater than 420 nm, such as greater than 470 nm, such as greater than 500 nm, such as greater than 600 nm.
  • the TCO layer can have a thickness in the range of 350 nm to 1,000 nm, such as 400 nm to 800 nm, such as 500 nm to 700 nm, such as 600 nm to 700 nm.
  • the TCO layer 20 can have a surface resistivity (sheet resistance) of less than 20 ohms per square ( ⁇ / ⁇ ), such as less than 15 ⁇ / ⁇ , such as less than 14 ⁇ / ⁇ , such as less than 13.5 ⁇ / ⁇ , such as less than 13 ⁇ / ⁇ , such as less than 12 ⁇ / ⁇ , such as less than 11 ⁇ / ⁇ , such as less than 10 ⁇ / ⁇ .
  • sheet resistance surface resistivity
  • the TCO layer 20 can have a surface roughness (RMS) in the range of 5 nm to 60 nm, such as 5 nm to 40 nm, such as 5 nm to 30 nm, such as 10 nm to 30 nm, such as 10 nm to 20 nm, such as 10 nm to 15 nm, such as 11 nm to 15 nm.
  • RMS surface roughness
  • the surface roughness of the first undercoating layer will be less than the surface roughness of the TCO layer 20 .
  • the TCO layer 20 is a fluorine doped tin oxide coating, with the fluorine present in an amount less than 20 wt. % based on the total weight of the coating, such as less than 15 wt. %, such as less than 13 wt. %, such as less than 10 wt. %, such as less than 5 wt. %, such as less than 4 wt. %, such as less than 2 wt. %, such as less than 1 wt. %.
  • the TCO layer 20 can be amorphous, crystalline, or at least partly crystalline. However, unlike prior TCO layers, the TCO layer of the invention does not necessarily have a uniform doping profile throughout the coating thickness. In the practice of the invention, the dopant content can be selected or varied in selected regions of the TCO layer by the TCO layer formation process described below.
  • the TCO layer 20 comprises fluorine doped tin oxide and has a thickness in the range of 350 nm to 1,000 nm, such as 400 nm to 800 nm, such as 500 nm to 700 nm, such as 600 nm to 700 nm, such as 650 nm.
  • the semiconductor layer 22 can be any conventional solar cell semiconductor material, such as crystalline silicon. Examples include monocrystalline silicon, polycrystalline silicon, and amorphous silicon. Other examples of semiconductor material include cadmium telluride and copper indium celenide/sulfide.
  • a layer of phosphorous-doped (n-type) silicon is on top of a thicker boron-doped (p-type) silicon. An electrical field is created at the small p-n junction resulting in a flow of current when the cell is connected to an electrical load.
  • An amorphous silicon layer 22 can have a thickness in the range of 200 nm to 1,000 nm, such as 200 nm to 800 nm, such as 300 nm to 500 nm, such as 300 nm to 400 nm, such as 350 nm.
  • the second conductive layer 24 can be a metallic layer or a metal containing layer and can include one or more metal oxide materials.
  • suitable metal oxide materials include, but are not limited to, oxides of one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials, such as zinc stannate.
  • the metal containing layer 24 can have a thickness in the range of 50 nm to 500 nm, such as 50 nm to 300 nm, such as 50 nm to 200 nm, such as 100 nm to 200 nm, such as 150 nm.
  • the optional second substrate 26 can be of any material described above for the first substrate 12 .
  • the first substrate 12 and second substrate 26 can be of the same or different material and can be of the same or different thickness.
  • the undercoating 18 , TCO layer 20 , semiconductor layer 22 , and the second conductive layer 24 can be formed over at least a portion of the substrate 12 by any conventional method, such as but not limited to, spray pyrolysis, chemical vapor deposition (CVD), or magnetron sputtered vacuum deposition (MSVD).
  • the layers can all be formed by the same method or different layers can be formed by different methods.
  • the optional undercoating layer 18 and TCO layer 20 can be formed by a CVD method.
  • a precursor composition is carried in a carrier gas, e.g., nitrogen gas, and is directed toward the heated substrate.
  • the TCO layer 20 is formed by a CVD coating system in a molten tin bath as described below.
  • the TCO layer 20 is deposited using a CVD coating system 50 positioned in a molten metal (tin) tin bath 52 of a conventional float glass process.
  • the CVD coating system 50 can have one coater or a plurality of coaters.
  • the coating system has a first CVD coater 54 and a second CVD coater 54 .
  • Each coater 52 and 54 has a plurality of coating cells (e.g., coating slots) to supply coating material onto an underlying glass substrate 56 as the glass substrate 56 moves along on top of the molten metal in the molten metal bath.
  • the general structure and operation of a CVD coater and a conventional float glass process will, be well understood by one of ordinary skill in the art and, therefore, will not be described in detail.
  • the first coater 52 has three coating cells A1-A3 and the second coater 54 has seven coating cells B1-B7.
  • This cell numbering is arbitrary and is presented simply to aid in discussion of the process described below.
  • Each coating cell can be connected to a manifold to supply a coating composition to the glass.
  • one or more of the cells or a set of the cells can be individually connected to a supply of a coating precursor material and/or a supply of a dopant precursor material. These connections can be via pipes, conduits, or any other conventional methods.
  • the coating cells B1-B7 of the second coater 54 are each individually connected to a respective coating precursor supply 60 and a dopant precursor supply 62 .
  • the first coater 52 can also be configured in similar manner.
  • the first coater 52 can be used to apply an undercoating on the glass and the second coater 54 can be used to supply a top coat, e.g. TCO coating having a selected dopant profile, as described below.
  • a top coat e.g. TCO coating having a selected dopant profile, as described below.
  • each of the coating cells is individually connected to a coating precursor supply 60 and a dopant precursor supply 62 , it is to be understood that two or more of the cells could be connected to the same coating precursor supply 60 , such as by a manifold, if desirable for a particular coating configuration.
  • a dopant precursor supply 62 could be operatively connected to two or more of the coating precursor supply 60 conduits, if acceptable for the desired final coating composition.
  • the coating precursor supplies 60 are a source or container containing the precursor materials that, when directed onto the hot glass 56 , react or break down to form a coating of a desired composition.
  • the coating precursor material can include materials that, when directed onto the hot glass 56 , react or combine with oxygen to form an oxide.
  • materials include precursors for oxides of one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials, such as zinc stannate.
  • Such precursor materials are commercially available and can be selected based on a desired coating composition.
  • MBTC monobutyltin trichloride
  • TEOS tetraethylorthosilicate
  • TIBAL triisobutylaluminum
  • the dopant precursor supplies 62 are a source or container containing a material or dopant to be mixed with the coating precursor material prior to deposition of the coating material onto the glass surface.
  • Common dopant materials include F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, and/or Sb.
  • tungsten hexafluoride is a precursor for tungsten
  • trifluoroacetic acid (TFA) is a precursor for fluorine.
  • TFA trifluoroacetic acid
  • Such precursor materials are commercially available and can be selected based on a desired dopant.
  • the coating composition supplied onto the glass 56 can be varied at each coating cell by selecting or varying the amount or the ratio of the coating precursor material and the dopant precursor material supplied to the individual cells of the coater from the various coating supplies.
  • each cell can be connected to a supply of a tin oxide precursor material (such as MBTC) as the coating precursor supply 60 and a fluorine precursor material (such as TFA) as the dopant precursor supply 62 .
  • the cells can also be connected to other supplies typical for a CVD coating process, such as a carrier gas supply (such as nitrogen or oxygen) and a water source supply, etc. However, for ease of discussion, these other sources are not specifically shown.
  • the ratio of the coating components e.g., coating precursor and dopant precursor
  • the dopant concentration through the resultant coating can be controlled as desired for a particular purpose.
  • the outer surface of the TCO layer is conductive (i.e., has a low sheet resistance).
  • this was achieved by adding a conductive dopant to a coating precursor material to form a coating composition and then applying the coating composition onto the glass surface.
  • the resultant coating had the dopant uniformly distributed throughout the coating. While this coating did have a conductive outer surface, the dopant located away from the outer surface deeper in the coating contributed little to the surface conductivity of the coating and actually was a detriment to the overall coating transparency.
  • the dopant concentration can be skewed or selectively limited to the outer part (upper portion) of the TCO coating to provide a desired sheet resistance but not be present in the depth of the coating to adversely impact upon the transmission of the layer.
  • the dopant material can be preferentially added to be near the bottom of the coating and not present near the top of the layer.
  • individual coating precursor supplies 60 and dopant precursor supplies 62 were in flow communication with the coating cells, it is also possible that individual coating cells are each connected to a single coating source having a mixture of a coating precursor material and a dopant precursor material, with the ratio of these components being different between the different coating sources connected to different coating cells.
  • Each of the following examples used clear glass substrates having a thickness of 3.2 mm.
  • the TCO coating was deposited by a second coater 54 as described above to have a thickness of 665 nm.
  • Cells B1-B7 were used. Each cell had a tin precursor (MBTC) flow rate of 52.3 pounds per hour (lb/hr) and a water flow rate of 14.6 lb/hr.
  • MBTC tin precursor
  • TSA fluorine precursor
  • the coating was sputter probed using x-ray photoemission spectrometry to determine the change in fluorine concentration versus coating depth.
  • the sputter time is an indication of depth, with one second of sputter time equal to about 1.5 Angstroms.
  • TFA was supplied to each cell as set forth in FIG. 3 .
  • This example used a uniform TFA flow rate to each cell.
  • the coating was sputter probed and the results shown in FIG. 4 . As can be seen from FIG. 4 , the fluorine concentration was relatively uniform through the coating depth.
  • the TCO coating had a sheet resistance of 8.6 ⁇ / ⁇ , a light transmittance of 82.6 percent, and a haze of 0.96 percent.
  • TFA was supplied to each cell as set forth in FIG. 5 .
  • This example used a lower initial TFA flow rate.
  • the coating was sputter probed and the results shown in FIG. 6 . As can be seen, the fluorine concentration was lower at the bottom of the coating and higher at the top of the coating.
  • the TCO coating had a sheet resistance of 8.8 ⁇ / ⁇ , a light transmittance of 82.8 percent, and a haze of 0.79 percent.
  • TFA was supplied to each cell as set forth in FIG. 7 .
  • This example used a higher initial TFA flow rate and a lower final flow rate.
  • the coating was sputter probed and the results shown in FIG. 8 . As can be seen, the fluorine concentration was higher at the bottom of the coating and lower at the top of the coating.
  • the TCO coating had a sheet resistance of 9.4 ⁇ / ⁇ , a light transmittance of 82.1 percent, and a haze of 1.09 percent.
  • This example shows a TCO coating with discrete step changes in fluorine composition as a function of coating depth.
  • the substrate was 3.2 mm clear glass and the coating had a thickness of 385 nm.
  • Six coater cells were used.
  • the MBTC flow rate was 43.6 lb/hr and the water flow rate was 7.9 lb/hr.
  • the TFA flow rate was 8.2 lb/hr in cell 5, 14.03 lb/hr in cells 1 and 3, and 0 lb/hr in cells 2, 4, and 6.
  • the coating had the composition profile shown in FIG. 11 .
  • FIG. 12 shows the F/Sn ratio versus depth for the coating. Discrete areas of fluorine composition were formed in the coating.
  • the TCO coating had a sheet resistance of 21.0 ⁇ / ⁇ , a light transmittance of 84.1 percent, and a haze of 0.70 percent.
  • This example illustrates a TCO having a step change in fluorine composition as a function of depth to enable the control of haze while maintaining a constant sheet resistance.
  • the glass was a low-iron glass having a thickness of 4.0 mm. Eight coating cells were used. Cell A3 of the first coater is designated “cell 8” in this example and cells 1-7 refer to cells B1-B7 described above. Each cell had an MBTC, Water, and TFA flow rate as shown in Table 1. All values are in lbs/hr.
  • the coatings had the haze and sheet resistance values shown in Table 2. Thickness values are in nm, haze is in percent, and sheet resistance is in ohms per square.
  • FIG. 13 is a graph showing the oxygen, tin, and fluorine versus depth for Sample 1.
  • FIG. 14 is a graph showing the oxygen, tin and fluorine content versus depth for Sample 2.
  • FIG. 15 is a graph showing oxygen, tin, and fluorine content versus depth for Sample 3.
  • FIG. 16 shows the total layer thickness versus haze for Samples 1-3. As can be seen, as the thickness increases, the haze increases.
  • FIG. 17 shows coating thickness versus sheet resistance for Samples 1-3. As can be seen, the sheet resistance remained relatively constant even as the coating thickness increased.
  • FIG. 18 is a graph of transmitted haze versus wavelength for Samples 1-3.

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