WO2008088570A1 - Reinforcing structures for thin-film photovoltaic device substrates, and associated methods - Google Patents

Reinforcing structures for thin-film photovoltaic device substrates, and associated methods Download PDF

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Publication number
WO2008088570A1
WO2008088570A1 PCT/US2007/066902 US2007066902W WO2008088570A1 WO 2008088570 A1 WO2008088570 A1 WO 2008088570A1 US 2007066902 W US2007066902 W US 2007066902W WO 2008088570 A1 WO2008088570 A1 WO 2008088570A1
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WIPO (PCT)
Prior art keywords
thin film
reinforced substrate
photovoltaic device
film photovoltaic
silicon
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Application number
PCT/US2007/066902
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English (en)
French (fr)
Inventor
Lawrence M. Woods
Joseph H. Armstrong
Rosine M. Ribelin
Thomas Duncan Barnard
Yukinari Harimoto
Hidekatsu Hatanaka
Maki Itoh
Dimitris Elias Katsoulis
Michitaka Suto
Bizhong Zhu
Nicole R. Anderson
Herschel Henry Reese
Original Assignee
Itn Energy Systems, Inc.
Dow Corning Corporation
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Application filed by Itn Energy Systems, Inc., Dow Corning Corporation filed Critical Itn Energy Systems, Inc.
Publication of WO2008088570A1 publication Critical patent/WO2008088570A1/en

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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
    • H01L31/036—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
    • H01L31/03921—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 only elements of Group IV of the Periodic System
    • 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
    • H01L31/03926—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 comprising a flexible substrate
    • H01L31/03928—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 comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar 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
    • 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

  • Flexible solar power arrays often include a plurality of flexible thin-film photovoltaic (TFPV) devices which are operable to convert electromagnetic energy into electric current.
  • TFPV device is formed of a plurality of different thin-film layers on a substrate. The substrate thus forms the base of the TFPV device and influences its characteristics.
  • Substrates today commonly consist of glass, metallic foils, or polyimides.
  • one reinforced substrate for use in a photovoltaic device includes a polymer base material and a reinforcing structure bonded with the base material to present the reinforced substrate.
  • the reinforced substrate presents a surface in a condition that is made-ready for deposition of thin film layers of the photovoltaic device.
  • one thin film photovoltaic device includes a reinforced substrate including a polymer base material and a reinforcing structure bonded with the base material to present the reinforced substrate. A plurality of thin film layers are formed on a surface of the reinforced substrate.
  • a process of producing a reinforced substrate includes combining a fluid base material and a fiber reinforcing structure to form an impregnated fiber reinforcement.
  • the impregnated fiber reinforcement is cured to form the reinforced substrate, and the reinforced substrate is annealed.
  • a process of producing an array of thin film photovoltaic devices on a reinforced substrate includes cutting a plurality of first scribes in a stack of thin film layers formed on the reinforced substrate down to a surface the reinforced substrate.
  • a plurality of second scribes in the stack of thin film layers are cut adjacent to the first scribes down to a surface of a back contact layer.
  • the plurality of first scribes are filled with an insulator, and a top contact layer is applied on a top surface of the stack of thin film layers.
  • a plurality of third scribes are cut through the top contact layer and the stack of thin film layers down to the surface of the back contact layer.
  • FIG. 1 is a top plan view of one solar power array including a reinforced substrate, according to an embodiment.
  • FIG. 2 is a mid sectional side view of one reinforced substrate including nano-filler, according to an embodiment.
  • FIG. 3 is a top perspective view of one reinforced substrate including metal foil, according to an embodiment.
  • FIG. 4A is a top perspective view of one reinforced substrate including a fiber reinforcing structure, according to an embodiment.
  • FIG. 4B is a top perspective view of the fiber reinforcing structure of FIG. 4A.
  • FIG. 5 is a flow chart of one process of producing a reinforced substrate, according to an embodiment.
  • FIG. 6 is a flow chart of one process of combining base material and a fiber reinforcing structure, according to an embodiment.
  • FIG. 7 is a mid sectional view of one TFPV device, according to an embodiment.
  • FIG. 8 is a mid sectional view of one TFPV device, according to an embodiment.
  • FIG. 9 is a mid sectional view of one TFPV device, according to an embodiment.
  • FIG. 10 is a mid sectional view of one array of TFPV devices monolithically integrated onto a common reinforced substrate, according to an embodiment.
  • FIG. 11 is a flow chart of one process of producing an array of TFPV devices monolithically integrated onto a common reinforced substrate, according to an embodiment.
  • a substrate forms the base of each TFPV device; accordingly, a substrate must possess certain characteristics in order for a TFPV device to meet such goals. Such characteristics include the following: [0023] First, the substrate must be flexible and lightweight in order for TFPV devices built on the substrate and a solar power array incorporating the TFPV devices to be flexible and lightweight.
  • the substrate possess sufficient mechanical strength to survive TFPV device production processing steps which are required for economical production of TFPV devices.
  • roll-to-roll processing techniques may be used to produce TFPV devices in a more efficient and lower cost manner than some other production techniques.
  • roll-to-roll processing techniques exert more mechanical stress on the substrate than some other processing techniques; accordingly, a substrate to be used with roll-to-roll processing techniques must possess significant mechanical strength.
  • the substrate should tolerate high processing temperatures to enable production of high conversion efficiency TFPV devices, which generally requires processing temperatures in excess of 500 degrees Celsius ( 0 C).
  • the substrate possess thermal expansion properties (e.g., a coefficient of thermal expansion) that are sufficiently matched to that of the materials forming the TFPV devices to avoid mechanical failures during device processing and/or subsequent operation of the TFPV devices.
  • the substrate should have an electrical resistivity high enough to support monolithic integration of TFPV devices on a common substrate, which is the formation of a plurality of TFPV devices on a common substrate. Monolithic integration may reduce the cost and size, increase the reliability, and promote ease of manufacturing of an array of TFPV devices.
  • FIG. 1 is a top plan view of a solar power array 100, illustrates one embodiment of a reinforced substrate.
  • Solar power array 100 includes a plurality of TFPV devices 104 formed on a common reinforced substrate 102. Accordingly, TFPV devices 104 are monolithically integrated onto reinforced substrate 102 in FIG. 1; however, reinforced substrate 102 is not restricted to monolithic integration applications.
  • TFPV devices 104 generate electric current from electromagnetic energy 106 (e.g., sunlight) incident on solar power array 100; the electric current may be accessed via electrical terminals 108(1) and 108(2).
  • An embodiment of solar power array 100 is relatively flexible and lightweight, and may be used to provide electric power to spacecrafts or high altitude airships. The relative flexibility of solar power array 100 for example allows its use in non-planar applications.
  • Reinforced substrate 102 is a hybrid or composite structure including a base material and a reinforcing structure bonded to the base material.
  • the areas or portions of reinforced substrate 102 that are composed of the base material and the reinforcing structure depend on the materials used to form reinforced substrate 102 as well as its intended use.
  • the base material may be a polymer such as a silicone composition
  • the reinforcing structure may include particles, fibers and/or metallic foil.
  • the reinforcing structure may provide mechanical strength to reinforced substrate 102, thereby enabling formation of reinforced substrate 102 of base materials that would otherwise possess insufficient mechanical strength for formation of an acceptable substrate. Accordingly, the reinforcing structure may allow reinforced substrate 102 to be formed of base materials that are flexible, have a high electrical resistivity and/or are tolerant of high processing temperatures.
  • the reinforcing structure may also be used to control the coefficient of thermal expansion ("CTE") of reinforced substrate 102.
  • the CTE may be critical because it may affect whether a TFPV device formed on reinforced substrate 102 cracks during its processing and/or its operation due to a mismatch in CTE between reinforced substrate 102 and thin film layers formed thereon.
  • the reinforcing structure can affect physical characteristics of reinforced substrate 102 on a macro and/or nano scale.
  • a reinforcing structure that affects characteristics of a reinforced substrate on a nano scale (“nano scale reinforcing structure”) is discussed below with respect to FIG. 2; reinforcing structures that affects characteristics of a reinforced substrate on a macro scale (“macro scale reinforcing structure”) are discussed below with respect to FIGS. 3, 4A and 4B.
  • FIG. 2 is a mid sectional side view of a nano scale reinforced substrate 202 including a base material 210, which may be a polymer such as a silicone composition, and nano-filler 212 disposed within base material 210.
  • Reinforced substrate 202 may have a high electrical resistivity enabling its use in monolithic integration applications.
  • Nano filler 212 which includes a plurality of small particles 214 (only three of which are labeled to promote illustrative clarity), affects the physical characteristics of reinforced substrate 202 on a nano scale.
  • Nano-filler 212 may increase mechanical strength of substrate 202 and/or reduce its CTE.
  • a low CTE may improve manufacturability of TFPV devices formed on reinforced substrate 202 by reducing a mismatch in coefficients of thermal expansion between reinforced substrate 202 and thin film layers formed thereon, thereby reducing cracking of the TFPV devices.
  • the portion of reinforced substrate 202 formed of nano-filler 12 will vary as a function of the characteristics of base material 210, the characteristics of nano-filler 212 and an intended use of reinforced substrate 202.
  • nano-filler 212 composes one of the following portions of reinforced substrate 202: at least 0.003% (w/w), 0.003% to 20% (w/w), or 0.003% to 0.2% (w/w).
  • Particles 214 are illustrated in FIG. 2 as being round. However, particles 214 may be of any acceptable shape, regular or irregular. Particles 214 may be in the form of discontinuous fibers; in such case, the fibers may act together in a web configuration in order to increase the mechanical strength of reinforced substrate 202. Particles 214 may have any sufficiently small size. In one embodiment, particles 214 have a diameter of less than 1 micrometer ( ⁇ m), with a typical diameter of less than 200 nanometer (nm). Furthermore, although particles 214 are illustrated as being uniformly distributed throughout reinforced substrate 202, particles 214 may be non-uniformly distributed throughout reinforced substrate 202.
  • Nano-filler 210 may be formed of suitable materials including, but not limited to, functionalized carbon nanof ⁇ bers, aluminum-based materials such as aluminum oxide and aluminum trihydroxide, boron-based materials such as boric oxide and boric acid, mica, colloidal silica and combinations thereof.
  • An exemplary nano-filler 212 is Pyrograph III carbon nano fiber, commercially available from Applied Sciences, Inc. of Cedarville, Ohio, United States of America.
  • Nano-filler 212 may cooperate with one or more macro scale reinforcing structures, such as metal foil discussed below with respect to FIG. 3, and/or fibers discussed below with respect to FIG. 4, to further reinforce a substrate.
  • nano filler 212 may be disposed in base material 210 using mixing methods known in the art, prior to combining base material 210 with one or more macro scale reinforcing structures, as discussed below.
  • An example of a macro scale reinforcing structure is a metal foil.
  • FIG. 3 is a top perspective view of a reinforced substrate 302 formed of base material 310 including an adjoining metal foil reinforcing structure 312.
  • Base material 310 may be a polymer; in an embodiment, base material 310 is one or more silicone composition layers, and the silicone composition layers and metal foil reinforcing structure 312 are bonded to each other.
  • base material 310 includes nano-filler 212 of FIG. 2.
  • Reinforced substrate 302 is illustrated in FIG. 3 as having two layers 310(1) and 310(2) of base material; however, reinforced substrate 302 can have any number of base material layers.
  • reinforced substrate 302 is illustrated in FIG. 3 as having a layer of base material 310 formed one two sides of metal foil reinforcing structure 312, a layer of base material 310 need only be formed on a single side of metal foil reinforcing structure 312.
  • Metal foil reinforcing structure 312 may, but need not, be formed from stainless steel, titanium, aluminum, kovar, invar, tantalum, brass, niobium and combinations thereof.
  • Embodiments of reinforced substrate 302 include base material 310 consisting of layers of a silicone composition.
  • the reinforced substrate has an overall thickness 318 of 13 to 1006 ⁇ m or of 15 to 500 ⁇ m
  • the silicone composition layers have a combined thickness of 0.5 to 6 ⁇ m
  • the metal foil reinforcing structure 312 has a thickness of 12.5 to 1,000 ⁇ m.
  • Another example of a macro scale reinforcing structure is a plurality of fibers forming a fiber reinforcing structure that is capable of being combined within a base material (e.g., a polymer) to create a reinforced substrate.
  • the fiber reinforcing structure can be any acceptable arrangement of fibers, such as a woven fabric (e.g., cloth), a nonwoven fabric (e.g., a mat or roving), or loose (e.g., individual) fibers.
  • the fibers may be cylindrical in shape and have one of the following ranges of diameters: 1 to 100 ⁇ m, 1 to 20 ⁇ m or 1 to 10 ⁇ m.
  • the fibers typically have a high modulus and a high tensile strength.
  • Loose fibers are typically continuous, meaning the fibers extend throughout the base material in a generally unbroken manner.
  • the fibers may be formed of materials including glass, quartz, metal, carbon, sapphire, graphite, nylon, polyester, aramid (e.g., Kevlar® and Nomex® fibers), polyethylene, polypropylene and silicon carbide. TABLE 1 below lists characteristics of exemplary fibers that may be used in a fiber reinforcing structure.
  • Embodiments of fiber reinforced substrates may, but need not, have characteristics listed below in TABLE 2.
  • Transparency in TABLE 2 is defined as the percentage of visible light incident on the fiber reinforced substrate that passes through the fiber reinforced substrate. Transparency is dependent on factors including the composition of the base material, the thickness of the fiber reinforced substrate, and the refractive index of the fiber reinforcing structure.
  • the fiber reinforced substrate has a flexibility such that it can be bent over a cylindrical steel mandrel having a diameter less than or equal to 3.2 millimeter (mm) without cracking, where the flexibility is determined as described in ASTM Standard D522-93a, Method B.
  • the fiber reinforcing structure is typically heat-treated prior to use to remove organic contaminants.
  • the fiber reinforcing structure may be heated in air at an elevated temperature (e.g., 575 °C) for a suitable period of time (e.g., 2 hours).
  • FIG. 4A is a top perspective view of a fiber reinforced substrate 402 including base material 410 and a fiber reinforcing structure 412.
  • base material 410 is a polymer (e.g., a silicone composition) that is flexible, has a high electrical resistivity and/or is tolerant of high processing temperatures.
  • Base material 410 includes one or more layers, and may include nano filler 212, as discussed above with respect to FIG. 2.
  • Reinforced substrate 402 has a thickness ranging from 20 to 60 ⁇ m.
  • Fiber reinforcing structure 412 and optional nano-filler 212 may permit fiber reinforced substrate 402 to possess sufficient mechanical strength to be used as a substrate for TFPV devices.
  • optional nano-filler 212 may reduce the overall CTE of fiber reinforced substrate 402, thereby improving manufacturability of TFPV devices built upon fiber reinforced substrate 402.
  • an embodiment of fiber reinforced substrate 402 including nano-filler 212 can withstand annealing temperatures in excess of 500 0C without exhibiting substantial cracking.
  • Fiber reinforcing structure 412 is illustrated in FIG. 4A as being disposed in an essentially horizontal plane located near the vertical center of base material 410. However, fiber reinforcement structure 412 may be disposed in other locations within base material 410.
  • FIG. 4B is a top perspective view of fiber reinforcing structure 412.
  • Fiber reinforcing structure 412 as illustrated in FIG. 4B includes bundles of fibers 414 woven in a web configuration.
  • fiber reinforcing structure 412 has a width 416 of 100 to 200 ⁇ m and a thickness of 20 to 40 ⁇ m, and bundles of fibers 414 each include 50 to 100 individual fibers with diameters ranging from 3 to 6 ⁇ m.
  • Fiber reinforcing structure 412 may also have other configurations.
  • fiber reinforcing structure 412 includes unidirectional bundles of fibers placed parallel to each other.
  • fiber reinforcing structure 412 may include bundles of fibers placed perpendicular to each other in grid configuration but not woven together.
  • reinforced substrates 102, 202, 302, and 402 are made ready for deposition of solid state circuitry (e.g., back contact layer 752, 852, or 952 or interface layer 750, 850, or 950) or other materials by, for example, plasma cleaning.
  • the plasma cleaning step is performed in an embodiment using a RF sputtering process under a pressure ranging from approximately twenty to five hundred millitorr in the presence of oxygen or air.
  • power sources for RF sputtering may range from approximately 100 to 500 Watts at a frequency of about 14 MHz from an approximately 182 square centimeter metal cathode.
  • FIG. 5 is a flow chart of a process 500 of producing a reinforced substrate including a fiber reinforcing structure.
  • Process 500 may be used to produce fiber reinforced substrate 402 of FIG. 4, for example.
  • Process 500 begins 522 and proceeds to step 524 where a base material and a fiber reinforcing structure are combined to form an impregnated fiber reinforcement.
  • a fluid base material is applied around the fiber reinforcing structure or the fiber reinforcing structure is introduced into the base material to form an impregnated fiber reinforcement.
  • a base material such as a liquid silicone composition is applied around a woven fiber reinforcing structure.
  • the impregnated fiber reinforcement is cured to form the reinforced substrate.
  • “Cured” as defined herein means that the base material, which can be in the form of the component parts, a mixture, a solution or a blend, is exposed to room temperature air, heated at elevated temperatures or exposed to UV electromagnetic energy, an electron beam or microwave electromagnetic energy. Heating can be achieved using any known conventional means, such as by placing the base material or, in this case, the impregnated fiber reinforcement, into an air-circulating oven.
  • an impregnated fiber reinforcement including a woven fabric reinforcing structure impregnated with a liquid silicone composition is thermally cured to form a fiber reinforced substrate.
  • Step 528 is optional; in step 528, the reinforced substrate is annealed at a high temperature to drive off residual gases an unreacted components. In one example of step 528, the reinforced substrate is annealed at a temperature ranging from 400 to 600 0 C in an air, oxygen, argon, nitrogen, or vacuum.
  • Process 500 subsequently ends 530 after annealing or after curing if step 528 is not executed.
  • Step 524 may be executed in a variety of manners.
  • FIG. 6 illustrates a process 624, which is one process of combining base material and a fiber reinforcing structure to form an impregnated fiber reinforcement.
  • Process 624 for example executes step 524 of process 500, FIG. 5.
  • Process 624 starts 632 and proceeds to step 634, where a silicone composition base material is applied to a release liner to form a silicone film.
  • the silicone composition can be applied to the release liner using conventional coating techniques, such as spin coating, dipping, spraying, brushing or screen-printing.
  • the silicone composition is applied in an amount sufficient to embed the fiber reinforcing structure, as described with respect to step 636, below.
  • the release liner can be any rigid or flexible material having a surface from which the reinforced silicone resin film can be removed without damage by delamination after the silicone composition is cured.
  • release liners include, but are not limited to, nylon, polyethyleneterephthalate and polyimide.
  • the fiber reinforcing structure is embedded in the silicone filmto form an embedded fiber reinforcement.
  • the fiber reinforcing structure may be embedded in the silicone film by simply placing the fiber reinforcing structure on the silicone film and allowing the silicone composition to saturate the fiber reinforcing structure.
  • the fiber reinforcing structure may first be deposited on the release liner, followed by the application of the silicone composition onto the fiber reinforcing structure.
  • steps 634 and 636 are substituted with a single step (not shown in FIG.
  • the fiber reinforcing structure can be impregnated with the silicone composition by passing it through the silicone composition without using the release liner.
  • the fabric is typically passed through the silicone composition at a rate of from 1 to 1,000 cm/s at room temperature (-23 ⁇ 2 0 C).
  • the embedded fiber reinforcement is degassed.
  • the embedded fiber reinforcement may be degassed by subjecting it to a vacuum at a temperature ranging from room temperature (-23 ⁇ 2 0 C) to 60 0 C, for a period of time sufficient to remove air entrapped in the embedded reinforcement.
  • the embedded fiber reinforcement is subjecting to pressure ranging from 1,000 to 20,000 Pa for 5 to 60 minutes at room temperature.
  • step 640 additional silicone composition is applied to the (optionally degassed) embedded fiber reinforcement to form an impregnated fiber reinforcement.
  • the silicone composition may be applied to the degassed embedded fiber reinforcement using conventional methods, as described above. Additional cycles (not shown in FIG. 6) of degassing (step 628) and application of silicone composition (step 640) may occur.
  • the impregnated fiber reinforcement is compressed to remove excess silicone composition and/or entrapped air, and to reduce the thickness of the impregnated fiber reinforcement.
  • the impregnated fiber reinforcement can be compressed using conventional equipment such as a stainless steel roller, a hydraulic press, a rubber roller or a laminating roll set.
  • the impregnated fiber reinforcement is typically compressed at a pressure ranging from 1,000 Pa to 10 MPa and at a temperature ranging from room temperature (-23 ⁇ 2 0 C) to 50 0 C.
  • Process 624 ends 644 after step 640 or optional step 642.
  • Curing step 526 of process 500 may be executed in a variety of manners.
  • the impregnated fiber reinforcement is heated at a temperature sufficient to cure the silicone composition and form the cured impregnated fiber reinforcement.
  • the impregnated fiber reinforcement may be heated at atmospheric, sub- atmospheric or supra-atmospheric pressure.
  • the impregnated fiber reinforcement is for example heated at atmospheric pressure, within one of the following temperature ranges: from room temperature (-23 ⁇ 2 0 C) to 250 0 C, from room temperature to 200 0 C or from room temperature to 150 0 C.
  • the impregnated fiber reinforcement is heated for a length of time sufficient to cure (cross-link) the base material.
  • the impregnated fiber reinforcement may be heated at 150 to 200 0 C for 0.1 to 3 hours.
  • the impregnated fiber reinforcement is heated in a vacuum at a temperature of 100 to 200 0 C and at a pressure of 1 ,000 to 20,000 Pa for 0.5 to 3 hours, to form the cured impregnated fiber reinforcement.
  • the impregnated fiber reinforcement may be heated in the vacuum using a conventional vacuum bagging process.
  • a bleeder e.g., polyester
  • a breather e.g., nylon, polyester
  • a vacuum bagging film e.g., nylon
  • a vacuum e.g., 1,000 Pa
  • Reinforced substrates including, but not limited to, reinforced substrates 102, 202, 302 and 402 of FIGS. 1 -4, respectively, may be used to form one or more flexible and lightweight TFPV devices having high conversion efficiency.
  • Such TFPV devices may be produced using roll to roll techniques, and a plurality of the TFPV devices may be monolithically integrated onto a single reinforced substrate.
  • FIG. 7 is a mid-sectional side view of a TFPV device 700 formed on reinforced substrate 702.
  • TFPV device 700 converts incident electromagnetic energy 106 into an electric current.
  • Reinforced substrates 102, 202, 302 or 402 may serve as reinforced substrate 702.
  • FIG. 7 illustrates a single TFPV device 700 formed on reinforced substrate 702, a plurality of TFPV devices may (and likely would) be formed on reinforced substrate 702.
  • reinforced substrate 702 has a width of about 33 cm, a thickness of about 0.005 cm and a length of up to about 300 m, and is obtained from a payout roll.
  • TFPV device 700 has a vertical stack of four to eight thin film layers deposited on reinforced substrate 702.
  • An optional interface layer 750 may be formed on reinforced substrate 702 to enhance adhesion of a back contact layer 752 to reinforced substrate 702 and to minimize back contact cracking.
  • Interface layer 750 may have a CTE between that of reinforced substrate 702 and back contact layer 752 to minimize back contact cracking.
  • Interface layer 750 may be formed of nickel-vanadium, copper, brass, indium tin oxide (ITO) and/or other materials known not to be detrimental to TFPV device 700 if diffusion of these materials were to occur.
  • Back contact layer 752 is formed on interface layer 750 if an interface layer is used; otherwise, back contact layer 752 is formed directly on reinforced substrate
  • back contract layer 752 is approximately 0.5 ⁇ m thick and includes molybdenum. If back contact layer 752 is formed of molybdenum directly on reinforced substrate 702, back contact layer 752 may further include oxygen to alter the properties of back contact layer 752 to reduce back contact cracking.
  • An additional stress relief layer 764 is optionally formed on a side 766 of reinforced substrate 702, opposite back contact layer 752. In an embodiment, stress relief layer 764 is formed of molybdenum or another inert metal. [0060]
  • a solar absorber layer 754 is formed on back contact layer 752.
  • solar absorber layer 754 is 2.0 ⁇ m thick and includes a copper based group I- III-VI material such as copper indium diselenide (CIS) and one or more silver based group I- III-VI materials such as silver indium diselenide (AIS).
  • Solar absorber layer 754 may include alloys of CIS or AIS; such alloys for example include gallium, aluminum, sulfur and/or tellurium. Furthermore, alloys of CIS or AIS may include endpoint alloys without indium or selenium.
  • solar absorber layer 754 includes a copper-indium-gallium- diselenide (CIGS) material.
  • CGS copper-indium-gallium- diselenide
  • reinforced substrate 702 may tolerate high processing temperatures to allow deposition of solar absorber layer 754 at a high temperature (i.e., in excess of 500 0 C), thereby increasing conversion efficiency of TFPV device 700.
  • CIS- based solar absorber layers are best formed by heating at temperatures in excess of 500 0 C for a period of 25 to 30 minutes.
  • a heterojunction partner or window layer 756 is formed on solar absorber layer 754.
  • window layer 756 is approximately 0.05 ⁇ m thick and includes cadmium sulfide, zinc sulfide, alloys of cadmium-zinc sulfide, zinc oxide, zinc hydroxide, zinc-magnesium oxide, magnesium hydroxide, or combinations thereof.
  • Window layer 756 may also include indium selenide.
  • Window layer 756 is typically applied by chemical bath deposition (CBD), but can also be applied by non-wet techniques such as sputtering, as discussed below.
  • CBD chemical bath deposition
  • An optional electrically insulating buffer layer 758 of an insulating oxide may be formed on window layer 756.
  • buffer layer 758 is 0.05 ⁇ m thick and includes an intrinsic zinc-oxide (i-ZnO), zinc-magnesium oxide alloy, zinc hydroxide, magnesium hydroxide, or combinations thereof.
  • i-ZnO intrinsic zinc-oxide
  • a top electrode or contact layer 760 is formed on buffer layer 758 if a buffer layer is incorporated in TFPV device 700; otherwise top contact layer 760 is formed directly on window layer 756.
  • Top contact layer 760 may include a semi transparent conducting oxide.
  • top contact layer 760 is 0.6 ⁇ m thick and includes a doped tin oxide, an undoped tin oxide, an indium-tin oxide (ITO) alloy, an undoped zinc oxide or a doped zinc-oxide using aluminum or gallium (ZnO:Al,Ga).
  • An optional metallic grid (not illustrated in FIG. 7) may be formed on a top surface 762 of top contact layer 760.
  • the metallic grid includes a thin layer of Ni and a thicker layer of Al or Ag.
  • Thin films layers may be formed on a reinforced substrate to produce TFPV device 700 of FIG. 7 or TFPV devices 800 and 900 (discussed below), using a wide variety of deposition processes.
  • Such deposition processes include, but are not limited to, a sputter plasma (RF, AC, DC and/or plasma assisted) process, an evaporation (thermal, electron beam, or cathodic arc) process, a chemical vapor deposition (low pressure, atmospheric pressure or plasma enhanced) process, a sublimation process, a physical vapor deposition process and/or a hot wire process. Exemplary deposition processes are discussed with respect to each thin film layer.
  • a plasma cleaning step is performed prior to the back contact layer (e.g., back contact layer 752, 852, or 952) or an interface layer (e.g., interface layer 750, 850, or 950 ) being formed on a reinforced substrate (e.g., reinforced substrate 702).
  • the plasma cleaning may be performed using a RF sputtering process under a pressure ranging from approximately twenty to five hundred millitorr in the presence of oxygen or air.
  • power sources for RF sputtering may range from approximately 100 to 500 Watts at a frequency of about 14 MHz from an approximately 182 square centimeter metal cathode.
  • a back contact layer (e.g., back contact layer 752) is for example formed on a reinforced substrate (e.g., reinforced substrate 702) or an interface layer (e.g., interface layer 750) using a DC sputtering process under a pressure ranging from approximately one to twenty millitorr.
  • power sources for DC sputtering may range from approximately 500 to 5,000 Watts on an approximately 60 square inches target.
  • a back contact layer of molybdenum formed on a reinforced substrate by sputtering has a thickness of 200 to 700 nm.
  • a back contact layer of molybdenum may include oxygen to alter its properties and reduce back contact cracking. Oxygen may be incorporated into the back contact layer during the sputter deposition process, as disclosed in Shafarman et al. at the Space Photovoltaic Research and Technology Conference at NASA Glenn in Cleveland, Ohio, United States of America, September, 2005.
  • a solar absorber layer (e.g., solar absorber layer 754) having a thickness of 1 to 3 ⁇ m is formed on a back contact layer via thermal co-evaporation.
  • Thermal co-evaporation may be conducted by a variety of methods known in the art, such as those disclosed in U.S. Patent No. 5,441,897 to Noufi et al., or in U.S. Patent No. 4,335,226 to Mickelsen et al.
  • a window layer (e.g., window layer 756) may be formed on a solar absorber layer via chemical bath deposition, chemical surface deposition or a non-wet process such as sputtering.
  • the chemical bath deposition process may be accomplished by a variety of methods that are known in the art.
  • U.S. Patent No. 6,537,845 discloses a method for applying a CdS bath solution on a solar absorber layer's surface.
  • a CdS layer may be formed on a solar absorber layer by submersion into an aqueous chemical bath.
  • chemical bath constituents include a cadmium salt and/or zinc salt, (NH 2 ) 2 CS (which is commonly referred to as thiourea), a hydroxide agent and water.
  • Exemplary salts include cadmium sulfate and zinc sulfate, and an example of the hydroxide agent is ammonium hydroxide (NH 4 OH).
  • the bath temperature is typically in the range of 60 to 85 °C.
  • the solar absorber layer's surface is first submersed into a solution containing the salt(s) and the hydroxide agent for a sufficient amount of time (e.g., 1 minute) for the reinforced substrate to reach a desired temperature. Thiourea is then applied to the substrate, and a chemical reaction is allowed to occur for several minutes.
  • the reinforced substrate is removed from the chemical bath, and unreacted bath solution is rinsed away from the solar absorber layer's surface.
  • the thickness of the resulting window layer film typically ranges from 10 to 100 nm.
  • a buffer layer (e.g., optional buffer layer 758) is formed on a window layer using pulsed DC or RF sputtering under a pressure ranging from approximately one to twenty millitorr.
  • power sources for the pulsed DC sputtering may range from approximately 50 to 500 Watts on an approximately 60 square inches target.
  • the buffer layer formed by such sputtering may be 10 to 100 nm thick.
  • a top contact layer (e.g., top contact layer 760) is formed on a window layer or a buffer layer using pulsed DC sputtering under a pressure ranging from approximately one to twenty millitorr.
  • power sources for the pulsed DC sputtering may range from approximately 500 to 1,500 Watts on an approximately 60 square inches target.
  • a typical film thickness of the top contact layer formed by such sputtering ranges from 200 to 500 nm.
  • Additional embodiments of a TFPV device can be formed on a reinforced substrate. For example, FIG.
  • TFPV device 800 converts incident electromagnetic energy 106 into an electric current.
  • Reinforced substrate 802 may be an embodiment of reinforced substrate 102, 202, 302, or 402.
  • FIG. 8 illustrates a single TFPV device 800 formed on reinforced substrate 802, a plurality of TFPV devices 800 may (and likely would) be formed on reinforced substrate 802.
  • a solar absorber layer 854 is formed of II- VI based materials.
  • Exemplary group II based materials include cadmium, zinc and magnesium; exemplary group VI based materials include sulfur, selenium and tellurium.
  • solar absorber layer 854 include cadmium telluride, alloys of cadmium telluride, cadmium selenide or alloys of cadmium selenide.
  • an optional stress relief layer 864, an optional interface layer 850, a back contact layer 852, a window layer 856, an optional buffer layer 858 and a top contact layer 860 correspond to layers 764, 750, 752, 756, 758 and 760 of TFPV device 700 of FIG. 7.
  • An interface layer 870 may adjoin solar absorber layer 854 and back contact layer 852; however, interface layer 870 may be excluded such that back contact layer 852 directly adjoins solar absorber layer 854.
  • both buffer layer 858 and top contact layer 860 are formed of tin oxide.
  • Back contact interface layer 870 is for example formed of a doped ZnTe material, and is disposed between contact layer 852 and solar absorber layer 854. Additional details regarding including a back contact interface layer and forming both a top contact layer and a buffer layer of tin oxide are taught in Ilvydas Matulionis, Sijin Han, Jennifer A. Drayton, Kent J. Price and Alvin D. Compaan, Mat. Res. Soc. Symp. Proc. Vol. 668, p.H8.23.1, April (2001), which is herein incorporated by reference in its entirety.
  • the characteristics of reinforced substrate 802 may enable deposition of solar absorber layer 854 at high temperatures (e.g., up to 600 0 C), thereby enabling production of a high-efficiency TFPV device 800.
  • a high-temperature chemical treatment is applied to the junction materials (e.g., to solar absorber layer 854/window layer 856 heterojunctions) or solely to solar absorber layer 854.
  • Such high temperature chemical treatment may be a wet or dry CdCl 2 application and subsequent application of high-temperatures (e.g., 350 to 450 0 C) to reinforced substrate 802 with the CdCl 2 for a period of 5 to 30 minutes.
  • FIG. 9 illustrates another TFPV device formed on a reinforced substrate.
  • FIG. 9 is a mid-sectional side view of a TFPV device 900 formed on reinforced substrate 902.
  • TFPV device 900 converts incident electromagnetic 106 energy into an electric current.
  • Reinforced substrate 902 may be an embodiment of reinforced substrate 102, 202, 302, or 402.
  • FIG. 9 illustrates a single TFPV device 900 formed on reinforced substrate 902, a plurality of TFPV devices may (and likely would) be formed on reinforced substrate 902.
  • TFPV device 900 includes a solar absorber layer 954 including amorphous-silicon based materials, micro-silicon based materials or their alloys with hydrogen and germanium.
  • TFPV device 900 is an amorphous-silicon based device and solar absorber layer 954 includes three sub layers 980(1), 980(2) and 980(3), forming a p-i-n structure.
  • Tandem or multi-junction TFPV devices 900 may likewise be formed, by stacking multiple p-i-n solar absorber structures (not shown in FIG. 9) on top of one another, with each i-layer tuned to a different portion of the solar spectrum, preferably with increasing bandgap in the direction of incident electromagnetic energy 106.
  • TFPV device 900 does not include a window layer - a window layer is not needed in TFPV device 900 due to the junction formed by the p-i-n structure of solar absorber layer 954.
  • An optional stress relief layer 964, an optional interface layer 950 and an optional buffer layer 958 generally correspond with layers 764, 750 and 758 of TFPV device 700, FIG. 7.
  • a back contact layer 952 generally corresponds with back contact layer 752, except that back contact layer 952 is commonly formed of aluminum or silver.
  • a top contact layer 960 generally corresponds with top contact layer 760, except that top contact layer 960 is commonly formed of a doped tin oxide material.
  • FIG. 10 is a mid-sectional view of an array 1000 of TFPV devices monolithically integrated onto a reinforced substrate 1002.
  • Array 1000 is illustrated in FIG. 10 as having three TFPV devices 1090(1), 1090(2) and 1090(3); however, array 1000 can have any quantity of TFPV devices.
  • Array 1000 is for example used in a solar power array.
  • Reinforced substrate 1002 may be an embodiment of reinforced substrate 102, 202, 302 or 402.
  • Each TFPV device 1090 is separated from one or more adjacent TFPV devices 1090 by scribes 1096 (also referred to as "third scribes 1096").
  • Each TFPV device 1090 includes a section of back contact layer 1052, solar absorber layer 1054, window layer 1056 and top contact layer 1060.
  • TFPV device 1090(1) includes a back contact layer 1052(1), a solar absorber layer 1054(1), a window layer 1056(1) and a top contact layer 1060(1).
  • Each TFPV device 1090 further includes a first scribe 1092 down to reinforced substrate 1002; each first scribe 1092 is filled with resistive filler 1098 to enable the first scribe to provide electrical isolation.
  • the resistive filler is a resistive ink or oxide.
  • TFPV devices 1090 may be electrically connected in parallel, series, or combinations thereof. Furthermore, one or more TFPV devices 1090 may be at least partially electrically isolated from one or more other TFPV devices 1090.
  • FIG. 10 illustrates TFPV devices 1090 electrically connected in series.
  • electric current enters array 1000 at a terminal 1102(1) and exits array 1000 at a terminal 1102(2).
  • electric current 1100 enters array 1000 via terminal 1102(1).
  • Electric current 1100 flows from terminal 1102(1) along the top of a TFPV device 1090(1) via a top contact layer 1060(1).
  • Electric current 1100 then flows from top contact layer 1060(1) to a back contact layer 1052(2) via a second scribe 1094 which is filled with the conductive material used to form top contact layer 1060.
  • Electric current 1100 flows through back contact layer 1052(2) to the next TFPV device 1090(2).
  • Electric current 1 100 then flows from back contact layer 1052(2) to a top contact layer 1060(2) via a solar absorber layer 1054(2) and a window layer 1056(2). Electric current 1100 continues to flow through the remainder of photovoltaic device 1090(2) in the same manner as in photovoltaic device 1090(1,) and then flows through a photovoltaic device 1090(3) in the same manner as in photovoltaic device 1090(2). Electric current 1100 finally exits array 1000 via terminal 1102(2).
  • Additional embodiments of array 1000 may be formed where TFPV devices 1090 include one or more features of TFPV devices 700, 800 and/or 900 discussed above.
  • TFPV devices 1090 may include an interface layer, a stress relief layer and/or a buffer layer.
  • solar absorber layer 1054 may form a p-i-n structure.
  • each TFPV device 1090 may include a plurality of junctions as discussed above with respect to FIG. 9.
  • FIG. 11 is a flow chart of a process 1120 of producing an array of TFPV devices monolithically integrated onto a reinforced substrate.
  • Process 1120 is for example used to produce array 1000 of FIG. 10.
  • a series of scribing and printing operations are interspersed with the thin-film layer deposition operations described above, to form a sequence of 'monolithically interconnected' photovoltaic devices on a single section of reinforced substrate.
  • Process 1120 starts 1122 and proceeds to step 1124 wherein first scribes are cut in a stack of thin film layers formed on a reinforced substrate (e.g., reinforced substrate 102, 202, 302, or 402).
  • the stack of thin film layers includes at least a back contact layer (e.g., layers 752, 852 or 952 of FIGS. 7-9, respectively) and a solar absorber layer or layers (e.g., layers 754, 854 or 954 of FIGS. 7-9, respectively).
  • the stack of thin film layers may optionally include additional layers including a stress relief layer (e.g., layers 764, 864 or 964 of FIGS. 7-9, respectively), an interface layer (e.g., layers 750, 850 or 950 of FIGS.
  • first scribes are cut through all deposited layers exposing the top of the bare, uncoated reinforced substrate, to functionally divide the deposited thin layers into plural individual segments and thereby isolate each segment electrically. The segments are held together by the reinforced substrate, which remains intact.
  • the scribing technique used is a matter of design choice. In one embodiment, scribing is accomplished using a high power density laser.
  • first scribes 1092 of array 1000 are laser-cut through top contact layer 1060, window layers 1056, solar absorber layer 1054 and back contact layer 1052 to expose substrate 1002.
  • step 1126 second scribes are cut in the stack of thin film layers formed on the reinforced substrate adjacent to the first scribes. In contrast to the first scribes, the second scribes are only cut down to the top surface of the deposited back contact layer. The second scribes form a via, or a channel, which will later be filled with a conductive oxide or other top conductor material.
  • second scribes 1094 of array 1000 (FIG. 10) are laser-cut through top contact layer 1060, window layer 1056 and solar absorber layer 1054 to expose the surface of back contact layer 1052.
  • the first scribe are filled with an insulator, in step 1128.
  • Step 1128 is for example executed by depositing a UV curable ink using a commercially adapted ink jet dispense head that is coincident with the high power density laser used to cut the first scribes.
  • first scribes 1092 of array 1000 are filled with resistive filler 1098.
  • an electrically insulating buffer layer is deposited on the top of the window layer, or the solar absorber layer if a window layer is not deposited.
  • the buffer layer is for example an intrinsic-zinc-oxide (i-ZnO) layer.
  • i-ZnO intrinsic-zinc-oxide
  • a buffer layer may already be deposited on the solar absorber layer or the window layer before the start of process 1120, or a buffer layer may be deposited on the solar absorber layer or the window layer between steps 1124 and 1126.
  • a window layer may optionally be deposited on the solar absorber layer before the start of process 1120, between steps 1124 and 1 126 and/or as an additional part of step 1130.
  • a top contact layer is deposited on the top surface of the top thin film layer of the stack.
  • the top thin film layer may be a window layer, a buffer layer, or a solar absorber layer.
  • top contact layer 1060 is deposited on window layer 1056 of array 1000 of FIG. 10.
  • step 1134 third scribes are cut in the stack of thin film layers. Like the second scribes, the third scribes are cut down to the top surface of the deposited back contact layer. The third scribes provide electrical isolation to complete formation of an array of TFPV devices.
  • third scribes 1096 are laser cut through top contact layer 1060, window layer 1056 and solar absorber layer 1054 of array 1000, electrically isolating photovoltaic devices 1090(1), 1090(2) and 1090(3) of FIG. 10.
  • Process 1120 ends 1136 after step 1134.
  • a base material of a reinforced substrate may be a silicone composition.
  • the silicone composition is a hydrosilylation-curable silicone composition including a silicone resin (A), an organosilicon compound (B) and a hydrosilylation catalyst (C).
  • the silicone resin (A) has silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms.
  • the silicone resin (A) is typically a copolymer including R2S1O3/2 units, i.e., T units and/or S1O4/2 units, i.e., Q units, in combination with Rl R ⁇ SiO 1/2 units, i.e., M units and/or R- ⁇ SiC ⁇ units, i.e., D units, wherein RI is a Cj to Ci Q hydrocarbyl group or a C ⁇ to Cj Q halogen-substituted hydrocarbyl group, both free of aliphatic unsaturation, and R ⁇ is Rl, an alkenyl group or hydrogen.
  • the silicone resin can be a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin or an MDQ resin.
  • the phrase "free of aliphatic unsaturation" means the hydrocarbyl or halogen-substituted hydrocarbyl group does not contain an aliphatic carbon- carbon double bond or carbon-carbon triple bond.
  • the C ⁇ to CI Q hydrocarbyl group and C ⁇ to Cj Q halogen-substituted hydrocarbyl group represented by RI more typically have from 1 to 6 carbon atoms.
  • Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
  • hydrocarbyl groups represented by RI include, but are not limited to: alkyl groups, such as methyl, ethyl, propyl, 1- methyl ethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1 -dimethyl ethyl, pentyl, 1- methylbutyl, 1 -ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1 ,2-dimethylpropyl, 2,2- dimethylpropyl, hexyl, heptyl, octyl, nonyl and decyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl and methylcyclohexyl; aryl groups, such as phenyl and naphthyl
  • halogen-substituted hydrocarbyl groups represented by R ⁇ include, but are not limited to: 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl.
  • the alkenyl groups represented by R ⁇ typically have from 2 to 10 carbon atoms (alternatively from 2 to 6 carbon atoms) and are exemplified by, but are not limited to: vinyl, allyl, butenyl, hexenyl and octenyl.
  • R ⁇ is predominantly the alkenyl group. In this embodiment, typically at least 50 mol%, alternatively at least 65 mol%, alternatively at least
  • the groups represented by R ⁇ in the silicone resin are alkenyl groups.
  • the mol% of alkenyl groups in R ⁇ is defined as a ratio of the number of moles of silicon-bonded alkenyl groups in the silicone resin to the total number of moles of the R ⁇ groups in the resin, multiplied by 100.
  • R ⁇ is predominantly hydrogen.
  • typically at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol%, of the groups represented by R ⁇ in the silicone resin are hydrogen.
  • the mol% of hydrogen in R ⁇ is defined as a ratio of the number of moles of silicon-bonded hydrogen in the silicone resin to the total number of moles of the R ⁇ groups in the resin, multiplied by 100.
  • the silicone resin (A) has the formula: (R 2 Si0 3 / 2 ) y (Si0 4 /2) z ( ⁇ ) wherein R ⁇ and R ⁇ are as described and exemplified above and w, x, y and z are mole fractions.
  • the silicone resin represented by formula (I) has an average of at least two silicon-bonded alkenyl groups per molecule.
  • the subscript w typically has a value of from 0 to 0.9, alternatively from 0.02 to 0.75, alternatively from 0.05 to 0.3.
  • the subscript x typically has a value of from 0 to 0.9, alternatively from 0 to 0.45, alternatively from 0 to 0.25.
  • the subscript y typically has a value of from 0 to 0.99, alternatively from 0.25 to 0.8, alternatively from 0.5 to 0.8.
  • the subscript z typically has a value of from 0 to 0.85, alternatively from 0 to 0.25, alternatively from 0 to 0.15.
  • the ratio y+z/(w+x+y+z) is typically from 0.1 to 0.99, alternatively from 0.5 to 0.95, alternatively from 0.65 to 0.9.
  • the ratio w+x/(w+x+y+z) is typically from 0.01 to 0.90, alternatively from 0.05 to 0.5, alternatively from 0.1 to 0.35.
  • silicone resins represented by formula (I) above include, but are not limited to, resins having the following formulae: (Vi 2 MeSiOi/2)o.25(PhSi0 3 /2)o.75, (ViMe2SiOiZ2) ⁇ .25(PhSi0 3 Z2) ⁇ .75 »
  • silicone resins represented by formula (I) above include, but are not limited to, resins having the following formulae:
  • the silicone resin represented by formula (I) typically has a number- average molecular weight (M n ) of from 500 to 50,000, alternatively from 500 to 10,000, alternatively 1,000 to 3,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector, or a refractive index detector and silicone resin (MQ) standards.
  • M n number- average molecular weight
  • the viscosity of the silicone resin represented by formula (I) at 25 0 C is typically from 0.01 to 100,000 Pa-s, alternatively from 0.1 to 10,000 Pa-s, alternatively from 1 to 100 Pa-s.
  • the silicone resin represented by formula (I) typically includes less than 10% (w/w), alternatively less than 5% (w/w), alternatively less than 2% (w/w), of silicon- bonded hydroxy groups, as determined by ⁇ 9gi NMR.
  • silicone resins represented by formula (I) are well known in the art; many of these resins are commercially available.
  • Silicone resins represented by formula (I) are typically prepared by cohydrolyzing the appropriate mixture of chlorosilane precursors in an organic solvent, such as toluene.
  • a silicone resin including R ⁇ R- ⁇ SiOi /2 units and R2siO 3 /2 units can be prepared by cohydrolyzing a first compound having the formula R* R ⁇ SiCl and a second compound having the formula
  • the silicone resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups.
  • first or second compounds containing hydrolysable groups other than chloro groups such as -Br, -I, -OCH3, -OC(O)CH 3 , -N(CH 3 ) 2 , NHCOCH 3 and -SCH 3 , can be cohydrolyzed to form the silicone resin.
  • the properties of the silicone resin depend on the types of first and second compounds, the mole ratio of first and second compounds, the degree of condensation and the processing conditions.
  • the hydrosilylation-curable silicone composition further includes a cross- linking agent (B) having silicon-bonded hydrogen atoms or silicon-bonded alkenyl groups capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the silicone resin.
  • the cross-linking agent (B) has an average of at least two silicon-bonded hydrogen atoms per molecule, alternatively at least three silicon-bonded hydrogen atoms per molecule. It is generally understood that cross-linking occurs when the sum of the average number of alkenyl groups per molecule in the silicone resin (A) and the average number of silicon-bonded hydrogen atoms per molecule in the cross-linking agent (B) is greater than four.
  • the cross-linking agent (B) is present in an amount sufficient to cure the silicone resin (A).
  • the cross-linking agent (B) is typically an organosilicon compound and may be further defined as an organohydrogensilane, an organohydrogensiloxane, or a combination thereof.
  • the structure of the organosilicon compound can be linear, branched, cyclic, or resinous.
  • the silicon-bonded hydrogen atoms can be located at terminal, pendant, or at both terminal and pendant positions.
  • Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.
  • the organohydrogensilane can be a monosilane, disilane, trisilane, or polysilane.
  • R ⁇ is predominantly the alkenyl group
  • specific examples of organohydrogensilanes that are suitable for purposes of the present invention include, but are not limited to, diphenylsilane, 2-chloroethylsilane, bis[(p-dimethylsilyl)phenyl]ether, 1 ,4-dimethyldisilylethane, 1 ,3,5-tris(dimethylsilyl)benzene, 1 ,3,5-trimethyl-l ,3,5-trisilane, poly(methylsilylene)phenylene and poly(methylsilylene)methylene.
  • organohydrogensilanes that are suitable for purposes of the present invention include, but are not limited to, silanes having the following formulae:
  • the organohydrogensilane can also have the formula:
  • organohydrogensilanes having the formula (III), wherein R.1 and R ⁇ are as described and exemplified above include, but are not limited to, organohydrogensilanes having a formula selected from the following structures:
  • organohydrogensilanes can be prepared by reaction of Grignard reagents with alkyl or aryl halides.
  • organohydrogensilanes having the formula HR ⁇ 2Si-R ⁇ - SiR ⁇ H can be prepared by treating an aryl dihalide having the formula R ⁇ X 2 with magnesium in ether to produce the corresponding Grignard reagent and then treating the Grignard reagent with a chlorosilane having the formula HRl 2 SiCl, where R ⁇ and R ⁇ are as described and exemplified above.
  • the organohydrogensiloxane can be a disiloxane, trisiloxane, or polysiloxane.
  • organosiloxanes suitable for use as the cross-linking agent (B) when R ⁇ is predominantly hydrogen include, but are not limited to, siloxanes having the following formulae:
  • organohydrogensiloxanes that are suitable for purposes of the present invention when R ⁇ is predominantly alkenyl group include, but are not limited to, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1,3,5-trimethylcyclotrisiloxane, a trimethylsiloxy- terminated poly(methylhydrogensiloxane), a trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), a dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane) and a resin including HMe 2 SiOy 2 units, Me 3 SiOy 2 units and SiO 4 Z 2 units, wherein Me is methyl.
  • the organohydrogensiloxane can also be an organohydrogenpolysiloxane resin.
  • the organohydrogenpolysiloxane resin is typically a copolymer including R ⁇ SiO 3 Z 2 units, i.e., T units and/or SiO 4 Z 2 units, i.e., Q units, in combination with units, i.e., M units, and/or R4 2 Si0 2 z 2 units, i.e., D units, wherein RI is as described and exemplified above.
  • the organohydrogenpolysiloxane resin can be a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.
  • the group represented by R ⁇ is either Rl or an organosilylalkyl group having at least one silicon-bonded hydrogen atom. Examples of organosilylalkyl groups represented by R ⁇ include, but are not limited to, groups having a formula selected from the following structures:
  • the groups represented by R ⁇ in the organohydrogenpolysiloxane resin are organosilylalkyl groups having at least one silicon-bonded hydrogen atom.
  • the mol% of organosilylalkyl groups in R ⁇ is defined as a ratio of the number of moles of silicon-bonded organosilylalkyl groups in the silicone resin to the total number of moles of the R ⁇ groups in the resin, multiplied by 100.
  • the organohydrogenpolysiloxane resin typically has the formula:
  • organohydrogenpolysiloxane resins represent by formula (IV) above include, but are not limited to, resins having the following formulae: ((HMe 2 SiC 6 H4SiMe 2 CH 2 CH 2 ) 2 MeSi0 1/2 )o.i 2 (PhSi ⁇ 3/ 2 )o.88, ((HMe 2 SiC 6 H 4 SiMe 2 CH 2 CH 2 ) 2 MeSiO 1/2 ) 0 .i7(PhSi ⁇ 3/ 2 )0.83, ((HMe 2 SiC 6 H4SiMe 2 CH 2 CH 2 ) 2 MeSiO 1 / 2 ) 0 . 1 7(MeSiO3 / 2)0.17( p hSiO 3/2 ) 0 . 66 ,
  • Me 2 SiOy 2 )COo(PhSiO 3 Z 2 )O -8 O wherein Me is methyl, Ph is phenyl, C5H4 denotes a para-phenylene group, and the numerical subscripts outside the parenthesis denote mole fractions.
  • the sequence of units in the preceding formulae is not to be viewed in any way as limiting to the scope of the invention.
  • the organohydrogenpolysiloxane resin having the formula (IV) can be prepared by reacting a reaction mixture including (a) a silicone resin having the formula
  • silicone resin (a) has an average of at least two silicon-bonded alkenyl groups per molecule, and the mole ratio of silicon-bonded hydrogen atoms in (b) to alkenyl groups in (a) is from 1.5 to 5.
  • Silicone resin (a) can be the same as or different than the specific silicone resin used as component (A) in the hydrosilylation-curable silicone composition.
  • organosilicon compound (b) has an average of from two to four silicon-bonded hydrogen atoms per molecule.
  • the organosilicon compound (b) has an average of from two to three silicon-bonded hydrogen atoms per molecule. As also set forth above, the organosilicon compound (b) typically has a molecular weight less than 1,000, alternatively less than 750, alternatively less than 500.
  • the organosilicon compound (b) further includes silicon-bonded organic groups that may be selected from the group of hydrocarbyl groups and halogen-substituted hydrocarbyl groups, both free of aliphatic unsaturation, which are as described and exemplified above for Rl.
  • Organosilicon compound (b) can be an organohydrogensilane or an organohydrogensiloxane, each of which are defined and exemplified in detail above.
  • Organosilicon compound (b) can be a single organosilicon compound or a mixture comprising two or more different organosilicon compounds, each as described above.
  • organosilicon compound (B) can be a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or a mixture of an organohydrogensilane and an organohydrogensiloxane.
  • the mole ratio of silicon-bonded hydrogen atoms in organosilicon compound (b) to alkenyl groups in silicone resin (a) is typically from 1.5 to 5, alternatively from 1.75 to 3, alternatively from 2 to 2.5.
  • Hydrosilylation catalyst (c) can be any of the well-known hydrosilylation catalysts comprising a platinum group metal (i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium) or a compound containing a platinum group metal. Typically, the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
  • Specific hydrosilylation catalysts suitable for (c) include the complexes of chloroplatinic acid and certain vinyl -containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, the portions of which address hydrosilylation catalysts are hereby incorporated by reference.
  • a catalyst of this type is the reaction product of chloroplatinic acid and l,3-diethenyl-l,l,3,3-tetramethyldisiloxane.
  • the hydrosilylation catalyst can also be a supported hydrosilylation catalyst comprising a solid support having a platinum group metal on the surface thereof.
  • a supported catalyst can be conveniently separated from the organohydrogenpolysiloxane resin represented by formula (IV), for example, by filtering the reaction mixture.
  • supported catalysts include, but are not limited to, platinum on carbon, palladium on carbon, ruthenium on carbon, rhodium on carbon, platinum on silica, palladium on silica, platinum on alumina, palladium on alumina and ruthenium on alumina.
  • the concentration of hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction of silicone resin (a) with organosilicon compound (b).
  • the concentration of hydrosilylation catalyst (c) is sufficient to provide from 0.1 to 1000 ppm of a platinum group metal, alternatively from 1 to 500 ppm of a platinum group metal, alternatively from 5 to 150 ppm of a platinum group metal, based on the combined weight of silicone resin (a) and organosilicon compound (b).
  • the rate of reaction is very slow below 0.1 ppm of platinum group metal.
  • Organic solvent (d) includes at least one organic solvent.
  • the organic solvent (d) can be any aprotic or dipolar aprotic organic solvent that does not react with silicone resin (a), organosilicon compound (b), or the resulting organohydrogenpolysiloxane resin under the conditions of the present method, and is miscible with components (a), (b) and the organohydrogenpolysiloxane resin.
  • organic solvents (d) that are suitable for purposes of the present invention include, but are not limited to, saturated aliphatic hydrocarbons such as n- pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • saturated aliphatic hydrocarbons such as n- pentane, hexane, n-heptane, isooctane and dode
  • Organic solvent (d) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as described above.
  • the concentration of organic solvent (d) is typically from 0 to 99% (w/w), alternatively from 30 to 80% (w/w), alternatively from 45 to 60% (w/w), based on the total weight of the reaction mixture.
  • the reaction to form the organohydrogenpolysiloxane resin represented by formula (IV) can be carried out in any standard reactor suitable for hydrosilylation reactions. Suitable reactors include glass and Teflon-lined glass reactors. Typically, the reactor is equipped with a means of agitation, such as stirring. Also, typically, the reaction is carried out in an inert atmosphere, such as nitrogen or argon, in the absence of moisture. [0125]
  • the silicone resin (a), organosilicon compound (b), hydrosilylation catalyst (c) and, optionally, organic solvent (d), can be combined in any order.
  • organosilicon compound (b) and hydrosilylation catalyst (c) are combined before the introduction of the silicone resin (a) and, optionally, organic solvent (d).
  • the reaction is typically carried out at a temperature of from 0 to 150 0 C, alternatively from room temperature (-23 ⁇ 2 0 C) to 115 0 C. When the temperature is less than 0 0 C, the rate of reaction is typically very slow.
  • the reaction time depends on several factors, such as the structures of the silicone resin (a) and the organosilicon compound (b), and the temperature.
  • the time of reaction is typically from 1 to 24 h at a temperature of from room temperature (-23 ⁇ 2 0 C) to 150 0 C. The optimum reaction time can be determined by routine experimentation.
  • the organohydrogenpolysiloxane resin represented by formula (IV) can be used without isolation or purification or the organohydrogenpolysiloxane resin can be separated from most of the organic solvent (d) by conventional methods of evaporation.
  • the reaction mixture can be heated under reduced pressure.
  • the hydrosilylation catalyst (c) is a supported catalyst, as described above, the organohydrogenpolysiloxane resin can be readily separated from the hydrosilylation catalyst (c) by filtering the reaction mixture.
  • the hydrosilylation catalyst may remain mixed with the organohydrogenpolysiloxane resin and be used as hydrosilylation catalyst (C).
  • the cross-linking agent (B) can be a single organosilicon compound or a mixture comprising two or more different organosilicon compounds, each as described above.
  • the cross-linking agent (B) can be a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or a mixture of an organohydrogensilane and an organohydrogensiloxane.
  • the cross-linking agent (B) can be a mixture comprising the organohydrogenpolysiloxane resin having the formula (IV) in an amount of at least 0.5% (w/w), alternatively at least 50% (w/w), alternatively at least 75% (w/w), based on the total weight of the cross-linking agent (B), with the cross-linking agent (B) further comprising an organohydrogensilane and/or organohydrogensiloxane, the latter different from the organohydrogenpolysiloxane resin.
  • the concentration of cross-linking agent (B) is sufficient to cure (crosslink) the silicone resin (A).
  • the exact amount of cross-linking agent (B) depends on the desired extent of cure.
  • the concentration of cross-linking agent (B) is typically sufficient to provide from 0.4 to 2 moles of silicon-bonded hydrogen atoms, alternatively from 0.8 to 1.5 moles of silicon-bonded hydrogen atoms, alternatively from 0.9 to 1.1 moles of silicon- bonded hydrogen atoms, per mole of alkenyl groups in silicone resin (A).
  • Hydrosilylation catalyst (C) includes at least one hydrosilylation catalyst that promotes the reaction between silicone resin (A) and cross-linking agent (B).
  • the hydrosilylation catalyst (C) may be the same as the hydrosilylation catalyst (c) described above for producing the organohydrogenpolysiloxane resin.
  • the hydrosilylation catalyst (C) can also be a microencapsulated platinum group metal- containing catalyst comprising a platinum group metal encapsulated in a thermoplastic resin.
  • Hydrosilylation-curable silicone compositions including microencapsulated hydrosilylation catalysts are stable for extended periods of time, typically several months or longer, under ambient conditions, yet cure relatively rapidly at temperatures above the melting or softening point of the thermoplastic resin(s).
  • Microencapsulated hydrosilylation catalysts and methods of preparing them are well known in the art, as exemplified in U.S. Pat. No. 4,766,176 and the references cited therein, and U.S. Pat. No. 5,017,654.
  • the hydrosilylation catalyst (C) can be a single catalyst or a mixture comprising two or more different catalysts that differ in at least one property, such as structure, form, platinum group metal, complexing ligand and thermoplastic resin.
  • the hydrosilylation catalyst (C) may be at least one photoactivated hydrosilylation catalyst.
  • the photoactivated hydrosilylation catalyst can be any hydrosilylation catalyst capable of catalyzing the hydrosilylation of the silicone resin (A) and the cross-linking agent (B) upon exposure to radiation having a wavelength of from 150 to 800 nm.
  • the photoactivated hydrosilylation catalyst can be any of the well-known hydrosilylation catalysts comprising a platinum group metal or a compound containing a platinum group metal.
  • the platinum group metals include platinum, rhodium, ruthenium, palladium, osmium and indium. Typically, the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
  • the suitability of particular photoactivated hydrosilylation catalysts for use in the silicone composition of the present invention can be readily determined by routine experimentation.
  • Suitable photoactivated hydrosilylation catalysts include, but are not limited to, platinum(II) ⁇ -diketonate complexes such as platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4- heptanedioate), platinum(II) bis(l -phenyl- 1, 3 -butanedioate, platinum(II) bis(l,3-diphenyl- 1,3-propanedioate), platinum(II) bis(l,l,l,5,5,5-hexafluoro-2,4-pentanedioate); ( ⁇ - cyclopentadienyl)trialkylplatinum complexes, such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (Cp)trie
  • the photoactivated hydrosilylation catalyst is a Pt(II) ⁇ -diketonate complex and more typically the catalyst is platinum(II) bis(2,4-pentanedioate).
  • the hydrosilylation catalyst (C) can be a single photoactivated hydrosilylation catalyst or a mixture comprising two or more different photoactivated hydrosilylation catalysts.
  • the concentration of the hydrosilylation catalyst (C) is sufficient to catalyze the addition reaction of the silicone resin (A) and the cross-linking agent (B).
  • the concentration of the hydrosilylation catalyst (C) is sufficient to provide typically from 0.1 to 1000 ppm of platinum group metal, alternatively from 0.5 to 100 ppm of platinum group metal, alternatively from 1 to 25 ppm of platinum group metal, based on the combined weight of the silicone resin (A) and the cross-linking agent (B).
  • the hydrosilylation-curable silicone composition further includes (D) a silicone rubber having a formula selected from the group of (i)
  • R 1 R 2 2 SiO(R 2 2 SiO) a SiR 2 2 R 1 and (ii) R 5 R ⁇ SiO(R 1 R 5 SiO ⁇ SiR 1 2 R 5 ; wherein R 1 and
  • R 2 are as defined and exemplified above, R ⁇ is R ⁇ or -H, subscripts a and b each have a value of from 1 to 4, alternatively from 2 to 4, alternatively from 2 to 3, and w, x, y, and z are also as defined and exemplified above, provided the silicone resin and the silicone rubber (D)(i) each have an average of at least two silicon-bonded alkenyl groups per molecule, the silicone rubber (D)(U) has an average of at least two silicon-bonded hydrogen atoms per molecule, and the mole ratio of silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the silicone rubber (D) to silicon-bonded alkenyl groups in the silicone resin (A) is from 0.01 to 0.5.
  • silicone rubbers suitable for use as component (D)(i) include, but are not limited to, silicone rubbers having the following formulae: ViMe 2 SiO(Me 2 SiCOaSiMe 2 Vi, ViMe 2 Si0(Ph 2 Si0) a SiMe 2 Vi and ViMe 2 SiO(PhMeSiO) a
  • Silicone rubber (D)(i) can be a single silicone rubber or a mixture comprising two or more different silicone rubbers that each satisfy the formula for (D)(i). [0136] Specific examples of silicone rubbers suitable for use as silicone rubber
  • (D)(U) include, but are not limited to, silicone rubbers having the following formulae: HMe 2 SiO(Me 2 SiCObSiMe 2 H, HMe 2 SiO(Ph 2 SiO) ⁇ SiMe 2 H, HMe 2 SiO(PhMeSiO)b
  • Component (D)(U) can be a single silicone rubber or a mixture comprising two or more different silicone rubbers that each satisfy the formula for (D)(U).
  • the mole ratio of silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the silicone rubber (D) to silicon-bonded alkenyl groups in the silicone resin (A) is typically from 0.01 to 0.5, alternatively from 0.05 to 0.4, alternatively from 0.1 to 0.3.
  • the concentration of the cross- linking agent (B) is such that the ratio of the number of moles of silicon-bonded hydrogen atoms in the cross-linking agent (B) to the sum of the number of moles of silicon-bonded alkenyl groups in the silicone resin (A) and the silicone rubber (D)(i) is typically from 0.4 to 2, alternatively from 0.8 to 1.5, alternatively from 0.9 to 1.1.
  • the concentration of the cross-linking agent (B) is such that the ratio of the sum of the number of moles of silicon-bonded hydrogen atoms in the cross- linking agent (B) and the silicone rubber (D)(U) to the number of moles of silicon-bonded alkenyl groups in the silicone resin (A) is typically from 0.4 to 2, alternatively from 0.8 to 1.5, alternatively from 0.9 to 1.1.
  • the hydrosilylation-curable silicone composition comprises (A ⁇ ) a rubber-modified silicone resin prepared by reacting the silicone resin (A) and at least one silicone rubber (D)(Ui) selected from rubbers having the following formulae: R 1 R 2 2SiO(R 2 2SiO)dSiR 2 2 R 1 , wherein R* and R ⁇ are as defined and exemplified above and c and d each have a value of from 4 to 1000, alternatively from 10 to 500, alternatively from 10 to 50, in the presence of the hydrosilylation catalyst (c) and, optionally, an organic solvent, provided the silicone resin (A) has an average of at least two silicon-bonded alkenyl groups per molecule, the silicone rubber (D)(Ui) has an average of at least two silicon-bonded hydrogen atom
  • the rubber-modified silicone resin (A ⁇ ) is miscible in the organic solvent and does not form a precipitate or suspension.
  • silicone resin (A), silicone rubber (D)(Ui), hydrosilylation catalyst (c), and organic solvent can be combined in any order.
  • silicone resin (A), silicone rubber (D)(Ui) and organic solvent are combined before the introduction of the hydrosilylation catalyst (c).
  • the reaction is typically carried out at a temperature of from room temperature (-23 ⁇ 2 0 C) to 150 0 C, alternatively from room temperature to 100 0 C.
  • the reaction time depends on several factors, including the structures of the silicone resin (A) and the silicone rubber (D)(Ui) and the temperature.
  • the components are typically allowed to react for a period of time sufficient to complete the hydrosilylation reaction. This means the components are typically allowed to react until at least 95 mol%, alternatively at least 98 mol%, alternatively at least 99 mol%, of the silicon-bonded hydrogen atoms originally present in the silicone rubber (D)(Ui) have been consumed in the hydrosilylation reaction, as determined by FTIR spectrometry.
  • the time of reaction is typically from 0.5 to 24 h at a temperature of from room temperature (-23 ⁇ 2 0 C) to 100 0 C.
  • the optimum reaction time can be determined by routine experimentation.
  • the mole ratio of silicon-bonded hydrogen atoms in the silicone rubber (D)(Ui) to silicon-bonded alkenyl groups in the silicone resin (A) is typically from 0.01 to 0.5, alternatively from 0.05 to 0.4, alternatively from 0.1 to 0.3.
  • the concentration of the hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction of the silicone resin (A) with the silicone rubber (D)(Ui).
  • the concentration of the hydrosilylation catalyst (c) is sufficient to provide from 0.1 to 1000 ppm of a platinum group metal, based on the combined weight of the resin and the rubber.
  • the concentration of the organic solvent is typically from 0 to 95% (w/w), alternatively from 10 to 75% (w/w), alternatively from 40 to 60% (w/w), based on the total weight of the reaction mixture.
  • the rubber-modified silicone resin (A ⁇ ) can be used without isolation or purification, or the rubber-modified silicone resin (A ⁇ ) can be separated from most of the solvent by conventional methods of evaporation.
  • the reaction mixture can be heated under reduced pressure.
  • the hydrosilylation catalyst (c) is a supported catalyst, described above, the rubber-modified silicone resin (A*) can be readily separated from the hydrosilylation catalyst (c) by filtering the reaction mixture.
  • the hydrosilylation catalyst (c) may be used as the hydrosilylation catalyst (C).
  • the hydrosilylation-curable silicone composition of the present invention can comprise additional ingredients, as known in the art.
  • additional ingredients include, but are not limited to, hydrosilylation catalyst inhibitors, such as 3- methyl-3-penten-l-yne, 3,5-dimethyl-3-hexen-l-yne, 3,5-dimethyl-l-hexyn-3-ol, 1-ethynyl- 1-cyclohexanol, 2-phenyl-3-butyn-2-ol, vinylcyclosiloxanes and triphenylphosphine; adhesion promoters, such as the adhesion promoters taught in U.S. Patent Nos.
  • condensation-curable silicone compositions are also suitable for use as the base material in embodiments.
  • the condensation-curable silicone composition typically includes a silicone resin (A ⁇ ) having silicon-bonded hydrogen atoms, silicon-bonded hydroxy groups, or silicon-bonded hydrolysable groups, optionally, a cross-linking agent (B ⁇ ) having silicon-bonded hydrolysable groups and, optionally, a condensation catalyst (C ⁇ ).
  • the condensation curable silicone resin (A ⁇ ) is typically a copolymer comprising R ⁇ SiC>3/2 units, i.e., T units and/or SiC>4/2 units, i.e., Q units, in combination with RlR ⁇ 2 SiO 1 /2 units, i.e., M units and/or R62Si ⁇ 2/2 units, i.e., D units, wherein R ⁇ is set forth above, R" is
  • the silicone resin can be a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.
  • the silicone resin (A ⁇ ) has the formula:
  • x' is from 0 to 0.95, alternatively from 0.05 to 0.8, alternatively from 0.1 to 0.3, y' is from 0 to 1, alternatively from 0.25 to 0.8, alternatively from 0.5 to 0.8 and z' is from 0 to 0.99, alternatively from 0.2 to 0.8, alternatively from 0.4 to
  • the silicone resin (A ⁇ ) has an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule.
  • hydrolysable group means the silicon-bonded group reacts with water in the absence of a catalyst at any temperature from room temperature ( ⁇ 23 ⁇ 2 0 C) to 100 0 C within several minutes, for example thirty minutes, to form a silanol (Si-OH) group.
  • Examples of hydrolysable groups represented by R 6 include, but are not limited to, -Cl, -Br, -OR 7 , -OCH 2 CH 2 OR 7 ,
  • R 7 is C 1 to C 8 hydrocarbyl or C 1 to Cg halogen-substituted hydrocarbyl.
  • the hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R 7 typically have from 1 to 8 carbon atoms, alternatively from 3 to 6 carbon atoms.
  • Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
  • hydrocarbyl groups represented by R 7 include, but are not limited to, unbranched and branched alkyl, such as methyl, ethyl, propyl, 1 -methyl ethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1,1- dimethylethyl, pentyl, 1 -methylbutyl, 1 -ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2- dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl and octyl; cycloalkyl, such as cyclopentyl, cyclohexyl and methylcyclohexyl; phenyl; alkaryl, such as tolyl and xylyl; aralkyl, such as benzyl and phenethyl; alkenyl, such as vinyl, allyl and propenyl; arylalkenyl,
  • the groups R ⁇ in the silicone resin (A ⁇ ) are hydrogen, hydroxy, or a hydrolysable group.
  • the mol% of groups in R ⁇ is defined as a ratio of the number of moles of silicon-bonded groups in the silicone resin (A ⁇ ) to the total number of moles of the R ⁇ groups in the silicone resin (A ⁇ ), multiplied by 100.
  • cured silicone resins formed from silicone resin (A ⁇ ) include, but are not limited to, cured silicone resins having the following formulae: (MeSiO 3 /2)0.9(Me(HO)SiO 2 /2)0.1» (PhSi0 3/2 )o.7(Ph(MeO)Si0 2/2 )o. 3 ,
  • the silicone resin (A ⁇ ) represented by formula (V) typically has a number-average molecular weight (M n ) of from 500 to 50,000.
  • the silicone resin (A ⁇ ) may have a M n of at least 300, alternatively 1,000 to
  • the viscosity of the silicone resin (A ⁇ ) at 25 0 C is typically from 0.01 Pa-s to solid, alternatively from 0.1 to 100,000 Pa-s, alternatively from 1 to 1,000 Pa-s.
  • the silicone resin (A ⁇ ) can have the same formula (V) as set forth above, but with different values for the subscripts x and z and with the proviso that the sum of R°Si ⁇ 3/2 units and SiC>4/2 units is greater than zero and with the further proviso that the silicone resin (A ⁇ ) of the second embodiment contains at least two silicon-bonded hydrogen atoms, at least two silicon-bonded hydroxy groups, or at least two silicon-bonded hydrolysable groups per molecule.
  • x' typically has a value of from 0 to 0.6, alternatively from 0 to 0.45, alternatively from 0 to 0.25
  • z' typically has a value of from 0 to 0.35, alternatively from 0 to 0.25, alternatively from 0 to 0.15
  • the sum of y'+z' is greater than zero and is typically from 0.2 to 0.99, alternatively from 0.5 to 0.95, alternatively from 0.65 to 0.9.
  • the sum of w'+x' can be zero but is typically from 0.01 to 0.80, alternatively from 0.05 to 0.5, alternatively from 0.1 to 0.35.
  • 1 mol% to 30 mol%, alternatively 1 to 15 mol%, of the R 6 groups in the silicone resin (A ⁇ ) of the second embodiment are hydrogen, hydroxy, or a hydrolysable group.
  • condensation curable silicone resins (A ⁇ ) of the second embodiment include, but are not limited to, silicone resins having the following formulae: (Me(MeO)Si2/2) ⁇ '(MeSi ⁇ 3/2)y, (Ph(HO)SiO 2 /2) ⁇ PhSi ⁇ 3/2)y, (Me3SiO 1 / 2 ) w .(CH3COOSiO 3 /2)y-(Si ⁇ 4/2) z -, (Ph(MeO)SiO 2 /2) ⁇ '(MeSiO 3 /2)y(PhSi ⁇ 3/2) y ⁇ ,
  • condensation curable silicone resins (A 2 ) of the second embodiment include, but are not limited to, silicone resins having the following formulae:
  • the condensation curable silicone resin (A 2 ) of the second embodiment typically has a number-average molecular weight (M n ) of from 500 to 50,000.
  • the condensation curable silicone resin (A) may have a M n of from
  • the viscosity of the condensation curable silicone resin (A 2 ) of the second embodiment at 25 0 C is typically from 0.01 Pa-s to a solid, alternatively from 0.1 to 10,000 Pa-s, alternatively from 1 to 100 Pa-s.
  • the condensation curable silicone resin (A) represented by formula (V) typically includes less than 20% (w/w), alternatively less than 10% (w/w), alternatively less than 2% (w/w), of silicon-bonded hydroxy groups, as determined by 29 Si NMR.
  • Methods of preparing silicone resins (A 2 ) represented by formula (V) are well known in the art; many of these resins are commercially available. Silicone resins
  • (A 2 ) represented by formula (V) are typically prepared by cohydrolyzing the appropriate mixture of chlorosilane precursors in an organic solvent, such as toluene.
  • a silicone resin including R ⁇ R ⁇ SiOi /2 units and R ⁇ SiC ⁇ units can be prepared by cohydrolyzing a first compound having the formula R ⁇ R ⁇ SiCl and a second compound having the formula R ⁇ SiC ⁇ in toluene, where R* and R ⁇ are as defined and exemplified above.
  • the cohydrolyzing process is described above in terms of the hydrosilylation- curable silicone composition.
  • the cohydrolyzed reactants can be further "bodied” to a desired extent to control the amount of crosslinkable groups and viscosity.
  • the silicone resins (A ⁇ ) represented by formula (V) can be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups.
  • N(CH3)2, NHCOCH3 and -SCH3, can be co-hydrolyzed to form the silicone resin (A ⁇ ).
  • the properties of the silicone resin (A ⁇ ) depend on the types of first and second compounds, the mole ratio of first and second compounds, the degree of condensation, and the processing conditions.
  • the Q units in formula (V) can be in the form of discrete particles in the silicone resin (A ⁇ ).
  • the particle size is typically from 1 nm to 20 ⁇ m. Examples of these particles include, but are not limited to, silica (SiC>4/2) particles of 15 nm in diameter.
  • the condensation-curable silicone composition comprises a rubber-modified silicone resin (A ⁇ ) prepared by reacting an organosilicon compound selected from (i) a silicone resin having the formula
  • Silicone resin (i) has an average of at least two silicon-bonded hydroxy or hydrolysable groups per molecule.
  • the silicone rubber (iii) has an average of at least two silicon-bonded hydrolysable groups per molecule.
  • the mole ratio of silicon- bonded hydrolysable groups in the silicone rubber (iii) to silicon-bonded hydroxy or hydrolysable groups in the silicone resin (i) is from 0.01 to 1.5, alternatively from 0.05 to 0.8, alternatively from 0.2 to 0.5.
  • typically at least 1 mol%, alternatively at least 5 mol%, alternatively at least 10 mol% of the groups R ⁇ in the silicone resin (i) are hydroxy or hydrolysable groups.
  • typically 1 mol% to 30 mol%, or alternatively 1 to 15 mol% of the groups R ⁇ in the silicone resin (i) are hydrogen, hydroxy, or a hydrolysable group.
  • the silicone resin (i) of the first embodiment typically has a number- average molecular weight (M n ) of at least 300, alternatively from 500 to 50,000, alternatively from 800 to 3,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector, or a refractive index detector and silicone resin (MQ) standards.
  • M n number- average molecular weight
  • silicone resins suitable for use as silicone resin (i) include, but are not limited to, resins having the following formulae: (Me(MeO)Si2/2) x '(MeSi ⁇ 3/2)y- 5 (Ph(HO)Si ⁇ 2/2) ⁇ '(PhSi ⁇ 3/2)y-, (Ph(MeO)Si ⁇ 2/2) ⁇ '(PhSi ⁇ 3/2)y ⁇ MeSi ⁇ 3/2)y ⁇ PhSi ⁇ 3/2)y'(PhMeSiO 2 /2) ⁇ ' and
  • silicone resins suitable for use as silicone resin (i) include, but are not limited to, resins having the following formulae: (Ph(HO)SiO 2 /2)0.03(PhSi ⁇ 3/2)0.37(MeSi ⁇ 3/2)0.45(PhSiO 3 /2)0.l(PhMeSi ⁇ 2/2)0.05 and
  • Silicone resin (i) can be a single silicone resin or a mixture comprising two or more different silicone resins, each having the specified formula. Silicone resin (i) can be a single silicone resin or a mixture comprising two or more different silicone resins, each having the specified formula.
  • hydrolysable precursors refers to silanes having hydrolysable groups that are suitable for use as starting materials (precursors) for preparation of the silicone resin (i).
  • the hydrolysable precursors (ii) can be represented by the formulae R 1 RS 2 SiX, R 8 2 SiX 2 , R 8 SiX 3 and SiX 4 , wherein R 1 , R 8 and X are as defined and exemplified above.
  • Specific examples of hydrolysable precursors (ii) include, but are not limited to, silanes having the formulae:
  • silicone rubbers (iii) include, but are not limited to, silicone rubbers having the following formulae: (EtO) 3 SiO(Me 2 SiO) 55 Si(OEt) 3 , (EtO) 3 SiO(Me 2 SiO) 16 Si(OEt) 3 ,
  • the reaction is typically carried out at a temperature of from room temperature (-23 ⁇ 2 0 C) to 180°C, alternatively from room temperature to 100 0 C.
  • the reaction time depends on several factors, including the structures of the silicone resin (i) and the silicone rubber (iii), and the temperature.
  • the components are typically allowed to react for a period of time sufficient to complete the condensation reaction. This means the components are allowed to react until at least 40 mol%, alternatively at least 65 mol%, alternatively at least 90 mol%, of the silicon-bonded hydrolysable groups originally present in the silicone rubber (iii) have been consumed in the condensation reaction, as determined by 29si NMR spectrometry.
  • the time of reaction is typically from 1 to 30 h at a temperature of from room temperature (-23 ⁇ 2 0 C) to 100 °C. The optimum reaction time can be determined by routine experimentation.
  • Suitable condensation catalysts (iv) are described in further detail below, and suitable organic solvents (v) are described above in the context of rubber-modified silicone resin (A ⁇ ) above.
  • the concentration of the condensation catalyst (iv) is sufficient to catalyze the condensation reaction of the silicone resin (i) with the silicone rubber (iii).
  • the concentration of the condensation catalyst (iv) is from 0.01 to 5% (w/w), alternatively from 0.01 to 3% (w/w), alternatively from 0.05 to 2.5% (w/w), based on the weight of the silicon resin (i).
  • the concentration of the organic solvent (v) is typically from 10 to 95% (w/w), alternatively from 20 to 85% (w/w), alternatively from 50 to 80% (w/w), based on the total weight of the reaction mixture.
  • the concentration of water in the reaction mixture depends on the nature of the groups R ⁇ in the organosilicon compound and the nature of the silicon-bonded hydrolysable groups in the silicone rubber.
  • the concentration of water is sufficient to effect hydrolysis of the hydrolysable groups in the silicon resin (i) and the silicone rubber (iii).
  • the concentration of water is typically from 0.01 to 3 moles, alternatively from 0.05 to 1 moles, per mole of hydrolysable groups in the silicone resin (i) and the silicone rubber (iii) combined.
  • the silicone resin (i) does not contain hydrolysable groups, only a trace amount, e.g., 100 ppm, of water is typically present in the reaction mixture. Trace amounts of water are normally present in the reactants and/or solvent.
  • the condensation-curable silicone composition can further comprise the cross-linking agent (B 1).
  • the cross-linking agent (B ⁇ ) can have the formula wherein R7 is Cj to Cg hydrocarbyl or Cj to Cg halogen-substituted hydrocarbyl, X is a hydrolysable group, and q is 0 or 1.
  • R7 is Cj to Cg hydrocarbyl or Cj to Cg halogen-substituted hydrocarbyl
  • X is a hydrolysable group
  • q is 0 or 1.
  • the hydrocarbyl and halogen- substituted hydrocarbyl groups represented by R7, and the hydrolysable groups represented by X are as described and exemplified above.
  • cross-linking agents (B ⁇ ) include, but are not limited to, alkoxy silanes such as MeSi(OCH 3 ) 3 , CH 3 Si(OCH 2 CH3)3, CH 3 Si(OCH 2 CH 2 CH 3 )S,
  • the cross-linking agent (B 1) can be a single silane or a mixture of two or more different silanes, each as described above. Also, methods of preparing tri- and tetra- functional silanes are well known in the art; many of these silanes are commercially available. [0180] When present, the concentration of the cross-linking agent (B ⁇ ) in the condensation-curable silicone composition is sufficient to cure (cross-link) the condensation-curable silicone resin.
  • the exact amount of the cross-linking agent (B 1) depends on the desired extent of cure, which generally increases as the ratio of the number of moles of silicon-bonded hydrolysable groups in the cross-linking agent (B ⁇ ) to the number of moles of silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups in the silicone resin (A ⁇ ) increases.
  • the concentration of the cross-linking agent (B 1) is sufficient to provide from 0.2 to 4 moles of silicon-bonded hydrolysable groups per mole of silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups in the silicone resin (A ⁇ ).
  • the optimum amount of the cross-linking agent (B 1) can be readily determined by routine experimentation.
  • Condensation catalyst (C ⁇ ) can be any condensation catalyst typically used to promote condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si linkages.
  • condensation catalysts include, but are not limited to, amines; and complexes of lead, tin, zinc and iron with carboxylic acids.
  • the condensation catalyst (C 1) can be selected from tin(II) and tin(IV) compounds such as tin dilaurate, tin dioctoate and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide.
  • the concentration of the condensation catalyst (C ⁇ ) is typically from 0.1 to 10% (w/w), alternatively from 0.5 to 5% (w/w), alternatively from 1 to 3% (w/w), based on the total weight of the silicone resin (A ⁇ ).
  • the condensation-curable silicone composition includes the condensation catalyst (C ⁇ )
  • the condensation-curable silicone composition is typically a two-part composition where the silicone resin (A ⁇ ) and condensation catalyst (C ⁇ ) are in separate parts.
  • the condensation-curable silicone composition can further contain inorganic fillers in particulate form, such as silica, alumina, calcium carbonate and mica.
  • the condensation-curable silicone composition further includes silica nanoparticles. The nanoparticles may help reduce the coefficient of thermal expansion of a reinforced substrate formed of the silicone composition. A low coefficient of thermal expansion may improve manufacturability of CIS-based photovoltaic devices. Nanoparticles may also increase mechanical strength of a substrate formed of the silicone composition.
  • the silica nanoparticles can be any silica material having at least one physical dimension (e.g., particle diameter, layer thickness) less than about 200 nm.
  • One particularly useful form of silica nanoparticles are fumed silica nanoparticles.
  • Examples of useful commercially available unmodified silica starting materials include nano-sized colloidal silicas available under the product designations NALCO 1040, 1042, 1050, 1060, 2326, 2327 and 2329 colloidal silica from Nalco Chemical Co., Naperville, Illinois, Aerosil® from Degussa, Ludox® from DuPont, Snowtex® from Nissan Chemical, Levasil® from Bayer, or Sylysia® from Fuji Silysia Chemical.
  • Suitable fumed silicas include for example, products commercially available from DeGussa AG, (Hanau, Germany) under the trade designation, "Aerosil series OX 50", as well as product numbers- 130,-150 and -200. Fumed silicas are also commercially available from Cabot Corp., Tuscola, I, under the Bade designations CAB O-SPERSE 2095", “CAB-O-SPERSE A105" and "CAB-O-SIL M5".
  • the silica nanoparticles may be in the form of a colloidal dispersion.
  • the silica nanoparticles thus may be dispersed in a polar solvent such as methanol, ethanol, isopropyl alcohol (IPA), ketones such as methyl isobutyl ketone, water, acetic acid, diols and trials such as propylene glycol, 2-methyl-l,3-propane diol HOCH2CH(CH3)CH2OH, 1,2-hexanediol CH3(CH2)3CH(OH)CH2OH and glycerol; glycerol esters such as glyceryl triacetate (triacetin), glyceryl tripropionate (tripropionin) and glyceryl tributyrate (tributyrin); and polyglycols such as polyethylene glycols and polypropylene glycols, among which are PPG- 14 butyl ether C4Hg(OCH(CH3)
  • the silica particle size typically ranges from 1 to 1000 nm, or alternatively from 1 to 100 nm, or alternatively from 5 to 30 nm.
  • the silica nanoparticles can be a single type of silica nanoparticles or a mixture comprising at least two different types of silica nanoparticles. It is known that silica nanoparticles may be of pure silicon dioxide, or they may contain a certain amount of impurities such as AI2O3, ZnO and/or cations such as Na + ,
  • the concentration of the silica nanoparticles is typically from 0.0001 to 99 wt%, alternatively from 0.001 to 75 wt%, alternatively from 10 to 65 wt%, alternatively from 5 to 50 wt%, alternatively from 20 to 40 wt%, based on the total weight of the condensation-curable silicone composition.
  • the condensation-curable silicone composition can be a one-part composition comprising the condensation-curable silicone resin (A ⁇ or
  • a ⁇ A ⁇ and any optional ingredients, and silica nanoparticles in a single part or, alternatively, a multi-part composition comprising these components in two or more parts.
  • the one-part condensation-curable silicone composition can be prepared by combining the condensation curable silicone resin (A ⁇ or A ⁇ ), the silica nanoparticles and any optional ingredients in the stated proportions at ambient temperature, with or without the aid of an organic solvent. Also, the silicone composition can be prepared by combining the components in each part.
  • the condensation-curable silicone compositions including the silica nanoparticles can also be prepared in-situ, i.e., the silica nanoparticles can be added during the process to manufacture the condensation-curable silicone resin (A ⁇ or A ⁇ ) described above. Mixing can be accomplished by any of the techniques known in the art such as milling, blending and stirring, either in a batch or continuous process.
  • the condensation-curable silicone composition can comprise additional ingredients, as known in the art and as described above for the hydrosilylation-curable silicone composition.
  • the silicone composition may be a free radical- curable silicone composition.
  • free radical-curable silicone compositions include peroxide-curable silicone compositions, radiation-curable silicone compositions containing a free radical photoinitiator, and high energy radiation-curable silicone compositions.
  • the free radical-curable silicone composition comprises a silicone resin (A ⁇ ) and, optionally, a cross-linking agent (B ⁇ ) and/or a free radical initiator (C ⁇ ) (e.g., a free radical photoinitiator or organic peroxide).
  • the silicone resin (A ⁇ ) can be any silicone resin that can be cured (i.e., cross-linked) by at least one method selected from (i) exposing the silicone resin to radiation having a wavelength of from 150 to 800 nm in the presence of a free radical photoinitiator, (ii) heating the silicone resin (A ⁇ ) in the presence of an organic peroxide and (iii) exposing the silicone resin (A ⁇ ) to an electron beam.
  • the silicone resin (A ⁇ ) is typically a copolymer containing T siloxane units and/or Q siloxane units in combination with M and/or D siloxane units.
  • R 9 The alkenyl groups represented by R 9 , which may be the same or different, are as defined and exemplified in the description of R 2 above.
  • the alkynyl groups represented by R 9 typically have from 2 to about 10 carbon atoms, alternatively from 2 to 6 carbon atoms, and are exemplified by, but are not limited to, ethynyl, propynyl, butynyl, hexynyl and octynyl.
  • the silicone resin (A ⁇ ) typically has a number-average molecular weight (M n ) of at least 300, alternatively from 500 to 10,000, alternatively from 1,000 to 3,000, where the molecular weight is determined by gel permeation chromatography employing a refractive index detector and silicone resin (MQ) standards.
  • M n number-average molecular weight
  • the silicone resin (A ⁇ ) can contain less than 10% (w/w), alternatively less than 5% (w/w), alternatively less than 2% (w/w), of silicon-bonded hydroxy groups, as determined by 29 Si NMR.
  • Specific examples of silicone resins (A ⁇ ) that are suitable for purposes of the present invention include, but are not limited to, silicone resins having the following formulae:
  • the free radical-curable silicone composition of the present method can comprise additional ingredients including, but not limited to, silicone rubbers; unsaturated compounds; free radical initiators; organic solvents; UV stabilizers; sensitizers; dyes; flame retardants; antioxidants; fillers, such as reinforcing fillers, extending fillers and conductive fillers; and adhesion promoters.
  • the free radical-curable silicone composition can further comprise an unsaturated compound selected from (i) at least one organosilicon compound having at least one silicon-bonded alkenyl group per molecule, (ii) at least one organic compound having at least one aliphatic carbon-carbon double bond per molecule, and (iii) mixtures comprising (i) and (ii), wherein the unsaturated compound has a molecular weight less than 500. Alternatively, the unsaturated compound has a molecular weight of less than 400 or less than 300. Also, the unsaturated compound can have a linear, branched, or cyclic structure.
  • the organosilicon compound (i) can be an organosilane or an organosiloxane.
  • the organosilane can be a monosilane, disilane, trisilane, or polysilane.
  • the organosiloxane can be a disiloxane, trisiloxane, or polysiloxane.
  • Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.
  • the silicon-bonded alkenyl group(s) can be located at terminal, pendant, or at both terminal and pendant positions.
  • organosiloxanes include, but are not limited to, siloxanes having the following formulae: PhSi(OSiMe 2 Vi) 3 , Si(OSiMe 2 Vi) 4 , MeSi(OSiMe 2 Vi) 3 and Ph 2 Si(OSiMe 2 Vi) 2 , wherein Me is methyl, Vi is vinyl and Ph is phenyl.
  • the organic compound can be any organic compound containing at least one aliphatic carbon-carbon double bond per molecule, provided the compound does not prevent the silicone resin (A ⁇ ) from curing to form a silicone resin film.
  • the organic compound can be an alkene, a diene, a triene, or a polyene. Further, in acyclic organic compounds, the carbon-carbon double bond(s) can be located at terminal, pendant, or at both terminal and pendant positions.
  • the organic compound can contain one or more functional groups other than the aliphatic carbon-carbon double bond.
  • the suitability of a particular unsaturated organic compound for use in the free-radical curable silicone composition of the present invention can be readily determined by routine experimentation.
  • the organic compound can be in a liquid or solid state at room temperature. Also, the organic compound can be soluble, partially soluble, or insoluble in the free-radical curable silicone composition.
  • the normal boiling point of the organic compound which depends on the molecular weight, structure and number and nature of functional groups in the compound, can vary over a wide range. Typically, the organic compound has a normal boiling point greater than the cure temperature of the composition. Otherwise, appreciable amounts of the organic compound may be removed by volatilization during cure.
  • Examples of organic compounds containing aliphatic carbon-carbon double bonds include, but are not limited to, 1,4-divinylbenzene, 1,3-hexadienylbenzene and 1 ,2-diethenylcyclobutane.
  • the unsaturated compound can be a single unsaturated compound or a mixture comprising two or more different unsaturated compounds, each as described above.
  • the unsaturated compound can be a single organosilane, a mixture of two different organosilanes, a single organosiloxane, a mixture of two different organosiloxanes, a mixture of an organosilane and an organosiloxane, a single organic compound, a mixture of two different organic compounds, a mixture of an organosilane and an organic compound, or a mixture of an organosiloxane and an organic compound.
  • the concentration of the unsaturated compound is typically from 0 to 70%
  • the free radical initiator is typically a free radical photoinitiator or an organic peroxide. Further, the free radical photoinitiator can be any free radical photoinitiator capable of initiating cure (cross-linking) of the silicone resin upon exposure to radiation having a wavelength of from 200 to 800 nm.
  • free radical photoinitiators include, but are not limited to, benzophenone; 4,4'-bis(dimethylamino)benzophenone; halogenated benzophenones; acetophenone; ⁇ -hydroxyacetophenone; chloro acetophenones, such as dichloroacetophenones and trichloroacetophenones; dialkoxyacetophenones, such as 2,2- diethoxyacetophenone; ⁇ -hydoxyalkylphenones, such as 2-hydroxy-2-methyl-l -phenyl- 1- propanone and 1-hydroxycyclohexyl phenyl ketone; ⁇ -aminoalkylphenones, such as 2- methyl-4'-(methylthio)-2-morpholiniopropiophenone; benzoin; benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether and benzoin isobutyl ether; benzil
  • the free radical photoinitiator can also be a polysilane, such as the phenylmethylpolysilanes defined by West in U.S. Pat. No. 4,260,780, the disclosure of which as it relates to the phenylmethylpolysilanes is hereby incorporated by reference; the aminated methylpolysilanes defined by Baney et al. in U.S. Pat. No. 4,314,956, the disclosure of which is hereby incorporated by reference as it relates to aminated methylpolysilanes; the methylpolysilanes defined by Peterson et al. in U.S. Pat. No.
  • the free radical photoinitiator can be a single free radical photoinitiator or a mixture comprising two or more different free radical photoinitiators.
  • the concentration of the free radical photoinitiator is typically from 0.1 to 6% (w/w), alternatively from 1 to
  • the free radical initiator can also be an organic peroxide.
  • organic peroxides include, diaroyl peroxides such as dibenzoyl peroxide, di-p- chlorobenzoyl peroxide and bis-2,4-dichlorobenzoyl peroxide; dialkyl peroxides such as di- t-butyl peroxide and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane; diaralkyl peroxides such as dicumyl peroxide; alkyl aralkyl peroxides such as t-butyl cumyl peroxide and 1 ,4-bis(t- butylperoxyisopropyl)benzene; and alkyl aroyl peroxides such as t-butyl perbenzoate, t- butyl peracetate and t-butyl peroctoate.
  • the organic peroxide can be a single peroxide or a mixture comprising two or more different organic peroxides.
  • concentration of the organic peroxide is typically from 0.1 to 5% (w/w), alternatively from 0.2 to 2% (w/w), based on the weight of the silicone resin (A ⁇ ).
  • the free radical-curable silicone composition can further comprise at least one organic solvent.
  • the organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with the silicone resin (A ⁇ ) or additional ingredient(s) and is miscible with the silicone resin (A ⁇ ).
  • organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • the organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, as described above.
  • the concentration of the organic solvent is typically from 0 to 99% (w/w), alternatively from 30 to 80% (w/w), alternatively from 45 to 60% (w/w), based on the total weight of the free radical-curable silicone composition.
  • the free-radical curable silicone composition described above contains one or more additional ingredients, for example, a free radical initiator
  • the composition can be a one-part composition comprising the silicone resin and optional ingredient(s) in a single part, or a multi-part composition comprising the components in two or more parts.
  • Another suitable silicone composition comprises cyclic dihydrogenpolysiloxanes, which have a weight-average molecular weight ranging in value from 1,500 to 1,000,000, are liquid at room temperature (-23 ⁇ 2 0 C), and comprise H2SiC>2/2 units.
  • the cyclic dihydrogenpolysiloxanes can be produced by subjecting dichlorosilane (H2S1CI2) to hydrolysis/condensation in a mixture of a non-polar organic solvent and water and removing volatile cyclic dihydrogenpolysiloxanes from the formed cyclic dihydrogenpolysiloxanes.
  • the non-polar organic solvents used herein are exemplified by aromatic hydrocarbon organic solvents and aliphatic hydrocarbon organic solvents, with the aromatic hydrocarbon organic solvents exemplified by toluene and xylene and the aliphatic hydrocarbon organic solvents exemplified by hexane, heptane, octane and cyclohexane.
  • the hydrolysis/condensation reaction is typically conducted via slow dropwise addition of a non-polar organic solvent solution of dichlorosilane while stirring the non-polar organic solvent and water.
  • the hydrolysis/condensation is typically conducted in a mixture of a non- polar organic solvent phase and an aqueous phase, followed by washing the non-polar organic solvent phase containing the formed cyclic dihydrogenpolysiloxane with water, drying it, and eluting the non-polar organic solvent and volatile cyclic dihydrogenpolysiloxanes.
  • the non-polar organic solvent layer is washed until it becomes neutral or until chlorine ions are no longer detected.
  • the non-polar organic solvent layer may also be washed to a certain extent and neutralized with a weak alkali, e.g. calcium carbonate, sodium carbonate, or sodium bicarbonate, followed by washing the formed salts with water.
  • the washed non-polar organic solvent layer may be dried and the non-polar organic solvent and volatile cyclic dihydrogenpolysiloxanes are typically eluted.
  • a powdered or granulated drying agent e.g. anhydrous magnesium sulfate, anhydrous sodium sulfate, or a molecular sieve
  • the resulting mixture is subjected to agitation, and the drying agent filtered off.
  • elution of the non-polar organic solvent and cyclic dihydrogenpolysiloxane so long as the cyclic dihydrogenpolysiloxanes are not altered.
  • Elution may be exemplified by heating under reduced pressure or blowing in dry nitrogen gas under heating.
  • the volatile cyclic dihydrogenpolysiloxanes mentioned herein are 3-mers ⁇ 15-mers.
  • the fact that the product is a cyclic dihydrogenpolysiloxane is ascertained by the absence of silanol group absorption when analyzed using FT-IR.
  • the cyclic dihydrogenpolysiloxanes can also be produced by subjecting dichlorosilane to co-hydrolysis/condensation in a mixture of the non-polar organic solvent, hydrochloric acid and an ionic surface active agent, and removing volatile cyclic dihydrogenpolysiloxanes from the formed dihydrogenpolysiloxanes as described above.
  • the hydrochloric acid is typically concentrated hydrochloric acid and, more typically, hydrochloric acid with a hydrogen chloride content of 15 wt% to 37 wt%.
  • the ionic surface active agents may include anionic surface active agents, cationic surface active agents and amphoteric surface active agents, with the anionic surface active agents exemplified by alkali metal salts of aliphatic hydrocarbon sulfonic acids, e.g. alkali metal salts of alkylsulfonic acids of 6 to 20 carbon atoms, alkali metal salts of alkenesulfonic acids of 6 to 20 carbon atoms and alkali metal salts of alkylbenzenesulfonic acids; aliphatic hydrocarbon sulfonic acids, e.g.
  • alkylsulfonic acids of 6 to 20 carbon atoms alkenesulfonic acids of 6 to 20 carbon atoms; alkylbenzenesulfonic acids; alkali metal salts of alkylsulfonic esters; and alkali metal salts of higher aliphatic acids.
  • Sodium and potassium are preferred as the alkali metals used herein.
  • the cationic surface active agents are exemplified by quaternary ammonium salts, e.g. tetramethylammonium chloride, benzyltributylammonium chloride, cetyltrimethylammonium chloride and tetrabutyl ammonium chloride; and by alkylamine hydrochlorides, e.g. decylamine hydrochloride.
  • the ionic surface active agents are typically used in an amount of from 0.01-50 wt%, more typically from 0.1-1.0 wt%, of the water contained in the hydrochloric acid.
  • the hydrolysis/condensation reaction is carried out via dropwise addition of the non-polar organic solvent solution containing dichlorosilane to a mixture including the non-polar organic solvent, hydrochloric acid and the ionic surface active agent.
  • agitation is continued during the dropwise addition.
  • the hydrolysis/condensation reaction typically occurs at a temperature of not more than 5 0 C in order to prevent volatilization of the dichlorosilane.
  • the hydrogenpolysiloxanes typically have a weight-average molecular weight ranging in value from 500 to 1,000,000 and are liquid at temperatures of 12O 0 C or less.
  • the hydrogenpolysiloxanes have the above-mentioned siloxane unit formulas in mole fractions of x'", y'" and z'", which does not imply an arrangement in the order of the above-mentioned siloxane units.
  • siloxane units are arranged randomly in the hydrogenpolysiloxanes, there may be cases in which some block portions are present, but the rest of the units are arranged in a random fashion.
  • R stands for an alkyl group, typically ethyl, and can be a methyl or propyl group as well.
  • the specific method steps are performed in the same manner as set forth above for the cyclic dihydrogenpolysiloxanes.
  • the hydrochloric acid is typically concentrated hydrochloric acid, and, even more typically, hydrochloric acid with a hydrogen chloride content of 15 wt% to 37 wt%. Because water contained in the hydrochloric acid is used for the hydrolysis of (A ) dichlorosilane (H2SiCl2), (B ) trichlorosilane (HS1CI3) and (C ) tetraalkoxysilane (Si(OR)4) or tetrachlorosilane (SiCl4), the hydrochloric acid is typically used in an amount that is equal to or higher than the equimolar amount necessary for the hydrolysis of (A ) dichlorosilane (H2SiCl2), (B ) trichlorosilane (HSiCl3) and (C ) tetraalkoxysilane (Si(OR)4) or tetrachlorosilane (S1CI4).
  • the ionic surface active agents are described above and suppress gelling due to independent condensation and rapid hydrolysis/condensation of trichlorosilane and promote its co-hydrolysis/condensation with dichlorosilane.
  • the cyclic dihydrogenpolysiloxanes, as well as the hydrogenpolysiloxanes that have the siloxane unit formula of [H2Si ⁇ 2/2] ⁇ "'[HSi ⁇ 3/2]y"'[Si ⁇ 4/2] z '” are heated to a temperature of 12O 0 C or higher, silicon-bonded hydrogen is turned into hydroxyl groups via an oxidation reaction and crosslinking takes place as a result of a dehydration condensation reaction with the silicon- bonded hydrogen atoms.
  • the heating may occur in an oxygen atmosphere.
  • Air is a representative example of the oxygen atmosphere.
  • the oxygen atmosphere may alternatively be an oxygen gas-containing nitrogen gas or helium gas with an oxygen concentration lower than that of air.
  • exposure to ozone, nitrous oxide, or wet ammonia may be used to induce reaction of the cyclic dihydrogenpolysiloxanes and hydrogenpolysiloxanes.
  • the ozone is exemplified by pure ozone, ozone-containing air, steam-containing ozone and ozone-containing nitrogen gas, any of which can be used.
  • the reaction when induced by ozone, occurs in a more efficient manner than when the reaction is induced by atmospheric oxygen.
  • the nitrous oxide is exemplified by pure nitrous oxide gas, nitrous oxide- containing air and nitrous oxide-containing nitrogen gas, any of which can be used.
  • the wet ammonia is exemplified by ammonia-containing air, ammonium hydroxide gas and nitrogen gas containing ammonia and steam, any of which can be used.
  • the exposure to ozone, exposure to nitrous oxide, or exposure to ammonia may be carried out under heating.
  • the above-mentioned cyclic dihydrogenpolysiloxanes and hydrogenpolysiloxanes may also be cured by high-energy irradiation. Electron beams and X-rays are representative examples of such irradiation. The amount of electron beam irradiation is typically not less than 3 Gry. [0237] The following examples are meant to illustrate reinforced substrates and are not to be viewed in any way as limiting the scope of the present disclosure.
  • a four-inch wide saturation trough was used.
  • Style 106 glass fabric obtained from BGF Industries and heat cleaned in air, was cut into strips 15" X 3.5" in size.
  • the impregnated fiber reinforcement was hung vertically in a fumed hood to dry and then transferred to an air-circulating oven to cure.
  • the impregnated fiber reinforcement was partially cured at 50 0 C for 10 min. and then impregnated again with the same resin. After drying, the impregnated fiber reinforcement was cured by the following procedure: 1 °C/min.
  • 0.031 grams of oxidized Pyrograf III was mixed into 50 grams of MPlOl Crystal Coat resin in a glass vial and placed in a Bransonic ultrasonic cleaning bath and dispersed for 30 minutes. The mixture was then centrifuged if there was un-dispersed powder and the top dispersion was taken for film preparation. [0240] The Style 106 glass fabric was heated, cleaned and cut into a shape that would fit into the saturation pan. The mixture of the Pyrograf III and MPlOl Crystal Coat resin was placed in the saturation pan, and the fabric was passed through the mixture in the saturation pan to form an impregnated fiber reinforcement.
  • the impregnated fiber reinforcement was hung vertically in a fumed hood to dry and then transferred to an air- circulating oven to cure by the following procedure: 1 °C/min. to 75 0 C, 75 °C/1 h., 1 °C/min. to 100 0 C, 100 °C/1 h., 1 °C/min. to 125 0 C and 125 °C/1 h to form the fiber reinforced substrate.
  • the fiber reinforced substrate was kept in the switched off oven to cool.
  • Molybdenum was sputtered onto the substrate prepared in Example 1 to form an approximately 0.5 micrometer thick layer of molybdenum. Copper, indium and gallium were co-evaporated onto the layer of molybdenum in a selenium atmosphere at a deposition substrate temperature of about 575 0 C for 20 minutes to form a CIS-based solar absorber layer of a thickness of around two micrometer thick. CdS was then deposited on the CIS-based solar absorber layer through a wet CBD bath process to form a window layer having a thickness of about 50 nm.
  • a ZnO electrically insulating layer and an ITO top contact layer were sputtered onto the window layer and then nickel-silver grids were evaporated onto the top contact layer.
  • the cell performance was tested under AMI .5 illumination condition and an efficiency of 1 to 2% was measured.
  • CIGS-based photovoltaic devices were fabricated in the same way as described in Example 4 on substrates prepared in Example 2.
  • the CIGS-based TFPV devices were tested under the same conditions as shown in Example 4. An efficiency of 6 to 9% was measured.
  • CIGS-based TFPV devices were fabricated in the same way as described in Example 4 on substrates prepared in Example 3. The CIGS-based TFPV devices were tested under the same conditions as shown in Example 4. Efficiencies up to 12.7% were measured.
  • Substrate including stainless steel foil layer and silicone layer formed from Dow Corning FOX resin
  • a Dow Corning 9-5101 Hydrogen Silsesquioxane resin was applied onto a 6"X6" stainless steel foil layer on a spin coater at 2000 rpm for 30 seconds.
  • the stainless steel foil layer was 25 micrometer thick 430 stainless steel and is available from Marubeni Corporation of Tokyo, Japan.
  • the resin on the stainless steel foil layer was cured in an air circulating oven at 200 0 C for 2 hours to form a silicone layer on the foil layer.
  • the thickness of the silicone layer was approximately 1 micrometer.
  • Substrate including stainless steel foil layer and silicone layer formed from hydrogenpolysiloxane resin.
  • a hydrogenpolysiloxane resin was prepared by cohydrolyzing trichlorosilane and dichlorosilane, washing, and condensing the hydrolyzate to yield a resin with an average composition of (H2Si ⁇ 2/2) ⁇ .29(HSi ⁇ 3/2)o.7l-
  • the resin was applied onto the stainless steel foil layer as described in Example 7.
  • the resin on the stainless steel foil layer was cured in an air circulating oven at 200 °C for 2 hours to form a silicone layer on the foil layer.
  • CIGS copper indium gallium diselenide
  • Molybdenum was sputtered onto the substrate prepared in Example 7 to form an approximately 0.5 micrometer thick layer of molybdenum. Copper, indium and gallium were co-evaporated onto the layer of molybdenum in a selenium atmosphere to form a CIS-based solar absorber layer of a thickness of about two micrometers. CdS was then deposited onto the CIS-based solar absorber layer through a wet CBD bath process to form a window layer having a thickness of about 50 nm. ITO was RF sputtered onto the window layer to form a top contact layer, and then copper grids were evaporated onto the top contact layer. The cell performance was tested under AMI .5 illumination condition and an efficiency of 5 to 7% was measured.
  • CIS-based photovoltaic device including substrate prepared in Example 8.
  • a CIS-based photovoltaic device was fabricated in the same way as described in Example 9 including the substrate prepared in Example 8. The CIS-based photovoltaic devices were tested under the same conditions as shown in Example 9. An efficiency of 6 to 14% was measured.
  • MPlOl Crystal Coat Resin was obtained from SDC Coating Technologies, Inc. The resin was 31 wt. %. Stainless steel foil was coated and the coating was cured in the same way as described in Example 7.
  • a CIS-based photovoltaic device was fabricated in the same way as described in Example 9 on the coated stainless steel foil prepared in Example 11. They were tested under the same conditions as shown in Example 9. An efficiency of 6 to 11% was measured.

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008026505A1 (de) * 2008-05-26 2010-02-18 Würth Elektronik GmbH & Co. KG Solarmodul, Solarfläche und Solaranlage
EP2161758A1 (en) * 2008-09-05 2010-03-10 Flexucell ApS Solar cell and method for the production thereof
WO2011084806A1 (en) * 2010-01-06 2011-07-14 Dow Global Technologies Inc. Moisture resistant photovoltaic devices with elastomeric, polysiloxane protection layer
US9786807B2 (en) 2011-04-19 2017-10-10 Empa Thin-film photovoltaic device and fabrication method
US9837565B2 (en) 2012-12-21 2017-12-05 Flison Ag Fabricating thin-film optoelectronic devices with added potassium
US9842952B2 (en) 2008-10-31 2017-12-12 Dow Corning Corporation Photovoltaic cell module and method of forming
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Families Citing this family (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007018756A1 (en) 2005-08-04 2007-02-15 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
ATE517947T1 (de) 2005-12-21 2011-08-15 Dow Corning Silikonharzfilm, herstellungsverfahren dafür und nanomaterialgefüllte silikonzusammensetzung
KR100753959B1 (ko) * 2006-01-12 2007-08-31 에이펫(주) 기판 건조장치를 이용한 기판 건조방법
US20090090413A1 (en) * 2006-04-18 2009-04-09 Dimitris Elias Katsoulis Cadmium Telluride-Based Photovoltaic Device And Method Of Preparing The Same
ATE448569T1 (de) * 2006-04-18 2009-11-15 Dow Corning Fotovoltaische anordnung auf kupfer-indium- diselenidbasis und herstellungsverfahren dafür
EP2325003A1 (en) * 2006-06-05 2011-05-25 Dow Corning Corporation Extruder die assembly for multilayers
WO2008013611A1 (en) * 2006-07-27 2008-01-31 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
WO2008036769A2 (en) * 2006-09-19 2008-03-27 Itn Energy Systems, Inc. Semi-transparent dual layer back contact for bifacial and tandem junction thin-film photovolataic devices
EP2066757A1 (en) * 2006-10-05 2009-06-10 Dow Corning Corporation Silicone resin film and method of preparing same
EP2125363A2 (en) * 2007-02-22 2009-12-02 Dow Corning Corporation Composite article having excellent fire and impact resistance and method of making the same
CN101627096B (zh) * 2007-02-22 2012-11-07 道康宁公司 增强硅树脂膜及其制备方法
KR20090120468A (ko) * 2007-02-22 2009-11-24 다우 코닝 코포레이션 우수한 내화성을 갖는 복합체 물품
EP2117836B1 (en) 2007-02-22 2012-11-07 Dow Corning Corporation Reinforced silicone resin films
KR20090110878A (ko) * 2007-02-22 2009-10-22 다우 코닝 코포레이션 우수한 내화성을 갖는 복합체 물품
EP2117835A1 (en) 2007-02-22 2009-11-18 Dow Corning Corporation Reinforced silicone resin films
US8716591B2 (en) * 2007-06-20 2014-05-06 Ascent Solar Technologies, Inc. Array of monolithically integrated thin film photovoltaic cells and associated methods
US8071179B2 (en) 2007-06-29 2011-12-06 Stion Corporation Methods for infusing one or more materials into nano-voids if nanoporous or nanostructured materials
US20090020149A1 (en) * 2007-07-16 2009-01-22 Woods Lawrence M Hybrid Multi-Junction Photovoltaic Cells And Associated Methods
JP2009043842A (ja) * 2007-08-07 2009-02-26 Sharp Corp 太陽電池モジュール
KR20100051738A (ko) * 2007-08-31 2010-05-17 어플라이드 머티어리얼스, 인코포레이티드 광전지 생산 라인
US20100047954A1 (en) * 2007-08-31 2010-02-25 Su Tzay-Fa Jeff Photovoltaic production line
US8525021B2 (en) * 2007-09-25 2013-09-03 First Solar, Inc. Photovoltaic devices including heterojunctions
US20090188603A1 (en) * 2008-01-25 2009-07-30 Applied Materials, Inc. Method and apparatus for controlling laminator temperature on a solar cell
CN101984772A (zh) * 2008-03-17 2011-03-09 夏普株式会社 太阳能电池模块和太阳能电池模块的制造方法
US20100236607A1 (en) * 2008-06-12 2010-09-23 General Electric Company Monolithically integrated solar modules and methods of manufacture
US7981778B2 (en) * 2009-07-22 2011-07-19 Applied Materials, Inc. Directional solid phase crystallization of thin amorphous silicon for solar cell applications
KR20110059724A (ko) 2008-08-26 2011-06-03 어플라이드 머티어리얼스, 인코포레이티드 레이저 재료 제거 방법 및 장치
US7947524B2 (en) 2008-09-30 2011-05-24 Stion Corporation Humidity control and method for thin film photovoltaic materials
US8383450B2 (en) * 2008-09-30 2013-02-26 Stion Corporation Large scale chemical bath system and method for cadmium sulfide processing of thin film photovoltaic materials
US20110018103A1 (en) * 2008-10-02 2011-01-27 Stion Corporation System and method for transferring substrates in large scale processing of cigs and/or cis devices
MY157233A (en) * 2009-03-11 2016-05-13 Shinetsu Chemical Co Connection sheet for solar battery cell electrode, process for manufacturing solar cell module, and solar cell module
US8241943B1 (en) 2009-05-08 2012-08-14 Stion Corporation Sodium doping method and system for shaped CIGS/CIS based thin film solar cells
US8372684B1 (en) 2009-05-14 2013-02-12 Stion Corporation Method and system for selenization in fabricating CIGS/CIS solar cells
US20100330711A1 (en) * 2009-06-26 2010-12-30 Applied Materials, Inc. Method and apparatus for inspecting scribes in solar modules
US8507786B1 (en) 2009-06-27 2013-08-13 Stion Corporation Manufacturing method for patterning CIGS/CIS solar cells
WO2011008254A1 (en) 2009-07-13 2011-01-20 First Solar, Inc. Solar cell front contact doping
US8398772B1 (en) 2009-08-18 2013-03-19 Stion Corporation Method and structure for processing thin film PV cells with improved temperature uniformity
US20110065227A1 (en) * 2009-09-15 2011-03-17 Applied Materials, Inc. Common laser module for a photovoltaic production line
WO2011035234A1 (en) * 2009-09-18 2011-03-24 The University Of Toledo Method of producing a flexible photovoltaic cell using a flexible polymer-fixture laminate
US8859880B2 (en) * 2010-01-22 2014-10-14 Stion Corporation Method and structure for tiling industrial thin-film solar devices
US8142521B2 (en) * 2010-03-29 2012-03-27 Stion Corporation Large scale MOCVD system for thin film photovoltaic devices
US9096930B2 (en) 2010-03-29 2015-08-04 Stion Corporation Apparatus for manufacturing thin film photovoltaic devices
MX2012013614A (es) 2010-05-26 2013-03-20 Univ Toledo Estructuras fotovoltaicas que tienen una capa de interfaz de difraccion de luz y metodos para fabricar las mismas.
US8461061B2 (en) 2010-07-23 2013-06-11 Stion Corporation Quartz boat method and apparatus for thin film thermal treatment
US9082903B2 (en) * 2010-09-22 2015-07-14 First Solar, Inc. Photovoltaic device with a zinc magnesium oxide window layer
US8906732B2 (en) * 2010-10-01 2014-12-09 Stion Corporation Method and device for cadmium-free solar cells
EP2658925A2 (en) * 2010-12-30 2013-11-06 Saint-gobain Performance Plastics Corporation Improved silicone membrane for lamination process
KR101349484B1 (ko) * 2011-11-29 2014-01-10 엘지이노텍 주식회사 태양전지 모듈 및 이의 제조방법
US20150047698A1 (en) * 2012-01-19 2015-02-19 NuvoSun, Inc. Protective coatings for photovoltaic cells
KR20130136739A (ko) * 2012-06-05 2013-12-13 엘지이노텍 주식회사 태양전지 및 이의 제조방법
US9306106B2 (en) 2012-12-18 2016-04-05 International Business Machines Corporation Monolithic integration of heterojunction solar cells
US20140261686A1 (en) * 2013-03-15 2014-09-18 First Solar, Inc Photovoltaic device with a zinc oxide layer and method of formation
KR101564961B1 (ko) 2013-04-02 2015-11-02 한국에너지기술연구원 황동광계 광흡수층의 형성방법
WO2015006382A1 (en) * 2013-07-08 2015-01-15 Solexel, Inc. Thin film solar cell lamination stack for high volume manufacturing
CN106459459A (zh) * 2014-05-27 2017-02-22 沙特基础工业全球技术公司 用于抗污的自清洁型超疏水聚合物材料
CN104393060B (zh) * 2014-11-26 2017-04-26 山东力诺光伏高科技有限公司 一种抗隐裂光伏组件
CN104576826B (zh) * 2014-12-17 2017-04-26 山东力诺太阳能电力股份有限公司 一种太阳能电池片的后处理方法
CN104576794B (zh) * 2014-12-17 2017-02-01 山东力诺光伏高科技有限公司 一种抗隐裂太阳能组件的生产方法
NL2014040B1 (en) * 2014-12-23 2016-10-12 Stichting Energieonderzoek Centrum Nederland Method of making a curent collecting grid for solar cells.
WO2017100393A2 (en) * 2015-12-09 2017-06-15 First Solar, Inc. Photovoltaic devices and method of manufacturing
CN106129147B (zh) * 2016-09-19 2017-06-27 中国电子科技集团公司第十八研究所 一种柔性铜铟镓硒薄膜太阳电池组件内联方法
WO2019147545A1 (en) * 2018-01-25 2019-08-01 Saint-Gobain Adfors Canada, Ltd. Photovoltaic textile
JP6864642B2 (ja) * 2018-03-22 2021-04-28 株式会社東芝 太陽電池、多接合型太陽電池、太陽電池モジュール及び太陽光発電システム
JP6897695B2 (ja) * 2019-01-28 2021-07-07 信越化学工業株式会社 紫外線硬化型シリコーン接着剤組成物および積層体の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4542257A (en) * 1984-04-27 1985-09-17 Hughes Aircraft Company Solar cell array panel and method of manufacture
WO2003022564A1 (en) * 2001-09-12 2003-03-20 Itn Energy Systems, Inc. Apparatus and method for the design and manufacture of multifunctional composite materials with power integration
EP1388572A1 (en) * 2002-08-08 2004-02-11 Shin-Etsu Chemical Co., Ltd. Addition reaction curable organopolysiloxane composition
WO2005052078A1 (en) * 2003-11-28 2005-06-09 Dow Corning Toray Co., Ltd. A method of manufacturing a layered silicone composite material

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL131800C (US20080115827A1-20080522-C00002.png) * 1965-05-17
US4018819A (en) * 1971-07-09 1977-04-19 Hoechst Aktiengesellschaft Process for the manufacture of 2-chloroethane-phosphonic acid
US4081819A (en) 1977-01-17 1978-03-28 Honeywell Inc. Mercury cadmium telluride device
US4087585A (en) * 1977-05-23 1978-05-02 Dow Corning Corporation Self-adhering silicone compositions and preparations thereof
US4260780A (en) * 1979-11-27 1981-04-07 The United States Of America As Represented By The Secretary Of The Air Force Phenylmethylpolysilane polymers and process for their preparation
US4276424A (en) * 1979-12-03 1981-06-30 Petrarch Systems Methods for the production of organic polysilanes
US4314956A (en) * 1980-07-23 1982-02-09 Dow Corning Corporation High yield silicon carbide pre-ceramic polymers
US4335266A (en) * 1980-12-31 1982-06-15 The Boeing Company Methods for forming thin-film heterojunction solar cells from I-III-VI.sub.2
US4324901A (en) * 1981-04-29 1982-04-13 Wisconsin Alumni Research Foundation Soluble polysilastyrene and method for preparation
DE3280293D1 (de) 1981-11-04 1991-02-21 Kanegafuchi Chemical Ind Biegsame photovoltaische einrichtung.
US4530879A (en) * 1983-03-04 1985-07-23 Minnesota Mining And Manufacturing Company Radiation activated addition reaction
US4510094A (en) * 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
US4766176A (en) * 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
JPH0214244A (ja) * 1988-06-30 1990-01-18 Toray Dow Corning Silicone Co Ltd 加熱硬化性オルガノポリシロキサン組成物
JPH02181975A (ja) 1989-01-07 1990-07-16 Nitto Denko Corp フィルム太陽電池
JP3029680B2 (ja) * 1991-01-29 2000-04-04 東レ・ダウコーニング・シリコーン株式会社 オルガノペンタシロキサンおよびその製造方法
JPH05218482A (ja) 1992-02-05 1993-08-27 Matsushita Electric Ind Co Ltd 太陽電池モジュール
US5441897A (en) * 1993-04-12 1995-08-15 Midwest Research Institute Method of fabricating high-efficiency Cu(In,Ga)(SeS)2 thin films for solar cells
JP3168811B2 (ja) 1994-03-23 2001-05-21 富士電機株式会社 薄膜光電変換装置およびその製造方法
DE4423195A1 (de) * 1994-07-01 1996-01-04 Wacker Chemie Gmbh Triazenoxid-Übergangsmetall-Komplexe als Hydrosilylierungskatalysatoren
JP3076895B2 (ja) 1994-12-21 2000-08-14 株式会社富士電機総合研究所 可撓性太陽電池モジュール
JP3117627B2 (ja) 1995-11-10 2000-12-18 ジーイー東芝シリコーン株式会社 太陽電池モジュール用保護シート用組成物および太陽電池モジュール用保護シート
US5702584A (en) * 1996-07-01 1997-12-30 Ford Motor Company Enhanced plating adhesion through the use of metallized fillers in plastic substrate
US5985691A (en) 1997-05-16 1999-11-16 International Solar Electric Technology, Inc. Method of making compound semiconductor films and making related electronic devices
JPH10321887A (ja) 1997-05-21 1998-12-04 Shibata Ind Co Ltd 太陽電池モジュール用保護シート
JPH10321888A (ja) 1997-05-21 1998-12-04 Shibata Ind Co Ltd 太陽電池モジュール用保護シート
US5972512A (en) * 1998-02-16 1999-10-26 Dow Corning Corporation Silicone resin composites for fire resistance applications and method for fabricating same
CN1225029C (zh) * 2000-03-13 2005-10-26 索尼株式会社 光能转换装置
US6447922B1 (en) 2000-11-20 2002-09-10 General Electric Company Curable silicon adhesive compositions
US7271333B2 (en) * 2001-07-20 2007-09-18 Ascent Solar Technologies, Inc. Apparatus and method of production of thin film photovoltaic modules
US6537845B1 (en) * 2001-08-30 2003-03-25 Mccandless Brian E. Chemical surface deposition of ultra-thin semiconductors
US20030059526A1 (en) * 2001-09-12 2003-03-27 Benson Martin H. Apparatus and method for the design and manufacture of patterned multilayer thin films and devices on fibrous or ribbon-like substrates
TW560102B (en) * 2001-09-12 2003-11-01 Itn Energy Systems Inc Thin-film electrochemical devices on fibrous or ribbon-like substrates and methd for their manufacture and design
JP4055053B2 (ja) 2002-03-26 2008-03-05 本田技研工業株式会社 化合物薄膜太陽電池およびその製造方法
US7037592B2 (en) * 2003-02-25 2006-05-02 Dow Coming Corporation Hybrid composite of silicone and organic resins
KR101410709B1 (ko) 2003-07-07 2014-06-25 다우 코닝 코포레이션 태양 전지의 캡슐화 방법
WO2005017058A1 (en) 2003-08-01 2005-02-24 Dow Corning Corporation Silicone based dielectric coatings and films for photovoltaic applications
JP2005089671A (ja) * 2003-09-19 2005-04-07 Shin Etsu Chem Co Ltd 硬化性シリコーン樹脂組成物
CN101087899A (zh) * 2004-11-10 2007-12-12 德斯塔尔科技公司 光电装置的垂直生产
US7695805B2 (en) * 2004-11-30 2010-04-13 Tdk Corporation Transparent conductor
PL1856206T3 (pl) 2005-02-16 2012-05-31 Dow Corning Błona ze wzmocnionej żywicy silikonowej i sposób jej wytwarzania
WO2006088645A1 (en) 2005-02-16 2006-08-24 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
US8092910B2 (en) * 2005-02-16 2012-01-10 Dow Corning Toray Co., Ltd. Reinforced silicone resin film and method of preparing same
WO2007092032A2 (en) 2005-06-14 2007-08-16 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
WO2007018756A1 (en) 2005-08-04 2007-02-15 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
JP5043317B2 (ja) 2005-08-05 2012-10-10 東レ・ダウコーニング株式会社 環状ジハイドロジェンポリシロキサン、ハイドロジェンポリシロキサン、それらの製造方法、シリカ系ガラス成形体およびその製造方法、光学素子およびその製造方法
ATE517947T1 (de) 2005-12-21 2011-08-15 Dow Corning Silikonharzfilm, herstellungsverfahren dafür und nanomaterialgefüllte silikonzusammensetzung
ATE516331T1 (de) 2006-02-02 2011-07-15 Dow Corning Silikonharzfilm, herstellungsverfahren dafür und mit nanomaterial gefüllte silikonzusammensetzung
US8084097B2 (en) 2006-02-20 2011-12-27 Dow Corning Corporation Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition
US8795560B2 (en) 2006-04-11 2014-08-05 Dow Corning Corporation Low thermal distortion silicone composite molds
ATE448569T1 (de) 2006-04-18 2009-11-15 Dow Corning Fotovoltaische anordnung auf kupfer-indium- diselenidbasis und herstellungsverfahren dafür
US20090084427A1 (en) 2006-04-18 2009-04-02 Anderson Nicole R Copper Indium Diselenide-Based Photovoltaic Device And Method Of Preparing the Same
US20090090413A1 (en) 2006-04-18 2009-04-09 Dimitris Elias Katsoulis Cadmium Telluride-Based Photovoltaic Device And Method Of Preparing The Same
EP2325003A1 (en) 2006-06-05 2011-05-25 Dow Corning Corporation Extruder die assembly for multilayers
WO2008013611A1 (en) 2006-07-27 2008-01-31 Dow Corning Corporation Reinforced silicone resin film and method of preparing same
WO2008036769A2 (en) 2006-09-19 2008-03-27 Itn Energy Systems, Inc. Semi-transparent dual layer back contact for bifacial and tandem junction thin-film photovolataic devices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4542257A (en) * 1984-04-27 1985-09-17 Hughes Aircraft Company Solar cell array panel and method of manufacture
WO2003022564A1 (en) * 2001-09-12 2003-03-20 Itn Energy Systems, Inc. Apparatus and method for the design and manufacture of multifunctional composite materials with power integration
EP1388572A1 (en) * 2002-08-08 2004-02-11 Shin-Etsu Chemical Co., Ltd. Addition reaction curable organopolysiloxane composition
WO2005052078A1 (en) * 2003-11-28 2005-06-09 Dow Corning Toray Co., Ltd. A method of manufacturing a layered silicone composite material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008026505A1 (de) * 2008-05-26 2010-02-18 Würth Elektronik GmbH & Co. KG Solarmodul, Solarfläche und Solaranlage
EP2161758A1 (en) * 2008-09-05 2010-03-10 Flexucell ApS Solar cell and method for the production thereof
WO2010025734A1 (en) * 2008-09-05 2010-03-11 Flexucell Aps Solar cell with flexible corrugated substrate and method for the production thereof
US9842952B2 (en) 2008-10-31 2017-12-12 Dow Corning Corporation Photovoltaic cell module and method of forming
WO2011084806A1 (en) * 2010-01-06 2011-07-14 Dow Global Technologies Inc. Moisture resistant photovoltaic devices with elastomeric, polysiloxane protection layer
CN102742017A (zh) * 2010-01-06 2012-10-17 陶氏环球技术有限责任公司 具有弹性聚硅氧烷保护层的耐湿光伏器件
US9786807B2 (en) 2011-04-19 2017-10-10 Empa Thin-film photovoltaic device and fabrication method
US10153387B2 (en) 2012-12-21 2018-12-11 Flisom Ag Fabricating thin-film optoelectronic devices with added potassium
US9837565B2 (en) 2012-12-21 2017-12-05 Flison Ag Fabricating thin-film optoelectronic devices with added potassium
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US10396218B2 (en) 2014-09-18 2019-08-27 Flisom Ag Self-assembly pattering for fabricating thin-film devices
US10651324B2 (en) 2016-02-11 2020-05-12 Flisom Ag Self-assembly patterning for fabricating thin-film devices
US10658532B2 (en) 2016-02-11 2020-05-19 Flisom Ag Fabricating thin-film optoelectronic devices with added rubidium and/or cesium
US10971640B2 (en) 2016-02-11 2021-04-06 Flisom Ag Self-assembly patterning for fabricating thin-film devices
US11257966B2 (en) 2016-02-11 2022-02-22 Flisom Ag Fabricating thin-film optoelectronic devices with added rubidium and/or cesium

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