WO2012163101A1 - 一种太阳能电池专用绒面导电玻璃及其制备方法与应用 - Google Patents

一种太阳能电池专用绒面导电玻璃及其制备方法与应用 Download PDF

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WO2012163101A1
WO2012163101A1 PCT/CN2012/070984 CN2012070984W WO2012163101A1 WO 2012163101 A1 WO2012163101 A1 WO 2012163101A1 CN 2012070984 W CN2012070984 W CN 2012070984W WO 2012163101 A1 WO2012163101 A1 WO 2012163101A1
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conductive glass
nano
suede
glass
transparent conductive
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PCT/CN2012/070984
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English (en)
French (fr)
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王洋
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惠州市易晖太阳能科技有限公司
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Priority to JP2013525133A priority Critical patent/JP5734431B2/ja
Priority to EP12793834.8A priority patent/EP2717320B1/en
Priority to KR1020137017506A priority patent/KR101510578B1/ko
Priority to US13/822,485 priority patent/US20140174521A1/en
Publication of WO2012163101A1 publication Critical patent/WO2012163101A1/zh

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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
    • H01L31/04—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
    • C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
    • C03C17/3678—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the invention belongs to the technical field of special glass production, and particularly relates to a suede conductive glass for solar battery and a preparation method and application thereof.
  • Conductive glass is a special type of glass that is coated with a transparent conductive film on one side of a common flat glass, so that the entire glass has both transparency and electrical conductivity.
  • conductive glass is often an integral part of photovoltaic thin film cells - used as transparent electrodes and substrates for batteries.
  • the photoelectric quality of conductive glass directly affects the performance of photovoltaic cells, and is therefore one of the key raw materials for preparing amorphous silicon, microcrystalline silicon, chromium telluride, and copper indium gallium selenide thin film batteries. How to prepare high-quality conductive glass for high-quality solar cells at low cost is a necessary prerequisite for the preparation of low-cost and high-efficiency solar cells to realize low-cost solar power generation.
  • the existing special conductive glass for producing solar cells and preparation methods are as follows:
  • ITO Indium tin oxide
  • FTO fluorine-doped tin dioxide
  • BZO Boron-doped zinc oxide
  • AZO zinc-aluminum oxide
  • the transparent conductive film of the conductive glass needs to have a nano/micron size, that is, unevenness, such that the light diffuses at the time of incidence (usually measured by the haze value), and the light is increased in the battery.
  • the optical path of the internal transmission (as shown in Figure 1).
  • FTO fluorine-doped tin dioxide
  • BZO Boron-doped zinc oxide
  • AZO zinc-aluminum oxide
  • the suede form of the transparent conductive film must ensure that the film material quality of the battery absorption layer is not affected by its unevenness. Since the preparation process of the battery is often superimposed and grown in sequence, the transparent conductive film acts as a direct substrate of the absorption layer when the absorption layer is grown, and its morphology directly affects the growth mode and quality of the absorption layer film. Taking the microcrystalline silicon absorber layer as an example (as shown in Fig. 5), different transparent conductive film topography results in different textures of the microcrystalline silicon absorber layer.
  • the microcrystalline silicon absorbing layer is liable to form cracks, which seriously affects the performance of the solar cell.
  • the suede topography resembles a U shape (Fig. 5B)
  • the microcrystalline silicon absorber layer has small cracks and even no cracks (Fig. 5C).
  • the chrome-plated absorbing layer is more demanding on the morphology of the suede than the microcrystalline silicon, and the suede must be composed entirely of shallow U-shaped depressions.
  • the primary object of the present invention is to provide a low-cost, large-area solar cell-specific suede conductive glass having a uniform and controllable nano-scale U-shaped suede.
  • Another object of the present invention is to provide a method for preparing the above-mentioned solar cell-specific fumed conductive glass, which is coated with a transparent conductive film (ITO, AZO, etc.) by magnetron sputtering, and then a nano/microsphere (diameter 10) by immersion plating. Nano-100 micron) is adsorbed on the surface as a mask, and the thickness of the transparent conductive film is increased in the nano/microsphere gap by magnetron sputtering. Finally, the nano/microsphere is removed by mechanical or chemical methods such as ultrasonic vibration to achieve a large area. Costly a conductive glass having a U-shaped suede is prepared.
  • a transparent conductive film ITO, AZO, etc.
  • Still another object of the present invention is to provide an application of the above-described suede conductive glass for solar cells.
  • the utility model relates to a suede conductive glass for solar battery, which has the structure and composition: a transparent conductive film is plated on the glass substrate, and the upper surface of the transparent conductive film is a suede with a nano-scale U-shaped pile;
  • the transparent conductive film has a thickness of 100-5000 nm
  • the transparent conductive film is one of indium tin oxide (ITO) or zinc aluminum oxide (AZO) or other transparent conductive film material (isoelectric point greater than 3).
  • the preparation method of the above-mentioned solar cell-specific suede conductive glass comprises the following steps (as shown in FIG. 6):
  • isoelectric point of a transparent conductive film such as ITO or AZO (isoelectric Point) is relatively large, generally 6-10, and the isoelectric point of silica or polystyrene nano/microsphere is relatively small, generally 2-4, so when the conductive glass is immersed in the nano/micro sphere
  • suspension pH 7
  • weakly acidic pH 3-6
  • the surface of the transparent conductive film is negatively charged, and the surface of the nano/microsphere is positively charged, causing the two materials to electrostatically attract each other.
  • the surface of the transparent conductive film is almost entirely adsorbed by a nano/microsphere.
  • the coverage area of the nano/microspheres on the conductive glass varies with the concentration of nano/microsphere ball suspension, pH, and immersion time.
  • a transparent conductive film is plated on the conductive glass B by magnetron sputtering to obtain a conductive glass C.
  • the thickness of the newly plated film does not exceed the radius of the nano/microsphere, and the transparent conductive
  • the total thickness of the film is 100-5000 nm;
  • the second reason for using magnetron sputtering is that the coating material can enter the underside of the nano/microsphere during magnetron sputtering to form a U-shaped surface without edges (as shown in Figure 7).
  • the conductive glass has a transmittance in the visible light band of 80% or more and a sheet resistance of less than 10 ohms.
  • the magnetron sputtering described in the steps (1) and (3) is as follows: basic vacuum: ⁇ 1 ⁇ 10 -5 Torr; working gas pressure: 1-10 mTorr; working gas: Ar + O 2 ; sputtering source : tributary or radio frequency 13.56MHz; power: 100-1000W; substrate temperature: 20-500 ° C; deposition rate: 10-100nm / min;
  • the nano/microsphere of the step (2) has a diameter of 10 nm to 100 ⁇ m;
  • the material of the nano/microsphere of the step (2) is one of silicon dioxide or polystyrene
  • the mass/volume concentration of the nano/microsphere in the suspension described in the step (2) is 0.01-1%
  • the solvent of the suspension according to the step (2) is one of water, methanol or ethanol;
  • the immersion time of the conductive glass in the suspension in the step (2) is preferably 8-10 minutes;
  • the above-mentioned suede conductive glass for solar cells can be used as a transparent electrode or substrate of a solar cell.
  • nano/microspheres of the present invention refer to nanospheres or microspheres; the nano/micron refers to nanometers or micrometers.
  • the flat glass magnetron sputtering, immersion plating, cleaning and other processes used in this method are matched with standard industrial production processes, high production efficiency, large applicable glass area, good repeatability, and yield.
  • the high-yield nano/microsphere ball is inexpensive to prepare, and is very suitable for the production of low-cost high-quality conductive glass for solar cells.
  • FIG. 1 is a schematic view showing the structure of a cut surface of an amorphous silicon thin film battery.
  • FIG. 2 is a schematic view showing the microstructure of a zinc aluminum oxide (AZO) conductive glass surface prepared by wet etching with hydrochloric acid after magnetron sputtering.
  • AZO zinc aluminum oxide
  • FIG 3 is a schematic view showing the microstructure of a fluorine-doped tin dioxide (FTO) conductive glass surface prepared by atmospheric pressure chemical vapor deposition.
  • FTO fluorine-doped tin dioxide
  • FIG. 4 is a schematic view showing the microstructure of a boron-doped zinc oxide (BZO) or zinc aluminum oxide (AZO) conductive glass prepared by a low pressure chemical vapor deposition method.
  • BZO boron-doped zinc oxide
  • AZO zinc aluminum oxide
  • Figure 5 is a comparison of the growth states of microcrystalline silicon films on different conductive glass substrates.
  • FIG. 6 is a schematic flow chart of a preparation method of a suede conductive glass for a solar cell of the present invention.
  • Fig. 7 is a schematic view showing the manner of film deposition during magnetron sputtering coating using a nano/microsphere ball as a mask.
  • Figure 8 is a conductive glass plated with nano/microspheres in Example 1.
  • Figure 9 is a conductive glass plated with nano/microspheres in Example 2.
  • Figure 10 is a conductive glass plated with nano/microspheres in Example 3.
  • Figure 11 is a conductive glass plated with nano/microspheres in Example 4.
  • Figure 12 is a conductive glass plated with nano/microspheres in Example 5.
  • Figure 13 is a conductive glass plated with nano/microspheres in Example 6.
  • Example 14 is a plan view showing the surface topography of the conductive glass of Example 1 after removing the nanospheres; A-magnification 10000, B-magnification 5000.
  • Example 15 is a side elevational view of a 30 degree inclination of a surface topography of the conductive glass of Example 1 after removing the nanospheres; A-magnification 10000, B-magnification 5000.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • AZO transparent conductive film is plated on the glass substrate by magnetron sputtering to obtain conductive glass A; the conditions of magnetron sputtering are as follows: basic vacuum: 0.8 ⁇ 10 -5 Torr; working pressure: 1 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 1000 W; substrate temperature: 20 ° C; deposition rate: 100 nm / min;
  • Figure 8 shows that a layer of nanospheres is immersed on the conductive glass B
  • an AZO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as in the step (1)) to obtain a conductive glass C, which is newly plated.
  • the film thickness does not exceed the radius of the nanosphere, and the total thickness of the transparent conductive film is 2000 nm;
  • Ultrasonic cleaning removes the nanospheres deposited on the surface of the transparent conductive film; a suede conductive glass for solar cells is obtained.
  • the surface morphology of the conductive glass is as shown in Fig. 14 and Fig. 15.
  • the recessed area of the suede topography has a large U-shaped shape and is uniformly distributed on the surface of the conductive glass; the conductive glass is in the visible light band.
  • the transmittance is 82% and the sheet resistance is 3 ohms, which can be used as a transparent electrode or substrate for a solar cell.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • AZO transparent conductive film is plated on the glass substrate by magnetron sputtering to obtain conductive glass A; the conditions of magnetron sputtering are as follows: basic vacuum: 0.7 ⁇ 10 -5 Torr; working pressure: 10 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 100 W; substrate temperature: 500 ° C; deposition rate: 10 nm / min;
  • Figure 9 shows that a layer of nanospheres is immersed on the conductive glass B
  • an AZO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as in the step (1)) to obtain a conductive glass C, new
  • the thickness of the plated film does not exceed the radius of the nano/microsphere, and the total thickness of the transparent conductive film is 3000 nm;
  • Ultrasonic cleaning removes the nano/microspheres deposited on the surface of the transparent conductive film, thereby forming a U-shaped nano/micron size on the surface C of the conductive glass to obtain a suede conductive glass for solar cells, which is in the visible light band.
  • the transmittance is 83% and the sheet resistance is 4 ohms, which can be used as a transparent electrode or substrate for a solar cell.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • the ITO transparent conductive film was plated on the glass substrate by magnetron sputtering to obtain conductive glass A.
  • the conditions of magnetron sputtering were as follows: basic vacuum: 0.9 ⁇ 10 -5 Torr; working pressure: 4 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 800 W; substrate temperature: 100 ° C; deposition rate: 80 nm / min;
  • Figure 10 shows that a layer of nanospheres is immersed on the conductive glass B
  • a ITO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as the step (1)) to obtain a conductive glass C, new
  • the thickness of the plated film does not exceed the radius of the nano/microsphere, and the total thickness of the transparent conductive film is 1000 nm;
  • Ultrasonic cleaning removes the nano/microspheres deposited on the surface of the transparent conductive film, thereby forming a U-shaped nano/micron size on the surface of the conductive glass C to obtain a suede conductive glass for solar cells, which is in the visible light band.
  • the transmittance is 81% and the sheet resistance is 2 ohms, which can be used as a transparent electrode or substrate for a solar cell.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • AZO transparent conductive film is plated on the glass substrate by magnetron sputtering to obtain conductive glass A.
  • the conditions of magnetron sputtering are as follows: basic vacuum: 0.5 ⁇ 10 -5 Torr; working pressure: 6 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 200 W; substrate temperature: 400 ° C; deposition rate: 40 nm / min;
  • Figure 11 shows that a layer of nanospheres is immersed on the conductive glass B, and the coverage rate is over 90%.
  • an AZO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as in the step (1)) to obtain a conductive glass C, new
  • the thickness of the plated film does not exceed the radius of the nano/microsphere, and the total thickness of the transparent conductive film is 100 nm;
  • Ultrasonic cleaning removes the nano/microspheres deposited on the surface of the transparent conductive film, thereby forming a U-shaped nano/micron size on the surface of the conductive glass C to obtain a suede conductive glass for solar cells, which is in the visible light band.
  • the transmittance is 84% and the sheet resistance is 5 ohms, which can be used as a transparent electrode or substrate for a solar cell.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • AZO transparent conductive film is plated on the glass substrate by magnetron sputtering to obtain conductive glass A.
  • the conditions of magnetron sputtering are as follows: basic vacuum: 0.6 ⁇ 10 -5 Torr; working pressure: 8 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 400 W; substrate temperature: 300 ° C; deposition rate: 20 nm / min;
  • Figure 12 shows that a layer of nanospheres is immersed on the conductive glass B, and the coverage is over 90%.
  • an AZO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as in the step (1)) to obtain a conductive glass C, new
  • the thickness of the plated film does not exceed the radius of the nano/microsphere, and the total thickness of the transparent conductive film is 5000 nm;
  • Ultrasonic cleaning removes the nano/microspheres deposited on the surface of the transparent conductive film, thereby forming a U-shaped nano/micron size on the surface of the conductive glass C to obtain a suede conductive glass for solar cells, which is in the visible light band.
  • the transmittance is 82% and the sheet resistance is 3 ohms, which can be used as a transparent electrode or substrate for a solar cell.
  • a method for preparing a suede conductive glass for a solar cell comprising the following steps (as shown in FIG. 6):
  • AZO transparent conductive film was plated on a glass substrate by magnetron sputtering to obtain conductive glass A.
  • the conditions of magnetron sputtering were as follows: basic vacuum: 0.4 ⁇ 10 -5 Torr; working pressure: 2 mTorr; Gas: Ar+O 2 ; sputtering source: tributary or radio frequency 13.56 MHz; power: 600 W; substrate temperature: 200 ° C; deposition rate: 60 nm / min;
  • Figure 13 shows that a layer of nanospheres is immersed on the conductive glass B
  • an AZO transparent conductive film is plated on the conductive glass B by magnetron sputtering (the conditions of magnetron sputtering are the same as in the step (1)) to obtain a conductive glass C, new
  • the thickness of the plated film does not exceed the radius of the nano/microsphere, and the total thickness of the transparent conductive film is 4000 nm;
  • Ultrasonic cleaning removes the nano/microspheres deposited on the surface of the transparent conductive film, thereby forming a U-shaped nano/micron size on the surface of the conductive glass C to obtain a suede conductive glass for solar cells, which is in the visible light band.
  • the transmittance is 82% and the sheet resistance is 3 ohms, which can be used as a transparent electrode or substrate for a solar cell.

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Abstract

公开了一种太阳能电池专用绒面导电玻璃及其制备方法与应用。一种太阳能电池专用绒面导电玻璃，在玻璃基片上镀有透明导电膜，透明导电膜的上表面是带有纳/微米级U形绒度的绒面；其制备方法是：采用磁控溅射镀透明导电膜，然后用浸镀的方法将纳/微米球吸附于其表面作为掩模，再通过磁控溅射在纳/微米球间隙增加透明导电膜厚度，最后用超声震动方法去除纳/微米球，实现大面积低成本制备具有纳/微米级U形绒面的导电玻璃。该方法得到的导电玻璃重复性好、U形绒面尺度合适、分布均匀、生产效率高、生产成本低，适合于推广应用。

Description

一种太阳能电池专用绒面导电玻璃及其制备方法与应用
技术领域
本发明属于特殊玻璃生产技术领域，具体涉及一种太阳能电池专用绒面导电玻璃及其制备方法与应用。
背景技术
导电玻璃是一种在普通平板玻璃的一侧镀有透明导电薄膜，使得整个玻璃具有透明和导电双重功效的特种玻璃。除了在液晶显示器、保温门窗等方面的应用外，导电玻璃在光伏薄膜电池中通常是必不可少的组成部分——用作电池的透明电极和基板。导电玻璃光电品质的高低直接影响光伏电池的性能，因此是制备非晶硅、微晶硅、碲化铬、铜铟镓硒薄膜电池等的关键原材料之一。如何低成本地制备高品质太阳能电池专用导电玻璃，是制备低成本高效率太阳能电池，实现太阳能廉价发电的必要前提条件。
目前，现有的用于生产太阳能电池的专用导电玻璃及制备方法有：
1）磁控溅射制备的氧化铟锡（ITO）导电玻璃；
2）磁控溅射制备的氧化锌铝（AZO）导电玻璃；
3）常压化学气相沉积法制备的掺氟二氧化锡（FTO）导电玻璃；
4）低压化学气相沉积法制备的掺硼氧化锌（BZO）或氧化锌铝（AZO）导电玻璃。
为增强电池的光吸收，导电玻璃的透明导电膜需要具有纳/微米尺度的绒度，即不平整度，使得光在入射时发生漫散射（通常通过雾度值来测量），增加光在电池内部传输的光程（如图1所示）。
目前实验室规模的导电玻璃样品中，主要有以下三种绒面：
1）磁控溅射后用盐酸湿法刻蚀制备的氧化锌铝（AZO）导电玻璃绒面（如图2所示）；
2）常压化学气相沉积法制备的掺氟二氧化锡（FTO）导电玻璃绒面（如图3所示）；
3）低压化学气相沉积法制备的掺硼氧化锌（BZO）或氧化锌铝（AZO）导电玻璃绒面（如图4所示）。
同时，透明导电膜的绒面形态必须保证电池吸收层的薄膜材料品质不会受其不平整度的影响。由于电池的制备过程往往都是各层薄膜按次序叠加生长的，透明导电膜在吸收层生长时是作为吸收层的直接衬底，其形貌直接影响着吸收层薄膜的生长方式和质量。以微晶硅吸收层为例（如图5所示），不同的透明导电膜形貌造成了不同质地的微晶硅吸收层。
当透明导电膜绒面形貌类似V形时（图5A），微晶硅吸收层容易形成裂缝，严重影响太阳能电池的性能。当绒面形貌类似U形时（图5B），微晶硅吸收层裂缝较小，甚至无裂缝（图5C）。此外，碲化铬吸收层对绒面形貌的要求比微晶硅更加苛刻，要求绒面必须全部由较浅的U形凹陷构成。
以上三种现有绒面导电玻璃小规模样品中，只有磁控溅射后湿法刻蚀制备的AZO导电玻璃和低压化学气相沉积的BZO（或AZO）导电玻璃有可能达到U形绒面形貌的要求，但前者在工业化批量生产时遇到了湿法刻蚀工艺不易控制而造成的产品不均匀、不稳定、成品率低的问题，而后者则需要使用长时间的等离子体刻蚀工艺，工业化生产的成本过高。因此，适合于生产微晶硅、碲化铬薄膜电池的U形绒面导电玻璃的工业化低成本生产方法在全世界至今一直是个空白。正因为如此，微晶硅薄膜电池的生产成本仍然很高，而碲化铬薄膜电池在生产时不得不只使用几乎没有任何绒度的平面FTO导电玻璃。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种成本低廉的、具有均匀可控的纳米级U形绒面的大面积太阳能电池专用绒面导电玻璃。
本发明的另一目的在于提供上述太阳能电池专用绒面导电玻璃的制备方法，采用磁控溅射镀透明导电膜（ITO、AZO等），然后用浸镀的方法将纳/微米球（直径10纳米-100微米）吸附于其表面作为掩模，再通过磁控溅射在纳/微米球间隙增加透明导电膜厚度，最后用超声震动等机械或化学方法去除纳/微米球，实现大面积低成本制备具有U形绒面的导电玻璃。
本发明的再一目的在于提供上述太阳能电池专用绒面导电玻璃的应用。
本发明的目的通过下述技术方案实现：
一种太阳能电池专用绒面导电玻璃，其结构和组成是：在玻璃基片上镀有透明导电膜，透明导电膜的上表面是带有纳米级U形绒度的绒面；
所述的透明导电膜的厚度是100-5000纳米；
所述的透明导电膜是氧化铟锡（ITO）或氧化锌铝（AZO）或其它透明导电薄膜材料（等电点大于3）中的一种。
上述太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上透明导电膜，得到导电玻璃A；
（2）取单分散纳/微米球悬浮液，调节该悬浮液的pH值为3-7；将导电玻璃A浸入悬浮液中，浸泡2-15分钟，取出，用水冲洗，得到导电玻璃B；
由于ITO、AZO等透明导电膜的等电点(isoelectric point)比较大，一般为6-10，而二氧化硅或聚苯乙烯纳/微米球的等电点比较小，一般为2-4，因此当把导电玻璃浸泡于含有纳/微米球的中性(PH值为7)或弱酸性(PH值为3-6)的悬浮液中时，透明导电膜表面带负电，而纳/微米球表面带正电，造成两种材料互相静电吸引，经过一段时间后，透明导电膜表面几乎全部被一层纳/微米球所吸附。纳/微米球在导电玻璃上的覆盖面积比例随纳/微米球悬浮液的浓度、pH值和浸镀时间而变化。
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射方式镀上透明导电膜，得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为100-5000纳米；
第二次使用磁控溅射镀膜的原因是磁控溅射过程中镀膜材料可以进入纳/微米球的侧下方，形成无棱角的U形表面形貌（如图7所示）。
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃C表面形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃。该导电玻璃在可见光波段的透过率为80%以上，面电阻小于10欧姆。
步骤（1）和（3）所述的磁控溅射，其条件如下：基础真空度：<1×10-5Torr；工作气压：1-10mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：100-1000W；衬底温度：20-500℃；沉积速率：10-100nm/min；
步骤（2）所述的纳/微米球的直径为10纳米-100微米；
步骤（2）所述的纳/微米球的材质是二氧化硅或聚苯乙烯中的一种；
步骤（2）所述的悬浮液中纳/微米球的质量体积浓度是0.01-1%；
步骤（2）所述的悬浮液的溶剂是水、甲醇或乙醇中一种；
步骤（2）所述的导电玻璃在悬浮液中的浸泡时间优选8-10分钟；
上述的太阳能电池专用绒面导电玻璃可以用作太阳能电池的透明电极或基板。
本发明所述的纳/微米球是指纳米球或微米球；所述的纳/微米是指纳米或微米。
本发明相对于现有技术具有如下的优点及效果：
从工业化生产的角度，本方法所使用的平板玻璃磁控溅射、浸镀、清洗等工艺均与标准工业生产工艺相匹配，生产效率高，可应用的玻璃面积大，重复性好，成品率高，且采用的纳/微米球制备成本低廉，十分适合于低成本高质量的太阳能电池专用导电玻璃的生产。
附图说明
图1是非晶硅薄膜电池的切面结构示意图。
图2是磁控溅射后用盐酸湿法刻蚀制备的氧化锌铝（AZO）导电玻璃绒面显微结构示意图。
图3是常压化学气相沉积法制备的掺氟二氧化锡（FTO）导电玻璃绒面显微结构示意图。
图4是低压化学气相沉积法制备的掺硼氧化锌（BZO）或氧化锌铝（AZO）导电玻璃绒面显微结构示意图。
图5是不同导电玻璃衬地上微晶硅薄膜的生长状态比较。
图6是本发明太阳能电池专用绒面导电玻璃的制备方法流程示意图。
图7是以纳/微米球为掩模进行磁控溅射镀膜时薄膜沉积的方式示意图。
图8是实施例1中镀上了纳/微米球的导电玻璃。
图9是实施例2中镀上了纳/微米球的导电玻璃。
图10是实施例3中镀上了纳/微米球的导电玻璃。
图11是实施例4中镀上了纳/微米球的导电玻璃。
图12是实施例5中镀上了纳/微米球的导电玻璃。
图13是实施例6中镀上了纳/微米球的导电玻璃。
图14是实施例1的导电玻璃去除纳米球后的表面形貌俯视图；A-放大倍数10000，B-放大倍数5000。
图15是实施例1的导电玻璃去除纳米球后的表面形貌30度倾角侧面图；A-放大倍数10000，B-放大倍数5000。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上AZO透明导电膜，得到导电玻璃A；磁控溅射的条件如下：基础真空度：0.8×10-5Torr；工作气压：1mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：1000W；衬底温度：20℃；沉积速率：100nm/min；
（2）取聚苯乙烯纳米球（直径1000纳米）在水中的悬浮液（质量体积浓度为0.25%），调节该悬浮液的pH值为4；将导电玻璃A浸入悬浮液中，浸泡2分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图8可见导电玻璃B上浸镀了一层纳米球；
（3）利用纳米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上AZO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳米球的半径，透明导电膜的总厚度为2000纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳米球；得到一种太阳能电池专用绒面导电玻璃。去除纳米球之后导电玻璃表面形貌如图14和图15所示，绒面形貌的凹陷区率较大，呈明显的U形，且在导电玻璃的表面分布均匀；该导电玻璃在可见光波段的透过率为82%、面电阻3欧姆，可以用作太阳能电池的透明电极或基板。
实施例2
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上AZO透明导电膜，得到导电玻璃A；磁控溅射的条件如下：基础真空度：0.7×10-5Torr；工作气压：10mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：100W；衬底温度：500℃；沉积速率：10nm/min；
（2）取二氧化硅纳米球（直径1000纳米）在乙醇中的悬浮液（质量体积浓度为0.5%），调节该悬浮液的pH值为7；将导电玻璃A浸入悬浮液中，浸泡4分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图9可见导电玻璃B上浸镀了一层纳米球；
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上AZO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为3000纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃表面C形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃，该导电玻璃在可见光波段的透过率为83%、面电阻4欧姆，可以用作太阳能电池的透明电极或基板。
实施例3
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上ITO透明导电膜，得到导电玻璃A，磁控溅射的条件如下：基础真空度：0.9×10-5Torr；工作气压：4mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：800W；衬底温度：100℃；沉积速率：80nm/min；
（2）取聚苯乙烯纳米球（直径1000纳米）在水中的悬浮液（质量体积浓度为0.1%），调节该悬浮液的pH值为6；将导电玻璃A浸入悬浮液中，浸泡6分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图10可见导电玻璃B上浸镀了一层纳米球；
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上ITO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为1000纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃C表面形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃，该导电玻璃在可见光波段的透过率为81%、面电阻2欧姆，可以用作太阳能电池的透明电极或基板。
实施例4
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上AZO透明导电膜，得到导电玻璃A，磁控溅射的条件如下：基础真空度：0.5×10-5Torr；工作气压：6mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：200W；衬底温度：400℃；沉积速率：40nm/min；
（2）取聚苯乙烯纳米球（直径1000纳米）在水中的悬浮液（质量体积浓度为0.75%），调节该悬浮液的pH值为3；将导电玻璃A浸入悬浮液中，浸泡8分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图11可见导电玻璃B上浸镀了一层纳米球，覆盖率达到90%以上。
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上AZO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为100纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃C表面形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃，该导电玻璃在可见光波段的透过率为84%、面电阻5欧姆，可以用作太阳能电池的透明电极或基板。
实施例5
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上AZO透明导电膜，得到导电玻璃A，磁控溅射的条件如下：基础真空度：0.6×10-5Torr；工作气压：8mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：400W；衬底温度：300℃；沉积速率：20nm/min；
（2）取聚苯乙烯纳米球（直径1000纳米）在甲醇中的悬浮液（质量体积浓度为1%），调节该悬浮液的pH值为3；将导电玻璃A浸入悬浮液中，浸泡10分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图12可见导电玻璃B上浸镀了一层纳米球，覆盖率达到90%以上。
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上AZO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为5000纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃C表面形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃，该导电玻璃在可见光波段的透过率为82%、面电阻3欧姆，可以用作太阳能电池的透明电极或基板。
实施例6
一种太阳能电池专用绒面导电玻璃的制备方法，包括以下步骤（如图6所示）：
（1）采用磁控溅射方式在玻璃基片上镀上AZO透明导电膜，得到导电玻璃A，磁控溅射的条件如下：基础真空度：0.4×10-5Torr；工作气压：2mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：600W；衬底温度：200℃；沉积速率：60nm/min；
（2）取聚苯乙烯纳米球（直径1000纳米）在甲醇中的悬浮液（质量体积浓度为0.01%），调节该悬浮液的pH值为4；将导电玻璃A浸入悬浮液中，浸泡15分钟，取出，用水轻轻冲洗，得到导电玻璃B；
图13可见导电玻璃B上浸镀了一层纳米球；
（3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射的方式镀上AZO透明导电膜（磁控溅射的条件同步骤（1）），得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为4000纳米；
（4）超声清洗去除沉积在透明导电膜表面的纳/微米球，从而在导电玻璃C表面形成U形纳/微米大小的绒度，得到太阳能电池专用绒面导电玻璃，该导电玻璃在可见光波段的透过率为82%、面电阻3欧姆，可以用作太阳能电池的透明电极或基板。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种太阳能电池专用绒面导电玻璃，其特征在于：在玻璃基片上镀有透明导电膜，透明导电膜的上表面是带有纳/微米级U形绒度的绒面。
  2. 根据权利要求1所述的太阳能电池专用绒面导电玻璃，其特征在于：所述的透明导电膜的厚度为100-5000纳米。
  3. 根据权利要求1或2所述的太阳能电池专用绒面导电玻璃，其特征在于：所述的透明导电膜是氧化铟锡或氧化锌铝中的一种。
  4. 权利要求1所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于包括以下步骤：
    （1）采用磁控溅射方式在玻璃基片上镀上透明导电膜，得到导电玻璃A；
    （2）取纳/微米球悬浮液，调节该悬浮液的pH值为3-7；将导电玻璃A浸入悬浮液中，浸泡2-15分钟，取出，用水冲洗，得到导电玻璃B；
    （3）利用纳/微米球作为掩模，在导电玻璃B上用磁控溅射方式镀上透明导电膜，得到导电玻璃C，新镀的膜厚度不超过纳/微米球的半径，透明导电膜的总厚度为100-5000纳米；
    （4）超声清洗去除沉积在透明导电膜表面的纳/微米球，得到太阳能电池专用绒面导电玻璃。
  5. 根据权利要求4所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于：步骤（1）和（3）所述的磁控溅射，其条件如下：基础真空度：<1×10-5Torr；工作气压：1-10mTorr；工作气体：Ar+O2；溅射源：支流或射频13.56MHz；功率：100-1000W；衬底温度：20-500℃；沉积速率：10-100nm/min。
  6. 根据权利要求4所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于：步骤（2）所述的纳/微米球的直径为10纳米-100微米。
  7. 根据权利要求4所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于：步骤（2）所述的纳/微米球的材质是二氧化硅或聚苯乙烯中的一种。
  8. 根据权利要求4所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于：
    步骤（2）所述的悬浮液中纳/微米球的质量体积浓度是0.01-1%；
    步骤（2）所述的悬浮液的溶剂是水、甲醇或乙醇中一种。
  9. 根据权利要求4所述的太阳能电池专用绒面导电玻璃的制备方法，其特征在于：步骤（2）所述的导电玻璃在悬浮液中的浸泡时间为8-10分钟。
  10. 权利要求1所述的太阳能电池专用绒面导电玻璃作为太阳能电池透明电极或基板的应用。
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