WO2023040120A1 - 透明导电氧化物薄膜及异质结太阳能电池 - Google Patents

透明导电氧化物薄膜及异质结太阳能电池 Download PDF

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WO2023040120A1
WO2023040120A1 PCT/CN2021/142673 CN2021142673W WO2023040120A1 WO 2023040120 A1 WO2023040120 A1 WO 2023040120A1 CN 2021142673 W CN2021142673 W CN 2021142673W WO 2023040120 A1 WO2023040120 A1 WO 2023040120A1
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film
amorphous silicon
oxide film
type doped
doped amorphous
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PCT/CN2021/142673
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French (fr)
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石建华
张海川
袁强
蒙春才
孟凡英
刘正新
程琼
周华
周丹
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中威新能源(成都)有限公司
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Priority to EP21893120.2A priority Critical patent/EP4174958A4/en
Priority to AU2021385099A priority patent/AU2021385099A1/en
Priority to US17/780,937 priority patent/US20240162364A1/en
Publication of WO2023040120A1 publication Critical patent/WO2023040120A1/zh

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    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • 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
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    • 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]
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    • 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]
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    • 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
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    • H01L31/03762—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 amorphous semiconductors including only elements of Group IV of the Periodic Table
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    • 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 potential barriers
    • 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 potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/074—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 potential barriers the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic Table, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
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    • 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 potential barriers
    • 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 potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0745—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 potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—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 potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
    • H—ELECTRICITY
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    • 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
    • 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 present application relates to the technical field of solar cells, in particular, to transparent conductive oxide thin films and heterojunction solar cells.
  • TCO Transparent conductive oxide
  • TCO thin films In the application of heterojunction solar cells (SHJ), TCO thin films have three important functions: 1. Act as an effective collection and transport carrier for photogenerated carriers, and need to have good conductivity; 2. Act as a surface anti-reflection window layer ; 3, as a surface protection layer. In addition, the TCO thin film must not only have the photoelectric performance required by the battery performance, but also strictly control the material and preparation costs of the TCO thin film.
  • the indium tin oxide (ITO) thin film is a commonly used TCO thin film, but the current price of indium is relatively high, resulting in a relatively high cost of the indium tin oxide (ITO) thin film.
  • Aluminum-doped zinc oxide (AZO) film is another commonly used TCO film. Because the main components of this film are Zn and Al, its cost is only about 1/10 of that of ITO film. In related technologies, in order to reduce costs, there are low-cost AZO films used instead of ITO films. However, the efficiency of SHJ cells prepared by using AZO films as TCO films is low and has serious battery attenuation problems. It is difficult for end products to meet the requirements of the National Standards Committee IEC : Requirements for related indicators of 61215.
  • Embodiments of the present application provide a transparent conductive oxide thin film and a heterojunction solar cell, which can ensure cell efficiency, reduce cell attenuation, and reduce costs at the same time.
  • a transparent conductive oxide film which may include a seed layer, a conductive layer and a protective layer
  • the seed layer may include an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film
  • the conductive layer may be Gallium/aluminum co-doped zinc oxide film
  • the protective layer can be indium tin oxide film
  • the thickness of the indium tin oxide film in the transparent conductive oxide film can be smaller than the thickness of the gallium/aluminum co-doped zinc oxide film.
  • heterojunction solar cell which may include:
  • the transparent conductive oxide film can be arranged on the surface of the P-type doped amorphous silicon film and the N-type doped amorphous silicon film; the seed layer is close to the P-type doped amorphous silicon film.
  • An amorphous silicon film and an N-type doped amorphous silicon film are provided;
  • Electrode the electrode can be set on the surface of the transparent conductive oxide film.
  • the silicon wafer may be a single crystal silicon wafer.
  • the carrier concentration of the seed layer may be >6 ⁇ 10 20 , and the thickness may be ⁇ 10 nm.
  • the carrier concentration of the conductive layer may be ⁇ 2 ⁇ 10 20 , and the thickness may be >40nm.
  • the thickness of the transparent conductive oxide film on the surface of the N-type doped amorphous silicon film may be 60 nm to 150 nm.
  • the carrier concentration of the seed layer may be ⁇ 1 ⁇ 10 20 , and the thickness may be ⁇ 10 nm.
  • the carrier concentration of the conductive layer may be >3 ⁇ 10 20 , and the thickness may be >40 nm.
  • the transparent conductive oxide film on the surface of the P-type doped amorphous silicon film may be 60nm to 250nm.
  • both the P-type doped amorphous silicon film and the N-type doped amorphous silicon film may contain microcrystalline silicon.
  • the crystallization rate of the P-type doped amorphous silicon film may be >20%; and/or, the crystallization rate of the N-type doped amorphous silicon film may be >25%.
  • neither the P-type doped amorphous silicon film nor the N-type doped amorphous silicon film may contain microcrystalline silicon.
  • the carrier concentration of the seed layer may be 5 ⁇ 10 20 and the thickness may be 12 nm, or the conductive The layer had a carrier concentration of 3 ⁇ 10 20 and a thickness of 35 nm.
  • the carrier concentration of the seed layer may be 1.5 ⁇ 10 20 and the thickness may be 12 nm, or the conductive The layer had a carrier concentration of 2.5 ⁇ 10 20 and a thickness of 35 nm.
  • the seed layer in the transparent conductive oxide film includes indium tin oxide film or gallium/aluminum co-doped zinc oxide film.
  • the contact barrier of the crystalline silicon film can obtain a lower contact resistance; at the same time, the indium tin oxide film is used as a protective layer, which can improve the stability of the transparent conductive oxide film, ensure battery efficiency and reduce battery attenuation.
  • the conductive layer is a gallium/aluminum co-doped zinc oxide film, and the thickness of the indium tin oxide film in the transparent conductive oxide film is smaller than that of the gallium/aluminum co-doped zinc oxide film, which can reduce the cost.
  • FIG. 1 is a schematic structural view of a heterojunction solar cell according to an embodiment of the present application
  • FIG. 2 is a schematic structural diagram of a transparent conductive oxide thin film according to an embodiment of the present application.
  • Icons 10-heterojunction solar cell; 11-silicon wafer; 12-intrinsic amorphous silicon film; 13-P-type doped amorphous silicon film; 14-N-type doped amorphous silicon film; 15-transparent conductive Oxide thin film; 151-seed layer; 152-conductive layer; 153-protective layer; 16-electrode.
  • a transparent conductive oxide thin film 15 please refer to FIG. /aluminum co-doped zinc oxide (GAZO) film
  • the conductive layer 152 may be a gallium/aluminum co-doped zinc oxide film
  • the protective layer 153 may be an indium tin oxide film.
  • the seed layer 151 in the transparent conductive oxide film 15 may include an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film, and the seed layer 151 can reduce the amount of doped amorphous silicon in the transparent conductive oxide film 15 and the solar cell.
  • the contact barrier of the film can obtain lower contact resistance; at the same time, the indium tin oxide film is used as the protective layer 153, which can improve the stability of the transparent conductive oxide film 15, ensure battery efficiency and reduce battery attenuation.
  • the cost of the gallium/aluminum co-doped zinc oxide film is lower than the cost of the indium tin oxide film, when the conductive layer 152 is a gallium/aluminum co-doped zinc oxide film, and the indium tin oxide film in the transparent conductive oxide film 15 When the thickness of the film is smaller than that of the gallium/aluminum co-doped zinc oxide film, the cost can be effectively reduced.
  • the inventors of the present application have found in research that if the indium tin oxide film is used as the conductive layer 152 and the gallium/aluminum co-doped zinc oxide film is used as the protective layer 153, the stability of the transparent conductive oxide film 15 is low, and the Affect battery efficiency and cause serious battery attenuation.
  • the thickness of the ITO film in the transparent conductive oxide film 15 is the sum of the thickness of the seed layer 151 and the protective layer 153 .
  • the thickness of the gallium/aluminum co-doped zinc oxide film in the transparent conductive oxide film 15 is the ratio of the thickness of the seed layer 151 to the thickness of the conductive layer 152. sum.
  • the doping ratio of tin in the ITO film is not more than 10wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%.
  • the indium tin oxide film in the transparent conductive oxide film 15 can be an indium tin oxide film with a tin doping ratio, or can be formed by stacking multiple layers of indium tin oxide films with different tin doping ratios. become.
  • the doping ratio of aluminum in the GAZO film is not more than 3wt%, such as 0.5wt%, 1wt%, 0.5wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%.
  • the gallium doping ratio in the GAZO film is 0.5-3.5wt%, such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, 0.5wt%, 2.5wt%, 3wt% or 3.5wt%.
  • the GAZO film in the transparent conductive oxide thin film 15 may be a GAZO film with one doping ratio, or may be formed by stacking multiple layers of GAZO films with different doping ratios.
  • FIG. 1 may include:
  • the transparent conductive oxide film 15 can be disposed on the surface of the P-type doped amorphous silicon film 13 and the N-type doped amorphous silicon film 14; the seed layer 151 can be Set close to the P-type doped amorphous silicon film 13 and the N-type doped amorphous silicon film 14; and
  • the electrode 16 may be disposed on the surface of the transparent conductive oxide film 15 .
  • the seed layer 151 in the transparent conductive oxide film 15 may include an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film
  • the seed layer 151 can reduce the contact between the transparent conductive oxide film 15 and the P-type doped amorphous silicon film. 13 and the contact barrier of N-type doped amorphous silicon thin film 14, obtain lower contact resistance;
  • Conductive layer 152 can be gallium/aluminum co-doped zinc oxide film, then can reduce cost; Simultaneously, by indium tin oxide film As the protective layer 153, the stability of the transparent conductive oxide thin film 15 can be improved to ensure battery efficiency and reduce battery attenuation.
  • both the P-type doped amorphous silicon film 13 and the N-type doped amorphous silicon film 14 may contain microcrystalline silicon.
  • Both the P-type doped amorphous silicon film 13 and the N-type doped amorphous silicon film 14 can have microcrystalline silicon, so that the conductivity of the P-type doped amorphous silicon film 13 and the N-type doped amorphous silicon film 14 Better, smaller activation energy, less bombardment damage, lower contact barrier between P-type doped amorphous silicon film 13 and N-type doped amorphous silicon film 14 and TCO film, which is beneficial to reduce contact resistance and improve battery performance. efficiency.
  • the crystallization rate of the P-type doped amorphous silicon film 13 may be >20%, such as 21%, 22%, 23%, 24%, 25%, 26%, 28% or 30%.
  • the crystallization rate of the N-type doped amorphous silicon film 14 may be >25%, such as 26%, 28%, 30%, 32%, 35% or 40%.
  • the silicon wafer 11 may be a single crystal silicon wafer 11 .
  • the carrier concentration of the seed layer 151 may be >6 ⁇ 10 20 , and the thickness may be ⁇ 10 nm.
  • the seed layer 151 can include an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film, and the carrier concentration of the seed layer 151 can be >6 ⁇ 10 20 , and the thickness can be ⁇ 10 nm, which can further reduce the N-type doping
  • the contact barrier between the amorphous silicon film 14 and the transparent conductive oxide film 15 can obtain lower contact resistance, which is beneficial to further improve the cell efficiency.
  • the carrier concentration of the seed layer 151 may be 6.2 ⁇ 10 20 , 6.5 ⁇ 10 20 , 7 ⁇ 10 20 , 8 ⁇ 10 20 , 9 ⁇ 10 20 or 10 ⁇ 10 20 .
  • the thickness of the seed layer 151 may be 1 nm, 3 nm, 5 nm, 7 nm or 9 nm.
  • the carrier concentration of the conductive layer 152 may be ⁇ 2 ⁇ 10 20 , and the thickness may be >40 nm.
  • the carrier concentration can be ⁇ 2 ⁇ 10 20 , and the thickness can be >40nm, the parasitic absorption of the transparent conductive oxide film 15 can be reduced, thereby further improving the cell efficiency of the heterojunction solar cell 10 , to reduce battery attenuation.
  • the carrier concentration of the conductive layer 152 can be 0.2 ⁇ 10 20 , 0.5 ⁇ 10 20 , 0.8 ⁇ 10 20 , 1 ⁇ 10 20 , 1 ⁇ 10 20 , 1.2 ⁇ 10 20 , 1.5 ⁇ 10 20 or 1.8 ⁇ 10 20 .
  • the thickness of the conductive layer 152 may be 42 nm, 45 nm, 50 nm, 52 nm or 55 nm.
  • the protective layer 153 may have a thickness of 10-40 nm, such as 10 nm, 20 nm, 30 nm or 40 nm.
  • the thickness of the transparent conductive oxide film 15 on the surface of the N-type doped amorphous silicon film 14 in the embodiment of the present application may be 60 to 150 nm, such as 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130nm, 140nm or 150nm.
  • the carrier concentration of the seed layer 151 may be ⁇ 1 ⁇ 10 20 , and the thickness may be ⁇ 10 nm.
  • the seed layer 151 includes an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film, and the carrier concentration of the seed layer 151 is less than 1 ⁇ 10 20 , and the thickness is less than 10 nm, the adaptability of the interface work function can be improved.
  • the contact barrier between the P-type doped amorphous silicon film 13 and the transparent conductive oxide film 15 is further reduced, thereby obtaining lower contact resistance, which is beneficial to further improving battery efficiency.
  • the carrier concentration of the seed layer 151 can be 0.2 ⁇ 10 20 , 0.5 ⁇ 10 20 , 0.8 ⁇ 10 20 or 0.9 ⁇ 10 20 .
  • the thickness of the seed layer 151 may be 1 nm, 3 nm, 5 nm, 7 nm or 9 nm.
  • the carrier concentration of the conductive layer 152 can be >3 ⁇ 10 20 , and the thickness can be >40 nm.
  • the transparent conductive oxide thin film 15 can be guaranteed to have better conductivity.
  • the carrier concentration of the conductive layer 152 can be 3.2 ⁇ 10 20 , 3.5 ⁇ 10 20 , 4 ⁇ 10 20 , 4.5 ⁇ 10 20 , 5 ⁇ 10 20 or 6 ⁇ 10 20 .
  • the thickness of the conductive layer 152 may be 42 nm, 45 nm, 50 nm, 52 nm or 55 nm.
  • the protective layer 153 may have a thickness of 10 nm to 40 nm, such as 10 nm, 20 nm, 30 nm or 40 nm.
  • the thickness of the transparent conductive oxide film 15 on the surface of the P-type doped amorphous silicon film 13 in the embodiment of the present application is 60nm to 250nm, such as 60nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, 220nm or 250nm.
  • the embodiment of the present application also provides a manufacturing process of a heterojunction solar cell 10, which may include:
  • the electrodes 16 are formed on the surface of the transparent conductive oxide film 15 by screen printing.
  • the transparent conductive oxide thin film 15 and the heterojunction solar cell 10 of the present application will be further described in detail below with reference to examples.
  • This implementation provides a heterojunction solar cell, which may include:
  • the P-type doped amorphous silicon film may contain microcrystalline silicon, and its crystallization rate may be 20%, and the N-type doped amorphous silicon film may contain microcrystalline silicon, and its crystallization rate may be 30%.
  • the TCO film can be arranged on the surface of the P-type doped amorphous silicon film and the N-type doped amorphous silicon film.
  • the TCO film on the surface of the N-type doped amorphous silicon film can include a seed layer with a thickness of 10nm, a conductive layer with a thickness of 60nm, and a protective layer with a thickness of 20nm, the seed layer can be an ITO film, carrying current
  • the carrier concentration can be 8 ⁇ 10 20 ;
  • the conductive layer can be a GAZO film, the carrier concentration can be 1 ⁇ 10 20 , and the protective layer can be an ITO film.
  • the TCO film on the surface of the P-type doped amorphous silicon film can include a seed layer with a thickness of 10nm, a conductive layer with a thickness of 60nm, and a protective layer with a thickness of 20nm, the seed layer can be an ITO film, carrying current
  • the carrier concentration can be 0.8 ⁇ 10 20 ;
  • the conductive layer can be a GAZO film, the carrier concentration can be 4 ⁇ 10 20 , and the protective layer can be an ITO film.
  • the seed layer of the TCO thin film is arranged close to the P-type doped amorphous silicon thin film and the N-type doped amorphous silicon thin film.
  • This implementation also provides a method for preparing a heterojunction solar cell, the steps of which may include:
  • the surface of the monocrystalline silicon wafer is textured and chemically cleaned to form a surface light-trapping structure, and a clean surface is formed after chemical cleaning again;
  • Intrinsic amorphous silicon thin films are respectively deposited on the two surfaces of the single crystal silicon wafer;
  • the magnetron sputtering process conditions of the seed layer of the TCO film include: the sputtering target is ITO, sputtering The sputtering power density is 5KW/m, the sputtering pressure is 0.45Pa, the sputtering temperature is 180°C, and the volume ratio of oxygen/argon is 1.0%; the magnetron sputtering process conditions of the conductive layer of the TCO film include: sputtering power The density is 5KW/m, the sputtering pressure is 0.45Pa, the sputtering temperature is 180°C, and the volume ratio of oxygen/argon is 2%; the magnetron sputtering process conditions of the protective layer of the TCO film include: sputtering power density 5KW /m, the sputtering pressure is 0.35 Pa, the sputtering temperature
  • a TCO film is formed on the surface of the N-type doped amorphous silicon film by magnetron sputtering coating.
  • the magnetron sputtering process conditions of the seed layer of the TCO film include: the sputtering target is ITO, the sputtering power The density is 5KW/m, the sputtering pressure is 0.45Pa, the sputtering temperature is 180°C, and the volume ratio of oxygen/argon is 3.0%; the magnetron sputtering process conditions of the conductive layer of the TCO film include: sputtering power density 5KW /m, sputtering pressure 0.45Pa, sputtering temperature 180°C, oxygen/argon volume ratio ratio of 2%; the magnetron sputtering process conditions of the protective layer of the TCO film include: sputtering power density 5KW/m , a sputtering pressure of 0.35 Pa, a sputtering temperature of 180° C., and an oxygen
  • Metal electrodes are formed on the surface of the TCO film by screen printing.
  • This embodiment provides a heterojunction solar cell. Compared with Embodiment 1, the only difference lies in the TCO of the surface of the P-type doped amorphous silicon film and the N-type doped amorphous silicon film of this embodiment.
  • the seed layer may be a GAZO film, and the thickness of the protective layer may be 10nm.
  • This embodiment also provides a method for preparing the aforementioned heterojunction solar cell. Compared with Embodiment 1, the only difference is that the magnetic field of the seed layer in step (5) and step (6) in Embodiment 1 is In the controlled sputtering process conditions, the sputtering target is replaced by ITO and the sputtering target is GAZO.
  • This embodiment provides a heterojunction solar cell. Compared with Embodiment 2, the only difference is that both the P-type doped amorphous silicon thin film and the N-type doped amorphous silicon thin film of this embodiment may not Contains microcrystalline silicon.
  • This embodiment provides a heterojunction solar cell. Compared with Embodiment 2, the only difference is that the carrier concentration and thickness of the seed layer and the conductive layer in the TCO thin film of this embodiment are different from Embodiment 2.
  • the carrier concentration of the seed layer in the TCO film on the surface of the N-type doped amorphous silicon film, may be 5 ⁇ 10 20 , and the thickness may be 12 nm.
  • the carrier concentration of the seed layer in the TCO film on the surface of the P-type doped amorphous silicon film, the carrier concentration of the seed layer may be 1.5 ⁇ 10 20 , and the thickness may be 12 nm.
  • This embodiment provides a heterojunction solar cell. Compared with Embodiment 2, the only difference is that the carrier concentration and thickness of the seed layer and the conductive layer in the TCO thin film of this embodiment are different from Embodiment 2.
  • the carrier concentration of the conductive layer in the TCO film on the surface of the N-type doped amorphous silicon film, the carrier concentration of the conductive layer may be 3 ⁇ 10 20 , and the thickness may be 35 nm.
  • the carrier concentration of the conductive layer in the TCO film on the surface of the P-type doped amorphous silicon film, the carrier concentration of the conductive layer may be 2.5 ⁇ 10 20 , and the thickness may be 35 nm.
  • This comparative example provides a heterojunction solar cell. Compared with Example 2, the only difference is that the TCO film of Comparative Example 1 is an ITO film.
  • This comparative example provides a heterojunction solar cell. Compared with Example 2, the only difference is that the conductive layer of Comparative Example 2 is an ITO film, and the protective layer is a GAZO film.
  • This comparative example provides a heterojunction solar cell. Compared with Example 2, the only difference is that the TCO film of Comparative Example 3 is a GAZO film.
  • the halm online I-V test system was selected to test the open circuit voltage (Voc), The results of short circuit current (Isc), fill factor (FF) and conversion efficiency (Eff) are recorded in Table 1.
  • Example 2 By comparing the experimental results of Example 2, Example 4 and Example 5, it can be found that the conversion efficiency of Example 2 is significantly higher than that of Example 4 and Example 5, which shows that the seed layer and the conductivity of the TCO film of Example 2 The carrier concentration and thickness of the layer are more conducive to improving the conversion efficiency.
  • test conditions of TC200 are: the heterojunction solar cell is cycled 200 times between -40 and 85°C, and Ipm is passed through when the temperature exceeds 25°C.
  • test conditions of DH100 are: the heterojunction solar cell is tested for 1000h under the condition of temperature of 85 ⁇ 2°C and humidity of 85% ⁇ 5%.
  • test conditions of HF10 are: cycle the heterojunction solar cell between -40 and 85°C for 10 cycles, keep the temperature at 85°C for 20h, keep at -40°C for 0.5h for one cycle, and cycle for 24h.
  • the application provides a transparent conductive oxide thin film and a heterojunction solar cell.
  • the transparent conductive oxide film includes a seed layer, a conductive layer and a protective layer, the seed layer includes an indium tin oxide film or a gallium/aluminum co-doped zinc oxide film, the conductive layer is a gallium/aluminum co-doped zinc oxide film, and the protective layer is an oxide film Indium tin film; the thickness of the indium tin oxide film in the transparent conductive oxide film is smaller than the thickness of the gallium/aluminum co-doped zinc oxide film. It can ensure battery efficiency and reduce battery attenuation, while reducing costs.
  • the transparent conductive oxide thin films and heterojunction solar cells of the present application are reproducible and can be used in various industrial applications.
  • the transparent conductive oxide thin film and the heterojunction solar cell of the present application can be used in the field of solar cell technology.

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Abstract

本申请提供一种透明导电氧化物薄膜及异质结太阳能电池，涉及太阳能电池技术领域领域。透明导电氧化物薄膜包括种子层、导电层和保护层，种子层包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，导电层为镓/铝共掺杂氧化锌膜，保护层为氧化铟锡膜；透明导电氧化物薄膜中的氧化铟锡膜的厚度小于镓/铝共掺杂氧化锌膜的厚度。其能够保证电池效率和减少电池衰减，同时能够减少成本。

Description

透明导电氧化物薄膜及异质结太阳能电池
相关申请的交叉引用
本申请要求于2021年09月15日提交中国国家知识产权局的申请号为202111080593.3、名称为“透明导电氧化物薄膜及异质结太阳能电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及太阳能电池技术领域，具体而言，涉及透明导电氧化物薄膜及异质结太阳能电池。
背景技术
透明导电氧化物(TCO)薄膜因其优异的光电性能在low-E玻璃、平板显示、发光二极管、光电探测、光电通信、太阳电池等泛光电半导体领域得到了广泛应用。
在异质结太阳电池(SHJ)应用中，TCO薄膜具有三大重要功能：1、充当光生载流子的有效收集和传输载体，需具备较好的导电性；2、充当表面减反射窗口层；3、充当表面保护层。此外，TCO薄膜除了必须具备满足电池性能所需要的光电性能外，还需严格控制TCO薄膜的物料及制备成本。
其中，氧化铟锡(ITO)薄膜是一种常用的TCO薄膜，但是目前铟的价格较高，导致氧化铟锡(ITO)薄膜的成本较高。而铝掺杂氧化锌(AZO)薄膜是另外一种常用的TCO薄膜，因该薄膜主要成分是Zn和Al，其成本仅为ITO薄膜的1/10左右。相关技术中，为了减少成本，有通过使用低成本的AZO薄膜替代ITO薄膜，但是AZO薄膜作为TCO薄膜制备的SHJ电池效率较低，且具有严重的电池衰减问题，终端产品很难满足国标委IEC：61215的相关指标要求。
发明内容
本申请实施例提供一种透明导电氧化物薄膜及异质结太阳能电池，其能够保证电池效率和减少电池衰减，同时能够减少成本。
本申请实施例是这样实现的：
本申请的一些实施例提供一种透明导电氧化物薄膜，其可以包括种子层、导电层和保护层，种子层可以包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，导电层可以为镓/铝共掺杂氧化锌膜，保护层可以为氧化铟锡膜；
透明导电氧化物薄膜中的氧化铟锡膜的厚度可以小于镓/铝共掺杂氧化锌膜的厚度。
本申请的另一些实施例提供一种异质结太阳能电池，其可以包括：
硅片；
在所述硅片的两个表面的本征非晶硅薄膜；
在其中一个本征非晶硅薄膜表面的P型掺杂非晶硅薄膜，以及在另一个本征非晶硅薄膜表面的N型掺杂非晶硅薄膜；
本申请的一些实施例的透明导电氧化物薄膜，透明导电氧化物薄膜可以设于所述P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜的表面；种子层靠近P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜设置；以及
电极，电极可以设于透明导电氧化物薄膜的表面。
可选地，所述硅片可以为单晶硅片。
可选地，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述种子层的载流子浓度可以>6×10 20，厚度可以<10nm。
可选地，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述导电层的载流子浓度可以<2×10 20，厚度可以>40nm。
可选地，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜的厚度可以为60nm至150nm。
可选地，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述种子层的载流子浓度可以<1×10 20，厚度可以<10nm。
可选地，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述导电层的载流子浓度可以>3×10 20，厚度可以>40nm。
可选地，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜可以为60nm至250nm。
可选地，所述P型掺杂非晶硅薄膜和所述N型掺杂非晶硅薄膜中均可以具有微晶硅。
可选地，所述P型掺杂非晶硅薄膜的晶化率可以>20％；和/或，所述N型掺杂非晶硅薄膜的晶化率可以>25％。
可选地，所述P型掺杂非晶硅薄膜和所述N型掺杂非晶硅薄膜中均可以不含有微晶硅。
可选地，所述N型掺杂非晶硅薄膜表面的所述透明氧化物薄膜中，所述种子层的载流子浓度可以为5×10 20、厚度可以为12nm，或者，所述导电层的载流子浓度为3×10 20、厚度为35nm。
可选地，所述P型掺杂非晶硅薄膜表面的所述透明氧化物薄膜中，所述种子层的载流子浓度可以为1.5×10 20、厚度可以为12nm，或者，所述导电层的载流子浓度为2.5×10 20、厚度为35nm。
本申请实施例的透明导电氧化物薄膜及异质结太阳能电池的有益效果至少包括：
透明导电氧化物薄膜中的种子层包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，该种子层能 够降低透明导电氧化物薄膜与P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜的接触势垒，获得较低的接触电阻；同时，由氧化铟锡膜作为保护层，能够提高透明导电氧化物薄膜的稳定性，保证电池效率和减少电池衰减。其中，导电层为镓/铝共掺杂氧化锌膜，且透明导电氧化物薄膜中的氧化铟锡膜的厚度小于镓/铝共掺杂氧化锌膜的厚度，则能够减少成本。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请实施例的异质结太阳能电池的结构示意图；
图2为本申请实施例的透明导电氧化物薄膜的结构示意图。
图标：10-异质结太阳能电池；11-硅片；12-本征非晶硅薄膜；13-P型掺杂非晶硅薄膜；14-N型掺杂非晶硅薄膜；15-透明导电氧化物薄膜；151-种子层；152-导电层；153-保护层；16-电极。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
以下针对本申请实施例的透明导电氧化物薄膜15及异质结太阳能电池10进行具体说明：
本申请的一些实施例提供一种透明导电氧化物薄膜15，请参照图2，其可以包括种子层151、导电层152和保护层153，种子层151可以包括氧化铟锡(ITO)膜或镓/铝共掺杂氧化锌(GAZO)膜，导电层152可以为镓/铝共掺杂氧化锌膜，保护层153可以为氧化铟锡膜。
透明导电氧化物薄膜15中的种子层151可以包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，该种子层151能够降低透明导电氧化物薄膜15与太阳能电池中的掺杂非晶硅薄膜的接触势垒，获得较低的接触电阻；同时，由氧化铟锡膜作为保护层153，能够提高透明导电氧化物薄膜15的稳定性，保证电池效率和减少电池衰减。由于镓/铝共掺杂氧化锌膜的成本低于氧化铟锡膜的成本，则当导电层152为镓/铝共掺杂氧化锌膜，且透明导电氧化物薄膜15中的氧化铟锡膜的厚度小于镓/铝共掺杂氧化锌膜的厚度时，能够有效减少成本。
本申请的发明人在研究中发现，如果以氧化铟锡膜作为导电层152，以镓/铝共掺杂氧 化锌膜作为保护层153，则透明导电氧化物薄膜15的稳定性较低，会影响电池效率，造成比较严重的电池衰减。
需要说明的是，当种子层151包括氧化铟锡膜时，透明导电氧化物薄膜15中的氧化铟锡膜的厚度即为种子层151的厚度与保护层153的厚度的总和。当种子层151包括镓/铝共掺杂氧化锌膜时，则透明导电氧化物薄膜15中的镓/铝共掺杂氧化锌膜的厚度即为种子层151的厚度与导电层152的厚度的总和。
示例性地，ITO膜中的锡的掺杂比例不大于10wt％，例如为1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％或10wt％。
需要说明的是，透明导电氧化物薄膜15中的氧化铟锡膜，可以是一种锡掺杂比例的氧化铟锡膜，也可以是多层不同的锡掺杂比例的氧化铟锡膜层叠而成。
示例性地，GAZO膜中的铝掺杂比例不大于3wt％，例如为0.5wt％、1wt％、0.5wt％、1.5wt％、2wt％、2.5wt％或3wt％。示例性地，GAZO膜中的镓掺杂比例为0.5～3.5wt％，例如为0.5wt％、1wt％、1.5wt％、2wt％、0.5wt％、2.5wt％、3wt％或3.5wt％。
需要说明的是，透明导电氧化物薄膜15中的GAZO膜，可以是一种掺杂比例的GAZO膜，也可以是多层不同的掺杂比例的GAZO膜层叠而成。
本申请的另一些实施例提供一种异质结太阳能电池10，请参照图1，其可以包括：
硅片11；
在硅片11的两个表面的本征非晶硅薄膜12；
在其中一个本征非晶硅薄膜12表面的P型掺杂非晶硅薄膜13，以及在另一个本征非晶硅薄膜12表面的N型掺杂非晶硅薄膜14；
根据本申请的一些实施例的透明导电氧化物薄膜15，透明导电氧化物薄膜15可以设于P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14的表面；种子层151可以靠近P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14设置；以及
电极16，电极16可以设于透明导电氧化物薄膜15的表面。
由于透明导电氧化物薄膜15中的种子层151可以包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，该种子层151能够降低透明导电氧化物薄膜15与P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14的接触势垒，获得较低的接触电阻；导电层152可以为镓/铝共掺杂氧化锌膜，则能够减少成本；同时，由氧化铟锡膜作为保护层153，能够提高透明导电氧化物薄膜15的稳定性，保证电池效率和减少电池衰减。
在一些实施方案中，P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14中均可以具有微晶硅。
P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14中均可以具有微晶硅，使得P型掺 杂非晶硅薄膜13和N型掺杂非晶硅薄膜14的导电性更好、激活能更小、轰击损伤更少、P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14与TCO膜的接触势垒更低，有利于降低接触电阻，提高电池效率。
示例性地，P型掺杂非晶硅薄膜13的晶化率可以>20％，例如可以为21％、22％、23％、24％、25％、26％、28％或30％。
示例性地，N型掺杂非晶硅薄膜14的晶化率可以>25％，例如为26％、28％、30％、32％、35％或40％。
可选地，硅片11可以为单晶硅片11。
可选地，在一些实施方案中，N型掺杂非晶硅薄膜14表面的透明导电氧化物薄膜15中，种子层151的载流子浓度可以>6×10 20，厚度可以<10nm。
由于种子层151可以包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，且种子层151的载流子浓度可以>6×10 20，厚度可以<10nm，能够建一步降低N型掺杂非晶硅薄膜14与透明导电氧化物薄膜15的接触势垒，从而获得更低的接触电阻，有利于进一步提高电池效率。
示例性地，种子层151的载流子浓度可以为6.2×10 20、6.5×10 20、7×10 20、8×10 20、9×10 20或10×10 20。示例性地，种子层151的厚度可以为1nm、3nm、5nm、7nm或9nm。
在一些实施方案中，N型掺杂非晶硅薄膜14表面的透明导电氧化物薄膜15中，导电层152的载流子浓度可以<2×10 20，厚度可以>40nm。
由于导电层152为GAZO膜，且载流子浓度可以<2×10 20，厚度可以>40nm，则能够降低透明导电氧化物薄膜15的寄生吸收，从而进一步提高异质结太阳能电池10的电池效率，减小电池的衰减。
示例性地，N型掺杂非晶硅薄膜14表面的透明导电氧化物薄膜15中，导电层152的载流子浓度可以为0.2×10 20、0.5×10 20、0.8×10 20、1×10 20、1×10 20、1.2×10 20、1.5×10 20或1.8×10 20。示例性地，导电层152的厚度可以为42nm、45nm、50nm、52nm或55nm。
在一些实施方案中，N型掺杂非晶硅薄膜14表面的透明导电氧化物薄膜15中，保护层153的厚度可以为10～40nm，例如为10nm、20nm、30nm或40nm。
可选地，本申请实施例的N型掺杂非晶硅薄膜14表面的透明导电氧化物薄膜15的厚度可以为60至150nm，例如为60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、140nm或150nm。
可选地，在一些实施方案中，P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15中，种子层151的载流子浓度可以<1×10 20，厚度可以<10nm。
由于种子层151包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，且种子层151的载流子浓度<1×10 20，厚度<10nm，能够提高界面功函数的适配度，建一步降低P型掺杂非晶硅薄膜13 与透明导电氧化物薄膜15之间的接触势垒，从而获得更低的接触电阻，有利于进一步提高电池效率。
示例性地，P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15中，种子层151的载流子浓度可以为0.2×10 20、0.5×10 20、0.8×10 20或0.9×10 20。示例性地，种子层151的厚度可以为1nm、3nm、5nm、7nm或9nm。
在一些实施方案中，P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15中，导电层152的载流子浓度可以>3×10 20，厚度可以>40nm。
由于导电层152为GAZO膜，且载流子浓度>3×10 20，厚度>40nm，则能够确保透明导电氧化物薄膜15具有更好的导电性。
示例性地，P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15中，导电层152的载流子浓度可以为3.2×10 20、3.5×10 20、4×10 20、4.5×10 20、5×10 20或6×10 20。示例性地，导电层152的厚度可以为42nm、45nm、50nm、52nm或55nm。
在一些实施方案中，P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15中，保护层153的厚度可以为10nm至40nm，例如为10nm、20nm、30nm或40nm。
可选地，本申请实施例的P型掺杂非晶硅薄膜13表面的透明导电氧化物薄膜15的厚度为60nm至250nm，例如为60nm、80nm、100nm、120nm、150nm、180nm、200nm、220nm或250nm。
本申请实施例还提供一种异质结太阳能电池10的制备工艺，其可以包括：
对硅片11进行表面制绒和化学清洗，形成表面陷光结构；
在硅片11的两个表面沉积本征非晶硅薄膜12；
在其中一个本征非晶硅薄膜12表面沉积P型掺杂非晶硅薄膜13，在另一个本征非晶硅薄膜12表面沉积N型掺杂非晶硅薄膜14；
通过激光溅射镀膜的方式在P型掺杂非晶硅薄膜13和N型掺杂非晶硅薄膜14的表面形成透明导电氧化物薄膜15；
通过丝网印刷的方式在透明导电氧化物薄膜15表面形成电极16。
以下结合实施例对本申请的透明导电氧化物薄膜15及异质结太阳能电池10作进一步的详细描述。
实施例1
本实施提供一种异质结太阳能电池，其可以包括：
单晶硅片、在硅片的两个表面的本征非晶硅薄膜、在其中一个本征非晶硅薄膜表面的P型掺杂非晶硅薄膜、在另一个本征非晶硅薄膜表面的N型掺杂非晶硅薄膜、TCO薄膜以及设于TCO薄膜的表面的电极。
其中，P型掺杂非晶硅薄膜中可以含有微晶硅，其晶化率可以为20％，N型掺杂非晶硅薄膜中可以含有微晶硅，其晶化率可以为30％。
TCO薄膜可以设于P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜的表面。其中，N型掺杂非晶硅薄膜表面的TCO薄膜可以包括依次设置的厚度为10nm的种子层、厚度为60nm的导电层和厚度为20nm的保护层，该种子层可以为ITO薄膜，载流子浓度可以为8×10 20；导电层可以为GAZO膜，载流子浓度可以为1×10 20，保护层可以为ITO膜。其中，P型掺杂非晶硅薄膜表面的TCO薄膜可以包括依次设置的厚度为10nm的种子层、厚度为60nm的导电层和厚度为20nm的保护层，该种子层可以为ITO薄膜，载流子浓度可以为0.8×10 20；导电层可以为GAZO膜，载流子浓度可以为4×10 20，保护层可以为ITO膜。
TCO薄膜的种子层靠近P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜设置。
本实施还提供一种异质结太阳能电池的制备方法，其步骤可以包括：
(1)以单晶硅片为衬底，对单晶硅片进行表面制绒和化学清洗，形成表面陷光结构，再次经过化学清洗后形成清洁的表面；
(2)在单晶硅片的两个表面分别沉积本征非晶硅薄膜；
(3)在其中一个本征非晶硅薄膜表面沉积P型掺杂非晶硅薄膜、在另一个本征非晶硅薄膜表面沉积N型掺杂非晶硅薄膜，完成表面钝化和场钝化；
(4)通过磁控溅射镀膜的方式在P型掺杂非晶硅薄膜表面形成TCO薄膜，其中，该TCO薄膜的种子层的磁控溅射工艺条件包括：溅射靶材为ITO、溅射功率密度5KW/m、溅射压力0.45Pa、溅射温度为180℃、氧/氩的体积比的比值为1.0％；该TCO薄膜的导电层的磁控溅射工艺条件包括：溅射功率密度5KW/m、溅射压力0.45Pa、溅射温度为180℃、氧/氩的体积比的比值为2％；该TCO薄膜的保护层的磁控溅射工艺条件包括：溅射功率密度5KW/m、溅射压力0.35Pa、溅射温度为180℃、氧/氩比为3.0％。
(5)通过磁控溅射镀膜的方式在N型掺杂非晶硅薄膜表面形成TCO薄膜，该TCO薄膜的种子层的磁控溅射工艺条件包括：溅射靶材为ITO、溅射功率密度5KW/m、溅射压力0.45Pa、溅射温度为180℃、氧/氩的体积比的比值为3.0％；该TCO薄膜的导电层的磁控溅射工艺条件包括：溅射功率密度5KW/m、溅射压力0.45Pa、溅射温度为180℃、氧/氩的体积比的比值为2％；该TCO薄膜的保护层的磁控溅射工艺条件包括：溅射功率密度5KW/m、溅射压力0.35Pa、溅射温度为180℃、氧/氩比为3.0％。
(6)通过丝网印刷的方式在TCO薄膜表面形成金属电极。
实施例2
本实施例提供一种异质结太阳能电池，与实施例1相比，其不同之处仅在于本实施例的P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜的表面的TCO薄膜中，种子层可以为GAZO 膜，保护层的厚度均可以为10nm。
本实施例还提供一种上述异质结太阳能电池的制备方法，与实施例1相比，其不同之处仅在于，将实施例1中步骤(5)和步骤(6)的种子层的磁控溅射工艺条件中的溅射靶材为ITO替换为溅射靶材为GAZO。
实施例3
本实施例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于本实施例的P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜中均可以不含有微晶硅。
实施例4
本实施例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于本实施例的TCO薄膜中种子层和导电层的载流子浓度、厚度与实施例2不同。本实施例中，N型掺杂非晶硅薄膜表面的TCO薄膜中，种子层的载流子浓度可以为5×10 20、厚度可以为12nm。本实施例中，P型掺杂非晶硅薄膜表面的TCO薄膜中，种子层的载流子浓度可以为1.5×10 20、厚度可以为12nm。
实施例5
本实施例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于本实施例的TCO薄膜中种子层和导电层的载流子浓度、厚度与实施例2不同。本实施例中，N型掺杂非晶硅薄膜表面的TCO薄膜中，导电层的载流子浓度可以为3×10 20、厚度可以为35nm。本实施例中，P型掺杂非晶硅薄膜表面的TCO薄膜中，导电层的载流子浓度可以为2.5×10 20、厚度可以为35nm。
对比例1
本对比例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于对比例1的TCO薄膜为ITO薄膜。
对比例2
本对比例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于对比例2的导电层为ITO膜，保护层为GAZO膜。
对比例3
本对比例提供一种异质结太阳能电池，与实施例2相比，其不同之处仅在于对比例3的TCO薄膜为GAZO薄膜。
试验例1
选用halm在线I-V测试系统，在25℃、AM 1.5、1个标准太阳的条件下测试实施例1～实施例5以及对比例1～对比例2的异质结太阳能电池的开路电压(Voc)、短路电流(Isc)、填充因子(FF)和转换效率(Eff)其结果记录在表1中。
表1.异质结太阳能电池的性能测试结果
Figure PCTCN2021142673-appb-000001
通过对比实施例2、对比例1～对比例3的实验结果可以发现，对比例1～对比例3的转换效率明显低于实施例2，说明了本申请实施例的TCO薄膜的组成能够减少成本的同时，保证电池效率。
通过对比实施例2、实施例4和实施例5的实验结果可以发现，实施例2的转换效率明显高于实施例4和实施例5，说明了实施例2的TCO薄膜中的种子层和导电层的载流子浓度、厚度更加有利于提高转换效率。
试验例2
对实施例1至实施例5以及对比例1～对比例3的异质结太阳能电池进行TC200、DH100和HF10测试，测试异质结太阳能电池在TC200、DH100和HF10测试过程中的老化衰减率，其结果记录在表2中。
TC200的测试条件是：异质结太阳能电池在-40至85℃之间循环200次，在温度超过25℃通入Ipm。
DH100的测试条件是：异质结太阳能电池在温度为85±2℃、湿度为85％±5％的条件下测试1000h。
HF10的测试条件是：异质结太阳能电池在-40至85℃之间循环10圈，85℃温度下保持稳定20h，-40℃保持0.5h一次循环，循环24h。
表2.异质结太阳能电池的老化衰减率测试结果
Figure PCTCN2021142673-appb-000002
Figure PCTCN2021142673-appb-000003
通过对比实施例2和对比例2、对比例3的实验结果可以发现，对比例3的老化衰减率明显高于实施例2，对比例2的DH100和HF10对应的老化衰减率明显高于实施例2，说明了本申请实施例的TCO薄膜的组成能够减少成本的同时，减少电池衰减。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。
工业实用性
本申请提供了一种透明导电氧化物薄膜及异质结太阳能电池。透明导电氧化物薄膜包括种子层、导电层和保护层，种子层包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，导电层为镓/铝共掺杂氧化锌膜，保护层为氧化铟锡膜；透明导电氧化物薄膜中的氧化铟锡膜的厚度小于镓/铝共掺杂氧化锌膜的厚度。其能够保证电池效率和减少电池衰减，同时能够减少成本。
此外，可以理解的是，本申请的透明导电氧化物薄膜及异质结太阳能电池是可以重现的，并且可以用在多种工业应用中。例如，本申请的透明导电氧化物薄膜及异质结太阳能电池可以用于太阳能电池技术的领域。

Claims (14)

  1. 一种透明导电氧化物薄膜，其特征在于，其包括种子层、导电层和保护层，所述种子层包括氧化铟锡膜或镓/铝共掺杂氧化锌膜，所述导电层为镓/铝共掺杂氧化锌膜，所述保护层为氧化铟锡膜；
    所述透明导电氧化物薄膜中的所述氧化铟锡膜的厚度小于所述镓/铝共掺杂氧化锌膜的厚度。
  2. 一种异质结太阳能电池，其特征在于，其包括：
    硅片；
    在所述硅片的两个表面的本征非晶硅薄膜；
    在其中一个所述本征非晶硅薄膜表面的P型掺杂非晶硅薄膜，以及在另一个所述本征非晶硅薄膜表面的N型掺杂非晶硅薄膜；
    权利要求1所述的透明导电氧化物薄膜，所述透明导电氧化物薄膜设于所述P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜的表面；所述种子层靠近所述P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜设置；以及
    电极，所述电极设于所述透明导电氧化物薄膜的表面。
  3. 根据权利要求2所述的异质结太阳能电池，其特征在于，所述硅片为单晶硅片。
  4. 根据权利要求2或3所述的异质结太阳能电池，其特征在于，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述种子层的载流子浓度>6×10 20，厚度<10nm。
  5. 根据权利要求2至4中的任一项所述的异质结太阳能电池，其特征在于，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述导电层的载流子浓度<2×10 20，厚度>40nm。
  6. 根据权利要求5所述的异质结太阳能电池，其特征在于，所述N型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜的厚度为60nm至150nm。
  7. 根据权利要求2至6中的任一项所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述种子层的载流子浓度<1×10 20，厚度<10nm。
  8. 根据权利要求2或7所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜中，所述导电层的载流子浓度>3×10 20，厚度>40nm。
  9. 根据权利要求8所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜表面的所述透明导电氧化物薄膜为60nm至250nm。
  10. 根据权利要求2至9中的任一项所述的异质结太阳能电池，其特征在于，所述P 型掺杂非晶硅薄膜和所述N型掺杂非晶硅薄膜中均具有微晶硅。
  11. 根据权利要求2至10中的任一项所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜的晶化率>20％；和/或，所述N型掺杂非晶硅薄膜的晶化率>25％。
  12. 根据权利要求2至9中的任一项所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜和所述N型掺杂非晶硅薄膜中均不含有微晶硅。
  13. 根据权利要求2或3所述的异质结太阳能电池，其特征在于，所述N型掺杂非晶硅薄膜表面的所述透明氧化物薄膜中，所述种子层的载流子浓度为5×10 20、厚度为12nm，或者，所述导电层的载流子浓度为3×10 20、厚度为35nm。
  14. 根据权利要求2或3所述的异质结太阳能电池，其特征在于，所述P型掺杂非晶硅薄膜表面的所述透明氧化物薄膜中，所述种子层的载流子浓度为1.5×10 20、厚度为12nm，或者，所述导电层的载流子浓度为2.5×10 20、厚度为35nm。
PCT/CN2021/142673 2021-09-15 2021-12-29 透明导电氧化物薄膜及异质结太阳能电池 WO2023040120A1 (zh)

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