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WO2013086963A1 - Solar cell and method for preparing same - Google Patents

Solar cell and method for preparing same Download PDF

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Publication number
WO2013086963A1
WO2013086963A1 PCT/CN2012/086350 CN2012086350W WO2013086963A1 WO 2013086963 A1 WO2013086963 A1 WO 2013086963A1 CN 2012086350 W CN2012086350 W CN 2012086350W WO 2013086963 A1 WO2013086963 A1 WO 2013086963A1
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Prior art keywords
silicon
layer
film layer
thin film
carbon nanotube
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PCT/CN2012/086350
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French (fr)
Chinese (zh)
Inventor
韦进全
王红光
白曦
贾怡
朱宏伟
王昆林
吴德海
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Tsinghua University
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Tsinghua University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • H10F77/164—Polycrystalline semiconductors
    • H10F77/1642—Polycrystalline semiconductors including only Group IV materials
    • H10F77/1645—Polycrystalline semiconductors including only Group IV materials including microcrystalline silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • H10F77/166—Amorphous semiconductors
    • H10F77/1662—Amorphous semiconductors including only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • 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
    • Y02E10/545—Microcrystalline silicon PV 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
    • Y02E10/548—Amorphous silicon PV 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
    • Y02E10/549—Organic PV 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of nanotechnology and solar photovoltaic technology, and in particular to a solar cell based on a carbon nanotube-silicon film laminate and a preparation method thereof. Background technique
  • Carbon nanotubes are tubular all-carbon molecules made of one or more layers of graphene and having a diameter of nanometers. Carbon nanotubes are the darkest materials synthesized to date, indicating that carbon nanotubes can absorb sunlight more efficiently than all existing materials. The carbon nanotubes convert the absorbed light energy into electrical energy, and generate photogenerated electron-hole pairs inside the carbon nanotube. Theoretical calculations by Stewart DA et al. show that the quantum efficiency of carbon nanotube photoelectric conversion can reach 18% (Stewart DA, et al., Phys. Rev. Lett., 93: 107401, 2004; Nano Lett., 5: 219,
  • the photoelectric response of carbon nanotubes has a broad spectral range that covers the full spectrum from ultraviolet, visible to infrared.
  • carbon nanotube macroscopic bodies have strong photo-generated current and photoconductive behavior, such as carbon nanotube macroscopic body with a diameter of 0.39 mm, and its photoinduced current Up to mA level, and the photocurrent response range covers the visible and infrared regions. It is shown that the carbon nanotubes can excite electron transitions under the irradiation of incident light, cause separation and migration of electron-hole pairs, and generate photogenerated carriers, thereby forming photocurrent.
  • the addition of dilute nitric acid or dilute sulfuric acid at the heterojunction interface can increase the conversion efficiency of the carbon nanotube-silicon heterojunction solar cell to 13.8% ( Jia Y, et al, Nano Lett, 11 : 1901 , 2011).
  • the carbon nanotube film acts both as a junction material of the heterojunction and as a transparent conductive Upper electrode.
  • researchers are also experimenting with different methods to treat and improve carbon nanotube-silicon heterojunction solar cells to further improve cell efficiency.
  • the battery is a single-junction heterojunction cell, and the carbon nanotubes are located on the upper surface of the silicon film, and the sunlight first penetrates the carbon nanotube film, and then is irradiated on the silicon film, so that the sunlight is irradiated as much as possible.
  • the carbon nanotube film should not be too thick. Summary of the invention
  • the present invention is directed to at least one of the technical problems of the lamination material matching, manufacturing process complexity, and stability existing in the prior art laminated battery technology.
  • the purpose is to combine the excellent optical electrical properties of carbon nanotubes with silicon thin film cells to improve the conversion efficiency of solar cells while reducing the manufacturing cost of solar cells.
  • the invention provides a solar cell.
  • the solar cell includes: a transparent substrate; a transparent conductive film layer, the transparent conductive film layer is laminated on the transparent substrate; a silicon thin film layer, the silicon thin film layer is laminated on the a transparent conductive film layer; a carbon nanotube (CNT) film layer, the carbon nanotube film layer is laminated on the silicon film layer; and a back electrode, the back electrode is laminated on the carbon nanotube film layer,
  • the silicon thin film layer includes at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon, and the silicon thin film layer and the carbon nanotube thin film layer form a heterojunction.
  • a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed by combining a carbon nanotube film layer and at least two layers of silicon film.
  • sunlight is incident from one side of the silicon film, and the carbon nanotube film layer is used as a final light absorbing layer, so that the carbon nanotube film layer can be thicker to fully absorb sunshine.
  • the carbon nanotube thin film carbon nanotube film layer continuously covers the silicon thin film layer for absorbing sunlight passing through the silicon thin film layer. And forming a heterojunction cell with the silicon thin film layer, and stacking a solar cell with the multilayer silicon thin film structure.
  • the solar cell of the invention has high open circuit voltage and conversion efficiency. Specifically, the open circuit voltage can reach 1.3 V, the short circuit current can reach 17 mA/cm 2 , the conversion efficiency can reach 7.0%, and the cost is low, and has broad application prospects.
  • the solar cell of the present invention further has the following additional technical features:
  • the silicon thin film layer is selected from the group consisting of a PN type double layer silicon film, a PIN type three layer silicon film, At least one of the group consisting of a NPN type three-layer silicon film and an NPIN type four-layer silicon film.
  • the silicon thin film layer has a thickness of 0.2 to 2 ⁇ m or 0.1 to 2 ⁇ m.
  • the silicon thin film layer is a PN type double-layer silicon thin film, and the PN-type double-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-P/N structure, wherein A P layer in the PN type double-layer silicon film is bonded to the carbon nanotube film layer.
  • the silicon thin film layer is a PIN type three-layer silicon thin film, and the PIN type three-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-P/I/N structure, wherein The P layer in the PIN type three-layer silicon film is bonded to the carbon nanotube film layer.
  • the silicon thin film layer is an NPN-type three-layer silicon thin film, and the NPN-type three-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-N/P/N structure, wherein The N layer in the NPN-type three-layer silicon film is bonded to the carbon nanotube film layer.
  • the silicon thin film layer is an NPIN type four-layer silicon thin film, and the NPIN type four-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-N/P/I/N structure.
  • the N layer of the NPIN type four-layer silicon film is bonded to the carbon nanotube film layer.
  • the carbon nanotube film layer is a single-walled carbon nanotube film layer, a double-walled carbon nanotube film layer or a multi-wall carbon nanotube film layer.
  • the carbon nanotube film layer used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell, and constitutes a laminated solar cell with the multilayer silicon film, thereby Increased open circuit voltage of the battery.
  • the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer provided in the solar cell of the present invention is advantageous for charge transfer and can improve the short-circuit current of the battery.
  • the carbon nanotube film layer can improve the absorption of infrared light and visible light by the solar cell, and contribute to improvement of conversion efficiency of the solar cell and the like.
  • the thickness of the carbon nanotube film layer is not particularly limited. According to a specific example of the present invention, the carbon nanotube film layer has a thickness of 0.05 to 2 ⁇ m.
  • the carbon nanotube film layer serves as both a conductive film and a heterojunction in the solar cell of the present invention, and also serves as an important photoelectric conversion material.
  • the kind of the transparent conductive film layer is not particularly limited.
  • the transparent conductive film layer is an indium tin oxide film, a zinc aluminum oxide film, a fluorine-doped tin oxide film, or a graphene film.
  • the thickness of the transparent conductive film layer is not particularly limited.
  • the transparent conductive film layer has a thickness of 0.1 to 2 ⁇ m.
  • the kinds of the transparent substrate and the back electrode are not particularly limited.
  • the transparent substrate is made of a rigid material or a flexible material; and the back electrode is made of Al, Mo, Ag, Au or graphene.
  • the present invention also provides a method of preparing a solar cell.
  • the method comprises the steps of: forming a transparent conductive thin film layer on a transparent substrate; forming a silicon thin film layer on the transparent conductive thin film layer; forming carbon nanotubes on the silicon thin film layer a thin film layer; and a back electrode formed on the carbon nanotube thin film layer to obtain the solar cell.
  • the method for preparing a solar cell of the invention has the advantages of low process and low production cost, and high open circuit voltage and conversion efficiency of the prepared solar cell. Specifically, the open circuit voltage can reach 1.3V, and the short circuit current can be Up to 17 mA/cm 2 with a conversion efficiency of 7.0%. Thus, the method of preparing a solar cell of the present invention is suitable for practical application.
  • the method of producing a solar cell of the present invention further has the following additional technical features:
  • the specific steps of forming the silicon thin film layer are not particularly limited, that is, these steps.
  • the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film and a P-type silicon film on the transparent conductive film layer to form a PN-type double-layer silicon film.
  • the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, an I-type silicon film, and a P-type silicon film on the transparent conductive film layer to form a PIN-type three-layer silicon. film.
  • the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form an NPN-type three-layer layer. Silicon film.
  • the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form NPIN type four-layer silicon film.
  • the transparent conductive film layer is evaporated on the transparent substrate and led out by a wire.
  • the present invention provides a carbon nanotube-silicon thin film stacked solar cell comprising: a transparent substrate, a transparent conductive film, a silicon thin film layer, a carbon nanotube film, and a back electrode, wherein: the silicon thin film layer is composed of at least two silicon thin films, wherein silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon; and the silicon thin film layer and the carbon nanotube thin film are formed Heterojunction.
  • the carbon nanotube-silicon film laminated battery can effectively improve the open circuit voltage and conversion efficiency of the battery, and has the characteristics of a single process and low cost.
  • the carbon nanotube thin film carbon nanotube film layer used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film and constitutes a different structure.
  • the junction cell and the multilayer silicon film form a laminated solar cell, which improves the open circuit voltage of the battery.
  • the carbon nanotube thin film carbon nanotube film layer has high conductivity, which is favorable for charge transfer and can improve short circuit current.
  • the carbon nanotube thin film carbon nanotube film layer enhances the absorption of infrared light and visible light by the battery, and helps to improve the conversion efficiency of the solar cell. Wait.
  • the solar cell based on the carbon nanotube film layer-silicon film stack has an open circuit voltage of 1.3 V, a short circuit current of 17 mA/cm 2 , and a conversion efficiency of 7.0%, and has broad application prospects.
  • FIG. 1 is a schematic structural view of a solar cell according to a first embodiment of the present invention
  • FIG. 2 is a schematic structural view of a solar cell according to a second embodiment of the present invention.
  • FIG. 3 is a schematic structural view of a solar cell according to a third embodiment of the present invention.
  • FIG. 4 is a schematic structural view of a solar cell according to a fourth embodiment of the present invention.
  • FIG. 5 is a schematic flow chart showing a method of preparing a solar cell according to an embodiment of the present invention
  • FIG. 6 is a schematic view of a scanning electron microscope photograph of carbon nanotube transfer on a silicon film according to an embodiment of the present invention
  • Figure 8 is a current density-voltage curve of a solar cell tested according to another embodiment of the present invention under a standard light source (AM 1.5, 100 mW/cm 2 );
  • Figure 9 is a graph showing the current density-voltage curve of a solar cell according to still another embodiment of the present invention under a standard light source (AM 1.5, 100 mW/cm 2 ). detailed description
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining “first” and “second” may include one or more of the features, either explicitly or implicitly. Further, in the description of the present invention, “multiple,” means two or more unless otherwise stated.
  • the test methods in the following examples, unless otherwise specified, are conventional test methods, and the reagents and materials mentioned below are commercially available unless otherwise specified.
  • the silicon thin film used in the following examples can be commercially available as a silicon thin film, or can be prepared by plasma enhanced chemical vapor deposition (PECVD) or physical vapor deposition (PCVD).
  • PECVD plasma enhanced chemical vapor deposition
  • PCVD physical vapor deposition
  • FIG. 1 is a schematic structural view of a solar cell based on a carbon nanotube-silicon film stack according to an embodiment of the present invention.
  • the invention provides a solar cell.
  • the solar cell comprises: a transparent substrate 5, a transparent conductive film layer 4, a silicon film layer, a carbon nanotube (CNT) film layer 2, and a back electrode 1.
  • the transparent conductive film layer 4 is laminated on the transparent substrate 5, and the silicon film layer is laminated on the transparent conductive film layer 4, and the carbon nanotube film layer 2 is laminated.
  • the back electrode 1 is laminated on the carbon nanotube film layer 2.
  • the silicon thin film layer includes at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon, and the silicon thin film layer and the carbon nanotube thin film layer 2 constitutes a heterojunction.
  • a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed by combining a carbon nanotube film layer and at least two layers of silicon film.
  • sunlight is incident from one side of the silicon film, and the carbon nanotube film layer is used as a final light absorbing layer, so that the carbon nanotube film layer can be thicker to fully absorb sunshine.
  • the solar cell of the invention has high open circuit voltage and conversion efficiency. Specifically, the open circuit voltage can reach 1.3 V, the short circuit current can reach 17 mA/cm 2 , the conversion efficiency can reach 7.0%, and the cost is low, and has broad application prospects.
  • the kind of the carbon nanotube film layer 2 is not particularly limited.
  • the carbon nanotube film layer 2 is a single-walled carbon nanotube film layer, a double-walled carbon nanotube film layer or a multi-wall carbon nanotube film layer.
  • the carbon nanotube film layer 2 used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell, and a laminated solar cell is formed with the multilayer silicon film. Thereby increasing the open circuit voltage of the battery.
  • the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer 2 provided in the solar cell of the present invention facilitates charge transfer and can improve the short-circuit current of the battery.
  • the carbon nanotube film layer 2 can improve the absorption of infrared light and visible light by the solar cell of the present invention, and contributes to improvement of conversion efficiency of the solar cell and the like.
  • the thickness of the carbon nanotube film layer 2 is not particularly limited. According to a specific example of the present invention, the carbon nanotube film layer 2 has a thickness of 0.05 to 2 ⁇ m.
  • the carbon nanotube film layer 2 serves as both a conductive film and a heterojunction in the solar cell of the present invention, and also serves as an important photoelectric conversion material.
  • the thickness of the transparent conductive film layer 4 is not particularly limited. According to a specific example of the present invention, the transparent conductive film layer 4 has a thickness of 0.1 to 2 ⁇ m. Further, the kind of the transparent conductive film layer 4 is not particularly limited.
  • the transparent conductive film layer 4 is an indium tin oxide film, a zinc aluminum oxide film, a fluorine-doped tin oxide film, or a graphene film.
  • the kinds of the transparent substrate 5 and the back electrode 1 are not particularly limited.
  • the transparent substrate 5 may be made of a rigid material or a flexible material.
  • the back electrode 1 may be made of Al, Mo, Ag, Au or graphene.
  • the thickness of the silicon thin film layer may be 0.1 to 2 ⁇ ⁇ . According to an embodiment of the invention, the silicon thin film layer may have a thickness of 0.2 to 2 ⁇ m.
  • the silicon thin film layer is at least one selected from the group consisting of a PN type double layer silicon film, a PIN type three-layer silicon film, an NPN type three-layer silicon film, and an NPIN type four-layer silicon film. .
  • Fig. 1 is a schematic structural view of a solar cell 100 according to a first embodiment of the present invention.
  • the silicon thin film layer 31 is a PN type double-layered silicon thin film 311, 312, and the PN-type double-layered silicon thin film 311, 312 and the carbon nanotube thin film layer 2 form a CNT/P+-P/N structure, wherein the PN The P layer 311 of the double-layered silicon films 311, 312 is bonded to the carbon nanotube film layer 2.
  • Fig. 2 is a schematic structural view of a solar cell 200 according to a second embodiment of the present invention.
  • the silicon film layer 32 is a PIN type three-layer silicon film 321, 322, 323.
  • the PIN type three-layer silicon film 321, 322, 323 and the carbon nanotube film layer 2 form a CNT/P+-P/I/N structure, wherein the P layer 321 of the PIN type three-layer silicon film 321, 322, 323 is The carbon nanotube film layer 2 is bonded.
  • Fig. 3 is a schematic structural view of a solar cell 300 according to a third embodiment of the present invention.
  • the silicon thin film layer 33 is an NPN-type three-layer silicon thin film 331, 332, 333, and the NPN-type three-layer silicon thin film 331, 332, 333 and the carbon nanotube thin film layer 2 form CNT/P+-N/P/ The N structure in which the N layer 331 of the NPN type three-layer silicon film 331, 332, 333 is bonded to the carbon nanotube film layer 2.
  • Fig. 4 is a schematic structural view of a solar cell 400 according to a fourth embodiment of the present invention.
  • the silicon thin film layer 34 is an NPIN type four-layer silicon film 341, 342, 343, 344, and the NPIN type four-layer silicon film 341, 342, 343, 344 forms a CNT/P+- with the carbon nanotube film layer 2.
  • a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed, which increases the open circuit voltage of the solar cell.
  • the method includes the steps of: forming a transparent conductive thin film layer on a transparent substrate (S100); forming a silicon thin film layer on the transparent conductive thin film layer (S200) Forming a carbon nanotube film layer on the silicon thin film layer (S300); and forming a back electrode on the carbon nanotube thin film layer to obtain the solar cell (S400)
  • the solar cell manufactured by the above method forms a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself by combining a carbon nanotube film layer and at least two layers of silicon film.
  • this The invention discloses a method for preparing a solar cell, the process cartridge is simple, the production cost is low, and the open circuit voltage and conversion efficiency of the prepared solar cell are high, specifically, the open circuit voltage can reach 1.3 V, and the short circuit current can reach 17 mA/cm 2 , and the conversion The efficiency can reach 7.0%.
  • each step in the above method is not particularly limited, that is, it is not limited to a specific execution order, and the above-described solar cell can be manufactured.
  • the step S200 of forming the silicon thin film layer may include: sequentially depositing an N-type silicon film and a P-type silicon film on the transparent conductive film layer to form a PN-type double-layer silicon film.
  • the step S200 of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, and a P-type silicon film on the transparent conductive film layer to form a PIN type three. Layer of silicon film.
  • the step S200 of forming the silicon thin film layer includes: sequentially depositing an N-type silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form NPN type three-layer silicon film.
  • the step S200 of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer, To form a NPIN type four-layer silicon film.
  • the transparent conductive film layer may be evaporated on the transparent substrate and drawn out by a wire.
  • the method for preparing a solar cell of the invention has the following advantages: the process cartridge is simple, the production cost is low; the open circuit voltage and the conversion efficiency of the prepared solar cell are high, specifically, the open circuit voltage Up to 1.3 V, short-circuit current up to 17 mA/cm 2 and conversion efficiency of 7.0%.
  • the carbon nanotube film layer used in the method for preparing a solar cell according to an embodiment of the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell and constitute a multilayer silicon film.
  • the solar cell is laminated so that the open circuit voltage of the battery can be increased.
  • the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer used in the method for preparing a solar cell of the present invention is advantageous for charge transfer and can improve short-circuit current of the prepared battery.
  • the carbon nanotube film layer can improve the absorption of infrared light and visible light by the solar cell, and contributes to improving the conversion efficiency of the solar cell.
  • the solar cell 200 is prepared as follows:
  • Fig. 7 shows a current density-voltage curve of the solar cell 200 prepared in this example under standard light source (AM 1.5, 100 mW/cm 2 ).
  • AM 1.5 100 mW/cm 2
  • the open circuit voltage of the solar cell 200 was measured to be 1.3 V
  • the short-circuit current was 16.7 mA/cm 2
  • the photoelectric conversion efficiency was 7.0%.
  • the solar cell 200 is prepared as follows:
  • a 20 nm thick aluminum electrode was vapor-deposited on the carbon nanotube film layer 2 as the back electrode 1 and led out by a wire.
  • the solar cell 200 shown in Fig. 2 was prepared.
  • Figure 6 shows a scanning electron micrograph of carbon nanotubes transferred onto a thin film of silicon. As shown in Fig. 6, the carbon nanotube film layer 2 is in close contact with the P-type silicon film layer 321 .
  • Fig. 8 shows a current density-voltage curve of the solar cell 200 prepared in the present example, which was tested under a standard light source (AM 1.5, 100 mW/cm 2 ).
  • the open circuit voltage was measured to be 1.1 V
  • the short-circuit current was 11.1 mA/cm 2
  • the photoelectric conversion efficiency was 3.8%.
  • Example 3 According to the method of producing a solar cell of the present invention, the solar cell 400 is prepared as follows:
  • a 100 nm thick N-type amorphous silicon layer, an 8 nm thick I-type amorphous silicon layer, and a 100 nm thick P-type amorphous silicon layer are sequentially deposited by plasma enhanced chemical vapor deposition. And a 50 nm thick N-type amorphous silicon layer to form a silicon thin film layer 34 having a NPIN type four-layer silicon film structure;
  • a 50 nm thick aluminum electrode was vapor-deposited on the carbon nanotube film layer 2 as the back electrode 1 and led out by a wire.
  • a solar cell 400 as shown in Fig. 4 was prepared.
  • the solar cell 400 obtained by the above preparation was subjected to performance test under a standard light source (AMI .5 , lOOmW/cm 2 ), and the results are shown in FIG. Fig. 9 shows a current density-voltage curve of the solar cell 400 prepared in the present example, which was tested under a standard light source (AM 1.5, 100 mW/cm 2 ).
  • AM 1.5 100 mW/cm 2
  • the open circuit voltage was measured to be 1.6 V
  • the short-circuit current was 4.6 mA/cm 2
  • the conversion efficiency was 5.7%.
  • the method for preparing a solar cell of the invention can be combined with the traditional silicon thin film solar cell process, the process tube is simple, the production cost is low, and the method is suitable for large-scale popularization and application. Moreover, the solar cell obtained by the preparation has high open circuit voltage and high conversion efficiency, and low cost.
  • Particular features, structures, materials or features described in the examples or examples are included in at least one embodiment or example of the invention.
  • the schematic representation of the above terms does not necessarily mean the same embodiment or example.
  • the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

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Abstract

Provided are a solar cell and a method for preparing the same. The solar cell comprises a transparent substrate (5), a transparent conductive thin film layer (4), a silicon thin film layer (31), a carbon nanotube thin film layer (2) and a back electrode (1) laminated in sequence. The silicon thin film layer (31) is formed by at least two layers of silicon thin films (311, 312), and the silicon in the silicon thin film layers (311, 312) is amorphous silicon or microcrystalline silicon. The silicon thin film layer (31) forms a heterogeneous junction with the carbon nanotube thin film layer (2).

Description

太阳能电池及其制备方法  Solar cell and preparation method thereof

优先权信息 Priority information

本申请请求 201 1 年 12 月 13 日向中国国家知识产权局提交的、 专利申请号为 201 1 10414526.0的专利申请的优先权和权益， 并且通过参照将其全文并入此处。 技术领域  This application claims priority to and the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit. Technical field

本发明涉及纳米技术和太阳能光伏技术领域， 具体而言， 涉及一种基于碳纳米管- 硅薄膜叠层的太阳能电池及其制备方法。 背景技术  The present invention relates to the field of nanotechnology and solar photovoltaic technology, and in particular to a solar cell based on a carbon nanotube-silicon film laminate and a preparation method thereof. Background technique

随着能源危机的出现，人们开始发现可再生能源的重要性， 可再生能源成为了大家 越来越关注的问题。 太阳能作为其中一种可再生的清洁能源， 在很多领域得到了应用。 其中， 太阳能光伏电池的应用尤为广泛， 当前市场上的太阳能电池主要以硅基为主。 硅 太阳能电池主要分为单晶硅电池， 多晶硅电池和非晶 （微晶）硅薄膜电池。 其中， 硅薄 膜电池具有制作材料消耗少， 面积大， 制作能耗低， 成本低的优点， 近年来得到了迅速 的发展。 目前大面积、 批量生产的非晶硅薄膜太阳能电池的光电转换效率为 5 ~ 8% , 其 中单节硅薄膜电池的开路电压为 0.8 V左右。  With the advent of the energy crisis, people began to discover the importance of renewable energy. Renewable energy has become an issue of increasing concern. As one of the renewable energy sources, solar energy has been used in many fields. Among them, the application of solar photovoltaic cells is particularly wide, and the current solar cells on the market are mainly based on silicon. Silicon solar cells are mainly classified into single crystal silicon cells, polycrystalline silicon cells, and amorphous (microcrystalline) silicon thin film cells. Among them, the silicon thin film battery has the advantages of low production cost, large area, low energy consumption and low cost, and has been rapidly developed in recent years. At present, the photoelectric conversion efficiency of large-area and mass-produced amorphous silicon thin film solar cells is 5 to 8%, and the open circuit voltage of the single-cell silicon thin film battery is about 0.8 V.

碳纳米管（Carbon nanotube, CNT)是由一层或多层石墨烯卷曲而成、 直径为纳米量 级的管状全碳分子。碳纳米管是迄今合成的最黑材料，表明了碳纳米管吸收太阳光的能 力可比现有的所有材料都高。碳纳米管可将吸收的光能转变成电能，在碳纳米管内部产 生光生电子一空穴对。 Stewart DA等人的理论计算表明，碳纳米管光电转换的量子效率 可达 18 % ( Stewart DA, et al.， Phys. Rev. Lett., 93: 107401 , 2004; Nano Lett., 5: 219, Carbon nanotubes (CNTs) are tubular all-carbon molecules made of one or more layers of graphene and having a diameter of nanometers. Carbon nanotubes are the darkest materials synthesized to date, indicating that carbon nanotubes can absorb sunlight more efficiently than all existing materials. The carbon nanotubes convert the absorbed light energy into electrical energy, and generate photogenerated electron-hole pairs inside the carbon nanotube. Theoretical calculations by Stewart DA et al. show that the quantum efficiency of carbon nanotube photoelectric conversion can reach 18% (Stewart DA, et al., Phys. Rev. Lett., 93: 107401, 2004; Nano Lett., 5: 219,

2005 )。 碳纳米管的光电响应的光谱范围很宽， 可以覆盖从紫外、 可见到红外的全光谱 范围。 2005). The photoelectric response of carbon nanotubes has a broad spectral range that covers the full spectrum from ultraviolet, visible to infrared.

韦进全等人研究发现 （ Wei et al, Small, 2: 988, 2006 ) , 碳纳米管宏观体具有很强 的光生电流和光电导行为， 如直径为 0.39 mm的碳纳米管宏观体， 其光致电流可达 mA 量级， 并且光致电流的响应区间涵盖了可见光和红外光区。 由此表明， 碳纳米管在入射 光的辐照下可以激发电子跃迁， 引起电子-空穴对的分离和迁移， 产生光生载流子， 从 而形成光电流。研究还发现， 当光照射在双壁和多壁碳纳米管连接处或者碳纳米管与金 属结时， 碳纳米管的光致电流明显增强 （Sun JL, et al., Appl. Phys. Lett., 88: 131 107, Wei Jinquan et al. (Wei et al, Small, 2: 988, 2006), carbon nanotube macroscopic bodies have strong photo-generated current and photoconductive behavior, such as carbon nanotube macroscopic body with a diameter of 0.39 mm, and its photoinduced current Up to mA level, and the photocurrent response range covers the visible and infrared regions. It is shown that the carbon nanotubes can excite electron transitions under the irradiation of incident light, cause separation and migration of electron-hole pairs, and generate photogenerated carriers, thereby forming photocurrent. The study also found that when light is irradiated at the junction of double-walled and multi-walled carbon nanotubes or carbon nanotubes and metal junctions, the photocurrent of carbon nanotubes is significantly enhanced (Sun JL, et al., Appl. Phys. Lett. , 88: 131 107,

2006 ) 。 由此表明， 如果构建出适当的碳纳米管异质结， 便有可能大幅度提高光电流， 构成高效的太阳电池。 2006). This shows that if a suitable carbon nanotube heterojunction is constructed, it is possible to greatly increase the photocurrent and constitute a highly efficient solar cell.

研究人员已经开展了碳纳米管在无机异质结太阳能电池、 有机太阳能电池及染料敏 化太阳能电池等领域的应用研究工作。 韦进全等人则利用 p型碳纳米管与 n型硅，构建 了碳纳米管-硅异质结太阳电池太阳电池 ( Wei JQ, et al, Nano Lett. 7:2317, 2007 ) 。 韦 进全研究小组将碳纳米管薄膜与 n型单晶硅结合， 构成异质结太阳能电池， 其转换效率 在 5 ~ 7% ( Jia Y et al, Adv. Mater., 20, 4594-4598, 2008 ) ； 而在异质结界面上滴加稀 硝酸或者稀硫酸， 可以将碳纳米管一硅异质结太阳能电池的转换效率提高至 13.8% ( Jia Y, et al, Nano Lett, 11 : 1901 , 2011 ) 。 该碳纳米管一硅异质结太阳能电池的结构中， 太 阳光从碳纳米管一侧入射到异质结表面； 碳纳米管薄膜均既作为异质结的结材料， 又充 当了透明导电的上电极。 研究人员也在尝试用不同的方法对碳纳米管-硅异质结太阳能 电池进行处理和改进， 以进一步提高电池效率。 Researchers have carried out research and application work on carbon nanotubes in inorganic heterojunction solar cells, organic solar cells and dye-sensitized solar cells. Wei Jinquan et al. constructed a carbon nanotube-silicon heterojunction solar cell solar cell using p-type carbon nanotubes and n-type silicon (Wei JQ, et al, Nano Lett. 7:2317, 2007). Wei The research team combined the carbon nanotube film with n-type single crystal silicon to form a heterojunction solar cell with a conversion efficiency of 5 to 7% ( Jia Y et al, Adv. Mater., 20, 4594-4598, 2008). The addition of dilute nitric acid or dilute sulfuric acid at the heterojunction interface can increase the conversion efficiency of the carbon nanotube-silicon heterojunction solar cell to 13.8% ( Jia Y, et al, Nano Lett, 11 : 1901 , 2011). In the structure of the carbon nanotube-silicon heterojunction solar cell, sunlight is incident from the side of the carbon nanotube to the surface of the heterojunction; the carbon nanotube film acts both as a junction material of the heterojunction and as a transparent conductive Upper electrode. Researchers are also experimenting with different methods to treat and improve carbon nanotube-silicon heterojunction solar cells to further improve cell efficiency.

为了降低太阳能电池的成本， 研究人员将碳纳米管与硅薄膜相结合， 以构成碳纳米 管-硅薄膜的异质结太阳能电池。 Gobbo SD等人（ Gobbo SD, et al., Appl. Phys. Lett., 98, 1831 13, 201 1 ) 将单壁碳纳米管分散到溶液中， 然后与非晶薄膜结合， 构成了异质结太 阳能电池， 但其性能很低， 开路电压为 0.2 ~ 0.5 V, 转换效率 <0.1%, 无法实际应用。 该电池为单结的异质结电池， 且碳纳米管均位于硅薄膜的上表面， 太阳光先穿透碳纳米 管薄膜， 然后才照射在硅薄膜上， 为了使太阳光尽可能多地照射在异质结上， 碳纳米管 薄膜不能太厚。 发明内容  In order to reduce the cost of solar cells, researchers have combined carbon nanotubes with silicon films to form carbon nanotube-silicon thin film heterojunction solar cells. Gobbo SD et al. (Gobbo SD, et al., Appl. Phys. Lett., 98, 1831 13, 201 1 ) Dispersing single-walled carbon nanotubes into a solution and then combining with an amorphous film to form a heterojunction Solar cells, but their performance is very low, the open circuit voltage is 0.2 ~ 0.5 V, and the conversion efficiency is <0.1%, which is not practical. The battery is a single-junction heterojunction cell, and the carbon nanotubes are located on the upper surface of the silicon film, and the sunlight first penetrates the carbon nanotube film, and then is irradiated on the silicon film, so that the sunlight is irradiated as much as possible. On the heterojunction, the carbon nanotube film should not be too thick. Summary of the invention

本发明旨在解决现有叠层电池技术中存在的叠层材料匹配、制作工艺复杂性和稳定 性等技术问题中的至少一个。  SUMMARY OF THE INVENTION The present invention is directed to at least one of the technical problems of the lamination material matching, manufacturing process complexity, and stability existing in the prior art laminated battery technology.

本发明的目的是提供一种基于碳纳米管 -硅薄膜叠层太阳能电池及其制备方法。 旨 在利用碳纳米管优异的光学电学性能与硅薄膜电池相结合，以提高太阳能电池的转换效 率， 同时降低太阳能电池的制作成本。  It is an object of the present invention to provide a carbon nanotube-silicon film-based tandem solar cell and a method of fabricating the same. The purpose is to combine the excellent optical electrical properties of carbon nanotubes with silicon thin film cells to improve the conversion efficiency of solar cells while reducing the manufacturing cost of solar cells.

根据本发明的一个方面， 本发明提供了一种太阳能电池。 根据本发明的一个实施例， 该太阳能电池包括： 透明衬底； 透明导电薄膜层， 所述透明导电薄膜层层叠在所述透明衬 底上； 硅薄膜层， 所述硅薄膜层层叠在所述透明导电薄膜层上； 碳纳米管 （CNT )薄膜层， 所述碳纳米管薄膜层层叠在所述硅薄膜层上； 以及背电极， 所述背电极层叠在所述碳纳米 管薄膜层上， 其中所述硅薄膜层包括至少两层硅薄膜， 且所述硅薄膜层中的硅为非晶硅或 微晶硅， 所述硅薄膜层与所述碳纳米管薄膜层构成异质结。  According to an aspect of the invention, the invention provides a solar cell. According to an embodiment of the present invention, the solar cell includes: a transparent substrate; a transparent conductive film layer, the transparent conductive film layer is laminated on the transparent substrate; a silicon thin film layer, the silicon thin film layer is laminated on the a transparent conductive film layer; a carbon nanotube (CNT) film layer, the carbon nanotube film layer is laminated on the silicon film layer; and a back electrode, the back electrode is laminated on the carbon nanotube film layer, The silicon thin film layer includes at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon, and the silicon thin film layer and the carbon nanotube thin film layer form a heterojunction.

根据本发明的一个实施例的太阳能电池，通过将碳纳米管薄膜层和至少两层的硅薄 膜结合起来， 形成由碳纳米管-硅薄膜以及硅薄膜本身组成的叠层电池。 在该具有碳纳 米管-硅薄膜叠层结构的太阳能电池中， 太阳光从硅薄膜一侧入射， 碳纳米管薄膜层作 为最后的吸光层， 因此碳纳米管薄膜层可以较厚， 以充分吸收太阳光。  According to the solar cell of one embodiment of the present invention, a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed by combining a carbon nanotube film layer and at least two layers of silicon film. In the solar cell having a carbon nanotube-silicon film laminate structure, sunlight is incident from one side of the silicon film, and the carbon nanotube film layer is used as a final light absorbing layer, so that the carbon nanotube film layer can be thicker to fully absorb sunshine.

所述碳纳米管薄膜碳纳米管薄膜层连续地覆盖在硅薄膜层上方，用于吸收穿透硅薄 膜层的太阳光。 且与所述硅薄膜层构成异质结电池， 同时与多层硅薄膜结构成叠层太阳 能电池。  The carbon nanotube thin film carbon nanotube film layer continuously covers the silicon thin film layer for absorbing sunlight passing through the silicon thin film layer. And forming a heterojunction cell with the silicon thin film layer, and stacking a solar cell with the multilayer silicon thin film structure.

本发明的太阳能电池开路电压及转换效率高， 具体地， 其开路电压可达 1.3 V, 短 路电流可达 17 mA/cm2 , 转换效率可达 7.0% , 且成本低廉， 具有广阔的应用前景。 根据本发明的一个实施例， 本发明的太阳能电池还具有以下附加技术特征： 根据本发明的一个实施例， 所述硅薄膜层为选自由 PN型双层硅薄膜、 PIN型三层硅薄 膜、 NPN型三层硅薄膜和 NPIN型四层硅薄膜组成的组的至少一种。 The solar cell of the invention has high open circuit voltage and conversion efficiency. Specifically, the open circuit voltage can reach 1.3 V, the short circuit current can reach 17 mA/cm 2 , the conversion efficiency can reach 7.0%, and the cost is low, and has broad application prospects. According to an embodiment of the present invention, the solar cell of the present invention further has the following additional technical features: According to an embodiment of the present invention, the silicon thin film layer is selected from the group consisting of a PN type double layer silicon film, a PIN type three layer silicon film, At least one of the group consisting of a NPN type three-layer silicon film and an NPIN type four-layer silicon film.

根据本发明的一个实施例， 所述硅薄膜层的厚度为 0.2 ~ 2 μ m或者 0.1 ~ 2 μ m。  According to an embodiment of the invention, the silicon thin film layer has a thickness of 0.2 to 2 μm or 0.1 to 2 μm.

根据本发明的一个实施例， 所述硅薄膜层为 PN型双层硅薄膜， 所述 PN型双层硅薄膜 与所述碳纳米管薄膜层形成 CNT/P+-P/N结构， 其中所述 PN型双层硅薄膜中的 P层与所述 碳纳米管薄膜层结合。  According to an embodiment of the present invention, the silicon thin film layer is a PN type double-layer silicon thin film, and the PN-type double-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-P/N structure, wherein A P layer in the PN type double-layer silicon film is bonded to the carbon nanotube film layer.

根据本发明的一个实施例， 所述硅薄膜层为 PIN型三层硅薄膜， 所述 PIN型三层硅薄 膜与所述碳纳米管薄膜层形成 CNT/P+-P/I/N结构， 其中所述 PIN型三层硅薄膜中的 P层与 所述碳纳米管薄膜层结合。  According to an embodiment of the present invention, the silicon thin film layer is a PIN type three-layer silicon thin film, and the PIN type three-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-P/I/N structure, wherein The P layer in the PIN type three-layer silicon film is bonded to the carbon nanotube film layer.

根据本发明的一个实施例， 所述硅薄膜层为 NPN型三层硅薄膜， 所述 NPN型三层硅 薄膜与所述碳纳米管薄膜层形成 CNT/P+-N/P/N结构， 其中所述 NPN型三层硅薄膜中的 N 层与所述碳纳米管薄膜层结合。  According to an embodiment of the present invention, the silicon thin film layer is an NPN-type three-layer silicon thin film, and the NPN-type three-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-N/P/N structure, wherein The N layer in the NPN-type three-layer silicon film is bonded to the carbon nanotube film layer.

根据本发明的一个实施例， 所述硅薄膜层为 NPIN型四层硅薄膜， 所述 NPIN型四层硅 薄膜与所述碳纳米管薄膜层形成 CNT/P+-N/P/I/N结构，其中所述 NPIN型四层硅薄膜中的 N 层与所述碳纳米管薄膜层结合。  According to an embodiment of the present invention, the silicon thin film layer is an NPIN type four-layer silicon thin film, and the NPIN type four-layer silicon thin film and the carbon nanotube thin film layer form a CNT/P+-N/P/I/N structure. Wherein the N layer of the NPIN type four-layer silicon film is bonded to the carbon nanotube film layer.

根据本发明的一个实施例， 所述碳纳米管薄膜层为单壁碳纳米管薄膜层、 双壁碳纳米 管薄膜层或者多壁碳纳米管薄膜层。 需要说明的是， 本发明中所用的碳纳米管薄膜层是一 种柔性薄膜， 能够连续地铺展到硅薄膜层表面， 构成异质结电池， 并与多层硅薄膜构成 叠层太阳能电池， 从而提高了电池的开路电压。 且碳纳米管薄膜为高导电性材料， 则本 发明的太阳能电池中所具备的碳纳米管薄膜层有利于电荷的传递，能够提高电池的短路 电流。  According to an embodiment of the invention, the carbon nanotube film layer is a single-walled carbon nanotube film layer, a double-walled carbon nanotube film layer or a multi-wall carbon nanotube film layer. It should be noted that the carbon nanotube film layer used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell, and constitutes a laminated solar cell with the multilayer silicon film, thereby Increased open circuit voltage of the battery. Further, the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer provided in the solar cell of the present invention is advantageous for charge transfer and can improve the short-circuit current of the battery.

此外，在根据本发明的一个实施例的太阳能电池中，碳纳米管薄膜层能够提高该太 阳能电池对红外光、 可见光的吸收， 有助于提高太阳能电池的转换效率等。  Further, in the solar cell according to an embodiment of the present invention, the carbon nanotube film layer can improve the absorption of infrared light and visible light by the solar cell, and contribute to improvement of conversion efficiency of the solar cell and the like.

根据本发明的一个实施例， 碳纳米管薄膜层的厚度不受特别限制。 根据本发明的具体 示例， 所述碳纳米管薄膜层的厚度为 0.05 ~ 2 μ ηι。 该碳纳米管薄膜层在本发明的太阳能 电池中既作为导电薄膜， 也作为异质结的组成部分， 同时还作为重要的光电转换材料。  According to an embodiment of the present invention, the thickness of the carbon nanotube film layer is not particularly limited. According to a specific example of the present invention, the carbon nanotube film layer has a thickness of 0.05 to 2 μm. The carbon nanotube film layer serves as both a conductive film and a heterojunction in the solar cell of the present invention, and also serves as an important photoelectric conversion material.

根据本发明的一个实施例， 透明导电薄膜层的种类不受特别限制。 根据本发明的具体 示例， 所述透明导电薄膜层为氧化铟锡薄膜、 氧化锌铝薄膜、 掺氟氧化锡薄膜或石墨烯薄 膜。  According to an embodiment of the present invention, the kind of the transparent conductive film layer is not particularly limited. According to a specific example of the present invention, the transparent conductive film layer is an indium tin oxide film, a zinc aluminum oxide film, a fluorine-doped tin oxide film, or a graphene film.

根据本发明的一个实施例， 透明导电薄膜层的厚度不受特别限制。 根据本发明的具体 示例， 所述透明导电薄膜层的厚度为 0.1 ~ 2 μ ηι。 根据本发明的一个实施例， 透明衬底及背电极的种类不受特别限制。 根据本发明的具 体示例， 所述透明衬底由刚性材料或柔性材料制成； 以及所述背电极由 Al、 Mo、 Ag、 Au 或石墨烯制成。 According to an embodiment of the present invention, the thickness of the transparent conductive film layer is not particularly limited. According to a specific example of the present invention, the transparent conductive film layer has a thickness of 0.1 to 2 μm. According to an embodiment of the present invention, the kinds of the transparent substrate and the back electrode are not particularly limited. According to a specific example of the present invention, the transparent substrate is made of a rigid material or a flexible material; and the back electrode is made of Al, Mo, Ag, Au or graphene.

根据本发明的又一方面， 本发明还提供了一种制备太阳能电池的方法。 根据本发明的 一个实施例， 该方法包括下述步骤： 在透明衬底上形成透明导电薄膜层； 在所述透明导电 薄膜层上形成硅薄膜层； 在所述硅薄膜层上形成碳纳米管薄膜层； 以及在所述碳纳米管薄 膜层上形成背电极， 以获得所述太阳能电池。  According to still another aspect of the present invention, the present invention also provides a method of preparing a solar cell. According to an embodiment of the present invention, the method comprises the steps of: forming a transparent conductive thin film layer on a transparent substrate; forming a silicon thin film layer on the transparent conductive thin film layer; forming carbon nanotubes on the silicon thin film layer a thin film layer; and a back electrode formed on the carbon nanotube thin film layer to obtain the solar cell.

与现有技术相比， 本发明的制备太阳能电池的方法， 工艺筒单、 生产成本低， 且制 备获得的太阳能电池开路电压及转换效率高， 具体地， 开路电压可达 1.3V, 短路电流 可达 17 mA/cm2, 转换效率可达 7.0%。 从而， 本发明的制备太阳能电池的方法适于实 际应用推广。 Compared with the prior art, the method for preparing a solar cell of the invention has the advantages of low process and low production cost, and high open circuit voltage and conversion efficiency of the prepared solar cell. Specifically, the open circuit voltage can reach 1.3V, and the short circuit current can be Up to 17 mA/cm 2 with a conversion efficiency of 7.0%. Thus, the method of preparing a solar cell of the present invention is suitable for practical application.

根据本发明的一个实施例， 本发明的制备太阳能电池的方法还具有以下附加技术特征： 根据本发明实施例， 形成硅薄膜层的具体步骤不受特别限制， 即这些步骤。  According to an embodiment of the present invention, the method of producing a solar cell of the present invention further has the following additional technical features: According to an embodiment of the present invention, the specific steps of forming the silicon thin film layer are not particularly limited, that is, these steps.

根据本发明的一个实施例， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上 依次沉积 N型硅薄膜、 P型硅薄膜， 以形成 PN型双层硅薄膜。  According to an embodiment of the invention, the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film and a P-type silicon film on the transparent conductive film layer to form a PN-type double-layer silicon film.

根据本发明的一个实施例， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上 依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜， 以形成 PIN型三层硅薄膜。  According to an embodiment of the invention, the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, an I-type silicon film, and a P-type silicon film on the transparent conductive film layer to form a PIN-type three-layer silicon. film.

根据本发明的一个实施例， 形成所述硅薄膜层的步骤包括： 在在所述透明导电薄膜层 上依次沉积 N型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPN型三层硅薄膜。  According to an embodiment of the invention, the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form an NPN-type three-layer layer. Silicon film.

根据本发明的一个实施例， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上 依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPIN型四层硅薄膜。  According to an embodiment of the invention, the step of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form NPIN type four-layer silicon film.

根据本发明的一个实施例， 所述透明导电薄膜层被蒸镀在所述透明衬底上， 且用导线 引出。  According to an embodiment of the present invention, the transparent conductive film layer is evaporated on the transparent substrate and led out by a wire.

根据本发明的再一方面， 本发明还提供了一种碳纳米管 -硅薄膜叠层太阳能电池， 其包 括依序层叠的： 透明衬底、 透明导电薄膜、 硅薄膜层、 碳纳米管薄膜和背电极， 其特征在 于： 所述硅薄膜层由至少两层硅薄膜组成， 所述硅薄膜层中的硅为非晶硅或微晶硅； 所述 硅薄膜层与所述碳纳米管薄膜构成异质结。  According to still another aspect of the present invention, the present invention provides a carbon nanotube-silicon thin film stacked solar cell comprising: a transparent substrate, a transparent conductive film, a silicon thin film layer, a carbon nanotube film, and a back electrode, wherein: the silicon thin film layer is composed of at least two silicon thin films, wherein silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon; and the silicon thin film layer and the carbon nanotube thin film are formed Heterojunction.

该碳纳米管-硅薄膜叠层电池可以有效提高电池的开路电压、 转换效率等， 并且具 有工艺筒单， 成本低廉的特点。  The carbon nanotube-silicon film laminated battery can effectively improve the open circuit voltage and conversion efficiency of the battery, and has the characteristics of a single process and low cost.

本发明与现有技术相比， 本发明有具有如下优点和突出效果： 本发明中所用的碳纳 米管薄膜碳纳米管薄膜层是一种柔性薄膜， 能够连续的铺展到硅薄膜表面，构成异质结 电池， 与多层硅薄膜构成叠层太阳能电池， 提高了电池的开路电压。 碳纳米管薄膜碳纳 米管薄膜层高导电性， 有利于电荷的传递， 能够提高短路电流。 此外， 碳纳米管薄膜碳 纳米管薄膜层提高了电池对红外光， 可见光的吸收，有助于提高太阳能电池的转换效率 等。 该基于碳纳米管薄膜层-硅薄膜叠层的太阳能电池， 其开路电压可达 1.3 V, 短路电 流可达 17 mA/cm2 , 转换效率可达 7.0% , 具有广阔的应用前景。 Compared with the prior art, the present invention has the following advantages and outstanding effects: The carbon nanotube thin film carbon nanotube film layer used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film and constitutes a different structure. The junction cell and the multilayer silicon film form a laminated solar cell, which improves the open circuit voltage of the battery. The carbon nanotube thin film carbon nanotube film layer has high conductivity, which is favorable for charge transfer and can improve short circuit current. In addition, the carbon nanotube thin film carbon nanotube film layer enhances the absorption of infrared light and visible light by the battery, and helps to improve the conversion efficiency of the solar cell. Wait. The solar cell based on the carbon nanotube film layer-silicon film stack has an open circuit voltage of 1.3 V, a short circuit current of 17 mA/cm 2 , and a conversion efficiency of 7.0%, and has broad application prospects.

本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得 明显， 或通过本发明的实践了解到。 附图说明  The additional aspects and advantages of the invention will be set forth in part in the description which follows. DRAWINGS

本发明的上述和 /或附加的方面和优点从结合下面附图对实施例的描述中将变得明 显和容易理解， 其中：  The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from

图 1为才艮据本发明的第一实施例的太阳能电池的结构示意图；  1 is a schematic structural view of a solar cell according to a first embodiment of the present invention;

图 2为才艮据本发明的第二实施例的太阳能电池的结构示意图；  2 is a schematic structural view of a solar cell according to a second embodiment of the present invention;

图 3为才艮据本发明的第三实施例的太阳能电池的结构示意图；  3 is a schematic structural view of a solar cell according to a third embodiment of the present invention;

图 4为才艮据本发明的第四实施例的太阳能电池的结构示意图；  4 is a schematic structural view of a solar cell according to a fourth embodiment of the present invention;

图 5显示了根据本发明的一个实施例的制备太阳能电池的方法的示意流程图； 图 6为根据本发明一个实施例的碳纳米管转移在硅薄膜上的扫描电镜照片示意图； 图 7为根据本发明的一个实施例的太阳能电池在标准光源（ AM1.5, 100 mW/cm2 )下测 试的电流密度一电压曲线； 5 is a schematic flow chart showing a method of preparing a solar cell according to an embodiment of the present invention; FIG. 6 is a schematic view of a scanning electron microscope photograph of carbon nanotube transfer on a silicon film according to an embodiment of the present invention; A current density-voltage curve of a solar cell of one embodiment of the present invention tested under a standard light source (AM 1.5, 100 mW/cm 2 );

图 8为才艮据本发明的另一个实施例的太阳能电池在标准光源（AM1.5, lOO mW/cm2 )下 测试的电流密度一电压曲线； 以及 Figure 8 is a current density-voltage curve of a solar cell tested according to another embodiment of the present invention under a standard light source (AM 1.5, 100 mW/cm 2 );

图 9为才艮据本发明的再一个的太阳能电池在标准光源（ AM1.5, lOO mW/cm2 )下测试的 电流密度一电压曲线。 具体实施方式 Figure 9 is a graph showing the current density-voltage curve of a solar cell according to still another embodiment of the present invention under a standard light source (AM 1.5, 100 mW/cm 2 ). detailed description

下面详细描述本发明的实施例， 所述实施例的示例在附图中示出， 其中自始至终相 同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附 图描述的实施例是示例性的， 仅用于解释本发明， 而不能理解为对本发明的限制。  The embodiments of the present invention are described in detail below, and the examples of the embodiments are illustrated in the drawings, wherein the same or similar reference numerals are used to refer to the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the drawings are intended to be illustrative only and not to limit the invention.

在本发明的描述中， 需要理解的是， 术语 "中心，， 、 "上" 、 "下" 、 "前" 、 "后" 、 "左" 、 "右" 、 "竖直，， 、 "水平，， 、 "顶" 、 "底" "内" 、 "外" 等指示的方位 或位置关系为基于附图所示的方位或位置关系， 仅是为了便于描述本发明和筒化描述， 而不是指示或暗示所指的装置或元件必须具有特定的方位、 以特定的方位构造和操作， 因此不能理解为对本发明的限制。  In the description of the present invention, it is to be understood that the terms "center,", "upper", "lower", "front", "back", "left", "right", "vertical,", "horizontal" Orientation or positional relationship of ",", "top", "bottom", "inside", "outside", etc. is based on the orientation or positional relationship shown in the drawings, only for the convenience of describing the present invention and the description of the cylinder, rather than It is to be understood that the device or elements referred to have a particular orientation, are constructed and operated in a particular orientation and are therefore not to be construed as limiting.

需要说明的是， 术语 "第一，， 、 "第二，， 仅用于描述目的， 而不能理解为指示或暗 示相对重要性或者隐含指明所指示的技术特征的数量。 由此， 限定有 "第一" 、 "第二" 的特征可以明示或者隐含地包括一个或者更多个该特征。进一步地，在本发明的描述中， 除非另有说明， "多个，， 的含义是两个或两个以上。 下述实施例中的测试方法， 如无特殊说明， 均为常规检测方法， 下文所提及的试剂和 材料如无特殊说明， 均可从商业途径获得。 It should be noted that the terms "first," and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" and "second" may include one or more of the features, either explicitly or implicitly. Further, in the description of the present invention, "multiple," means two or more unless otherwise stated. The test methods in the following examples, unless otherwise specified, are conventional test methods, and the reagents and materials mentioned below are commercially available unless otherwise specified.

下述实施例中所采用的硅薄膜可从市场购买到的硅薄膜， 也可以通过等离子体增强化 学气相沉积（PECVD )或者物理气相沉积（PCVD )等方法制备。  The silicon thin film used in the following examples can be commercially available as a silicon thin film, or can be prepared by plasma enhanced chemical vapor deposition (PECVD) or physical vapor deposition (PCVD).

下面结合附图， 对本发明的太阳能电池及其制备方法进行详细描述。 其中图 1 为根据 本发明一个实施例的一种基于碳纳米管-硅薄膜叠层的太阳能电池结构示意图。  The solar cell of the present invention and its preparation method will be described in detail below with reference to the accompanying drawings. 1 is a schematic structural view of a solar cell based on a carbon nanotube-silicon film stack according to an embodiment of the present invention.

根据本发明的一个方面， 本发明提供了一种太阳能电池。 根据本发明的一个实施例， 该太阳能电池包括： 透明衬底 5、 透明导电薄膜层 4、 硅薄膜层、 碳纳米管 （CNT ) 薄膜层 2以及背电极 1。 根据本发明的一个实施例， 所述透明导电薄膜层 4层叠在所述透明衬底 5 上， 所述硅薄膜层层叠在所述透明导电薄膜层 4上， 所述碳纳米管薄膜层 2层叠在所述硅 薄膜层上， 所述背电极 1层叠在所述碳纳米管薄膜层 2上。 如图 1 中所示， 所述硅薄膜层 包括至少两层硅薄膜， 且所述硅薄膜层中的硅为非晶硅或微晶硅， 所述硅薄膜层与所述碳 纳米管薄膜层 2构成异质结。  According to an aspect of the invention, the invention provides a solar cell. According to an embodiment of the present invention, the solar cell comprises: a transparent substrate 5, a transparent conductive film layer 4, a silicon film layer, a carbon nanotube (CNT) film layer 2, and a back electrode 1. According to an embodiment of the present invention, the transparent conductive film layer 4 is laminated on the transparent substrate 5, and the silicon film layer is laminated on the transparent conductive film layer 4, and the carbon nanotube film layer 2 is laminated. On the silicon thin film layer, the back electrode 1 is laminated on the carbon nanotube film layer 2. As shown in FIG. 1 , the silicon thin film layer includes at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon, and the silicon thin film layer and the carbon nanotube thin film layer 2 constitutes a heterojunction.

根据本发明的一个实施例的太阳能电池，通过将碳纳米管薄膜层和至少两层的硅薄 膜结合起来， 形成由碳纳米管-硅薄膜以及硅薄膜本身组成的叠层电池。 在该具有碳纳 米管-硅薄膜叠层结构的太阳能电池中， 太阳光从硅薄膜一侧入射， 碳纳米管薄膜层作 为最后的吸光层， 因此碳纳米管薄膜层可以较厚， 以充分吸收太阳光。  According to the solar cell of one embodiment of the present invention, a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed by combining a carbon nanotube film layer and at least two layers of silicon film. In the solar cell having a carbon nanotube-silicon film laminate structure, sunlight is incident from one side of the silicon film, and the carbon nanotube film layer is used as a final light absorbing layer, so that the carbon nanotube film layer can be thicker to fully absorb sunshine.

本发明的太阳能电池开路电压及转换效率高， 具体地， 其开路电压可达 1.3 V, 短 路电流可达 17 mA/cm2 , 转换效率可达 7.0% , 且成本低廉， 具有广阔的应用前景。 The solar cell of the invention has high open circuit voltage and conversion efficiency. Specifically, the open circuit voltage can reach 1.3 V, the short circuit current can reach 17 mA/cm 2 , the conversion efficiency can reach 7.0%, and the cost is low, and has broad application prospects.

根据本发明的一个实施例， 碳纳米管薄膜层 2 的种类不受特别限制。 根据本发明的具 体示例， 所述碳纳米管薄膜层 2 为单壁碳纳米管薄膜层、 双壁碳纳米管薄膜层或者多壁碳 纳米管薄膜层。 需要说明的是， 本发明中所用的碳纳米管薄膜层 2是一种柔性薄膜， 能 够连续地铺展到硅薄膜层表面，构成异质结电池，并与多层硅薄膜构成叠层太阳能电池， 从而提高了电池的开路电压。 且碳纳米管薄膜为高导电性材料， 则本发明的太阳能电池 中所具备的碳纳米管薄膜层 2有利于电荷的传递， 能够提高电池的短路电流。  According to an embodiment of the present invention, the kind of the carbon nanotube film layer 2 is not particularly limited. According to a specific example of the present invention, the carbon nanotube film layer 2 is a single-walled carbon nanotube film layer, a double-walled carbon nanotube film layer or a multi-wall carbon nanotube film layer. It should be noted that the carbon nanotube film layer 2 used in the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell, and a laminated solar cell is formed with the multilayer silicon film. Thereby increasing the open circuit voltage of the battery. Further, the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer 2 provided in the solar cell of the present invention facilitates charge transfer and can improve the short-circuit current of the battery.

此外， 碳纳米管薄膜层 2能够提高本发明的太阳能电池对红外光、 可见光的吸收， 有助于提高太阳能电池的转换效率等。  Further, the carbon nanotube film layer 2 can improve the absorption of infrared light and visible light by the solar cell of the present invention, and contributes to improvement of conversion efficiency of the solar cell and the like.

根据本发明的一个实施例， 碳纳米管薄膜层 2 的厚度不受特别限制。 根据本发明的具 体示例， 所述碳纳米管薄膜层 2的厚度为 0.05 ~ 2 μ ηι。 该碳纳米管薄膜层 2在本发明的 太阳能电池中既作为导电薄膜， 也作为异质结的组成部分， 同时还作为重要的光电转换 材料。 根据本发明的一个实施例， 透明导电薄膜层 4的厚度不受特别限制。 根据本发明的 具体示例， 所述透明导电薄膜层 4的厚度为 0.1 ~ 2 μ ηι。 此外， 透明导电薄膜层 4的种类 不受特别限制。 根据本发明的具体示例， 所述透明导电薄膜层 4 为氧化铟锡薄膜、 氧化锌 铝薄膜、 掺氟氧化锡薄膜或石墨烯薄膜。 根据本发明的一个实施例， 透明衬底 5及背电极 1 的种类不受特别限制。 根据本发明 的具体示例， 透明衬底 5 可以由刚性材料或柔性材料制成。 根据本发明的一个实施例， 背 电极 1可以由 Al、 Mo、 Ag、 Au或石墨烯制成。 According to an embodiment of the present invention, the thickness of the carbon nanotube film layer 2 is not particularly limited. According to a specific example of the present invention, the carbon nanotube film layer 2 has a thickness of 0.05 to 2 μm. The carbon nanotube film layer 2 serves as both a conductive film and a heterojunction in the solar cell of the present invention, and also serves as an important photoelectric conversion material. According to an embodiment of the present invention, the thickness of the transparent conductive film layer 4 is not particularly limited. According to a specific example of the present invention, the transparent conductive film layer 4 has a thickness of 0.1 to 2 μm. Further, the kind of the transparent conductive film layer 4 is not particularly limited. According to a specific example of the present invention, the transparent conductive film layer 4 is an indium tin oxide film, a zinc aluminum oxide film, a fluorine-doped tin oxide film, or a graphene film. According to an embodiment of the present invention, the kinds of the transparent substrate 5 and the back electrode 1 are not particularly limited. According to a specific example of the present invention, the transparent substrate 5 may be made of a rigid material or a flexible material. According to an embodiment of the present invention, the back electrode 1 may be made of Al, Mo, Ag, Au or graphene.

根据本发明的一个实施例， 所述硅薄膜层的厚度可以为 0.1 ~ 2 μ ηι。 根据本发明的一 个实施例， 所述硅薄膜层的厚度可以为 0.2 ~ 2 μ m。  According to an embodiment of the present invention, the thickness of the silicon thin film layer may be 0.1 to 2 μ η. According to an embodiment of the invention, the silicon thin film layer may have a thickness of 0.2 to 2 μm.

根据本发明的一个实施例， 所述硅薄膜层为选自由 PN型双层硅薄膜、 PIN型三层硅薄 膜、 NPN型三层硅薄膜和 NPIN型四层硅薄膜组成的组的至少一种。  According to an embodiment of the present invention, the silicon thin film layer is at least one selected from the group consisting of a PN type double layer silicon film, a PIN type three-layer silicon film, an NPN type three-layer silicon film, and an NPIN type four-layer silicon film. .

下面将结合图 1-4详细描述上述的硅薄膜层。  The above silicon thin film layer will be described in detail below with reference to Figs.

图 1为根据本发明的第一实施例的太阳能电池 100的结构示意图。 参照图 1 , 该硅薄膜 层 31为 PN型双层硅薄膜 311、 312, 该 PN型双层硅薄膜 311、 312与碳纳米管薄膜层 2形 成 CNT/P+-P/N结构， 其中该 PN型双层硅薄膜 311、 312中的 P层 311与碳纳米管薄膜层 2 结合。  Fig. 1 is a schematic structural view of a solar cell 100 according to a first embodiment of the present invention. Referring to FIG. 1, the silicon thin film layer 31 is a PN type double-layered silicon thin film 311, 312, and the PN-type double-layered silicon thin film 311, 312 and the carbon nanotube thin film layer 2 form a CNT/P+-P/N structure, wherein the PN The P layer 311 of the double-layered silicon films 311, 312 is bonded to the carbon nanotube film layer 2.

图 2为根据本发明的第二实施例的太阳能电池 200的结构示意图。 参照图 2, 该硅薄膜 层 32为 PIN型三层硅薄膜 321、 322、 323。 该 PIN型三层硅薄膜 321、 322、 323与碳纳米 管薄膜层 2形成 CNT/P+-P/I/N结构，其中该 PIN型三层硅薄膜 321、 322、 323中的 P层 321 与碳纳米管薄膜层 2结合。  Fig. 2 is a schematic structural view of a solar cell 200 according to a second embodiment of the present invention. Referring to Fig. 2, the silicon film layer 32 is a PIN type three-layer silicon film 321, 322, 323. The PIN type three-layer silicon film 321, 322, 323 and the carbon nanotube film layer 2 form a CNT/P+-P/I/N structure, wherein the P layer 321 of the PIN type three-layer silicon film 321, 322, 323 is The carbon nanotube film layer 2 is bonded.

图 3为根据本发明的第三实施例的太阳能电池 300的结构示意图。 参照图 3 , 该硅薄膜 层 33为 NPN型三层硅薄膜 331、 332、 333 , 该 NPN型三层硅薄膜 331、 332、 333与碳纳 米管薄膜层 2形成 CNT/P+-N/P/N结构， 其中该 NPN型三层硅薄膜 331、 332、 333中的 N 层 331与碳纳米管薄膜层 2结合。  Fig. 3 is a schematic structural view of a solar cell 300 according to a third embodiment of the present invention. Referring to FIG. 3, the silicon thin film layer 33 is an NPN-type three-layer silicon thin film 331, 332, 333, and the NPN-type three-layer silicon thin film 331, 332, 333 and the carbon nanotube thin film layer 2 form CNT/P+-N/P/ The N structure in which the N layer 331 of the NPN type three-layer silicon film 331, 332, 333 is bonded to the carbon nanotube film layer 2.

图 4为根据本发明的第四实施例的太阳能电池 400的结构示意图。 参照图 4, 该硅薄膜 层 34为 NPIN型四层硅薄膜 341、 342、 343、 344, 该 NPIN型四层硅薄膜 341、 342、 343、 344与碳纳米管薄膜层 2形成 CNT/P+-N/P/I/N结构， 其中该 NPIN型四层硅薄膜 341、 342、 343、 344中的 N层 341与碳纳米管薄膜层 2结合。  Fig. 4 is a schematic structural view of a solar cell 400 according to a fourth embodiment of the present invention. Referring to FIG. 4, the silicon thin film layer 34 is an NPIN type four-layer silicon film 341, 342, 343, 344, and the NPIN type four-layer silicon film 341, 342, 343, 344 forms a CNT/P+- with the carbon nanotube film layer 2. The N/P/I/N structure in which the N layer 341 of the NPIN type four-layer silicon film 341, 342, 343, and 344 is bonded to the carbon nanotube film layer 2.

通过将碳纳米管薄膜层和至少两层的硅薄膜结合起来， 形成由碳纳米管-硅薄膜以 及硅薄膜本身组成的叠层电池， 这样提高了该太阳能电池的开路电压。  By combining a carbon nanotube film layer and at least two layers of silicon film, a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself is formed, which increases the open circuit voltage of the solar cell.

下面将对制备上述的太阳能电池的方法进行详细描述。  A method of preparing the above solar cell will be described in detail below.

才艮据本发明的一个实施例， 参照图 5 , 该方法包括下述步骤： 在透明衬底上形成透明导 电薄膜层 （S100 ); 在所述透明导电薄膜层上形成硅薄膜层（S200 ); 在所述硅薄膜层上形 成碳纳米管薄膜层（S300 ); 以及在所述碳纳米管薄膜层上形成背电极， 以获得所述太阳能 电池 ( S400 )„  According to an embodiment of the present invention, referring to FIG. 5, the method includes the steps of: forming a transparent conductive thin film layer on a transparent substrate (S100); forming a silicon thin film layer on the transparent conductive thin film layer (S200) Forming a carbon nanotube film layer on the silicon thin film layer (S300); and forming a back electrode on the carbon nanotube thin film layer to obtain the solar cell (S400)

通过上述方法制造的太阳能电池， 通过将碳纳米管薄膜层和至少两层的硅薄膜结合 起来， 形成由碳纳米管-硅薄膜以及硅薄膜本身组成的叠层电池。 与现有技术相比， 本 发明的制备太阳能电池的方法， 工艺筒单、 生产成本低， 且制备获得的太阳能电池开路 电压及转换效率高， 具体地， 开路电压可达 1.3 V, 短路电流可达 17 mA/cm2, 转换效 率可达 7.0%。 The solar cell manufactured by the above method forms a laminated battery composed of a carbon nanotube-silicon film and a silicon film itself by combining a carbon nanotube film layer and at least two layers of silicon film. Compared with the prior art, this The invention discloses a method for preparing a solar cell, the process cartridge is simple, the production cost is low, and the open circuit voltage and conversion efficiency of the prepared solar cell are high, specifically, the open circuit voltage can reach 1.3 V, and the short circuit current can reach 17 mA/cm 2 , and the conversion The efficiency can reach 7.0%.

需要说明的是， 在上述的方法中的各步骤的执行顺序并不特别受到限制， 即不受限于 特定的执行顺序， 只要能实现上述的太阳能电池的制造即可。  It should be noted that the order of execution of each step in the above method is not particularly limited, that is, it is not limited to a specific execution order, and the above-described solar cell can be manufactured.

才艮据本发明的一个实施例， 形成所述硅薄膜层的步骤 S200可以包括： 在所述透明导电 薄膜层上依次沉积 N型硅薄膜、 P型硅薄膜， 以形成 PN型双层硅薄膜。  According to an embodiment of the present invention, the step S200 of forming the silicon thin film layer may include: sequentially depositing an N-type silicon film and a P-type silicon film on the transparent conductive film layer to form a PN-type double-layer silicon film. .

根据本发明的另一个实施例， 形成所述硅薄膜层的步骤 S200包括： 在所述透明导电薄 膜层上依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜， 以形成 PIN型三层硅薄膜。  According to another embodiment of the present invention, the step S200 of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, and a P-type silicon film on the transparent conductive film layer to form a PIN type three. Layer of silicon film.

才艮据本发明的又一个实施例， 形成所述硅薄膜层的步骤 S200包括： 在在所述透明导电 薄膜层上依次沉积 N型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPN型三层硅薄膜。  According to still another embodiment of the present invention, the step S200 of forming the silicon thin film layer includes: sequentially depositing an N-type silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer to form NPN type three-layer silicon film.

根据本发明的再一个实施例， 形成所述硅薄膜层的步骤 S200包括： 在所述透明导电薄 膜层上依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPIN型四层 硅薄膜。  According to still another embodiment of the present invention, the step S200 of forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer, To form a NPIN type four-layer silicon film.

根据本发明的一个实施例， 所述透明导电薄膜层可以被蒸镀在所述透明衬底上， 且用 导线引出。  According to an embodiment of the present invention, the transparent conductive film layer may be evaporated on the transparent substrate and drawn out by a wire.

需要说明的是， 与现有技术相比， 本发明的制备太阳能电池的方法具有如下优点效 果： 工艺筒单、 生产成本低； 制备获得的太阳能电池开路电压及转换效率高， 具体地， 开路电压可达 1.3 V , 短路电流可达 17 mA/cm2 , 转换效率可达 7.0%。 It should be noted that, compared with the prior art, the method for preparing a solar cell of the invention has the following advantages: the process cartridge is simple, the production cost is low; the open circuit voltage and the conversion efficiency of the prepared solar cell are high, specifically, the open circuit voltage Up to 1.3 V, short-circuit current up to 17 mA/cm 2 and conversion efficiency of 7.0%.

此外，根据本发明的实施例的制备太阳能电池的方法所用的碳纳米管薄膜层是一种 柔性薄膜， 能够连续地铺展到硅薄膜层表面， 构成异质结电池， 并与多层硅薄膜构成叠 层太阳能电池， 从而能够提高电池的开路电压。 且碳纳米管薄膜为高导电性材料， 则本 发明制备太阳能电池的方法所采用的碳纳米管薄膜层有利于电荷的传递，能够提高制备 获得的电池的短路电流。 此外， 碳纳米管薄膜层能够提高太阳能电池对红外光、 可见光 的吸收， 有助于提高太阳能电池的转换效率等。  In addition, the carbon nanotube film layer used in the method for preparing a solar cell according to an embodiment of the present invention is a flexible film which can be continuously spread onto the surface of the silicon film layer to form a heterojunction cell and constitute a multilayer silicon film. The solar cell is laminated so that the open circuit voltage of the battery can be increased. Further, the carbon nanotube film is a highly conductive material, and the carbon nanotube film layer used in the method for preparing a solar cell of the present invention is advantageous for charge transfer and can improve short-circuit current of the prepared battery. In addition, the carbon nanotube film layer can improve the absorption of infrared light and visible light by the solar cell, and contributes to improving the conversion efficiency of the solar cell.

下面将结合具体示例对本发明的上述的太阳能电池及其制备方法进行说明。 本领域技 术人员将会理解， 下面的示例仅用于说明本发明， 而不应视为限定本发明的范围。 实施例 中未注明具体技术或条件的， 按照本领域内的文献所描述的技术或条件或者按照产品说明 书进行。 所用试剂或仪器未注明生产厂商者， 均为可以通过市购获得的常规产品。  The above solar cell of the present invention and a method of producing the same will be described below with reference to specific examples. Those skilled in the art will appreciate that the following examples are merely illustrative of the invention and should not be considered as limiting the scope of the invention. Where no specific technique or condition is indicated in the examples, it is carried out according to the techniques or conditions described in the literature in the field or in accordance with the product description. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products that can be obtained commercially.

示例 1  Example 1

根据本发明的制备太阳能电池的方法， 按照以下步骤制备太阳能电池 200:  According to the method of producing a solar cell of the present invention, the solar cell 200 is prepared as follows:

1 )在玻璃透明衬底 5上蒸镀一层 200 nm厚的氧化铟锡透明导电薄膜层 4, 并用导线引 出； 2 )在透明导电薄膜层 4上用等离子增强化学气相沉积方法依次沉积 50 nm厚的 N型非 晶硅层， 5 nm厚的 I型非晶硅层和 50 nm厚的 P型非晶硅层， 以便形成具有 PIN型三层硅 薄膜结构的硅薄膜层 32; 1) depositing a 200 nm thick indium tin oxide transparent conductive film layer 4 on the glass transparent substrate 5, and drawing it with a wire; 2) sequentially depositing a 50 nm thick N-type amorphous silicon layer, a 5 nm thick I-type amorphous silicon layer, and a 50 nm thick P-type amorphous silicon layer on the transparent conductive thin film layer 4 by plasma enhanced chemical vapor deposition. , in order to form a silicon film layer 32 having a PIN type three-layer silicon film structure;

3 )将厚度 200 nm的单壁碳纳米管薄膜层 2铺展到 P型非晶硅层上， 并使碳纳米管薄 膜层 2与硅薄膜层 32紧密接触；  3) spreading the single-walled carbon nanotube film layer 2 having a thickness of 200 nm onto the P-type amorphous silicon layer, and bringing the carbon nanotube film layer 2 into close contact with the silicon film layer 32;

4 )在碳纳米管薄膜层 2上蒸镀 20 nm厚的铝电极作为背电极 1 , 并用导线引出。 由此， 制备获得如图 2所示的太阳能电池 200。  4) A 20 nm thick aluminum electrode was vapor-deposited on the carbon nanotube film layer 2 as the back electrode 1 and led out by a wire. Thus, the solar cell 200 shown in Fig. 2 was prepared.

下面将对通过上述工艺获得的太阳能电池 200的性能进行测试。  The performance of the solar cell 200 obtained by the above process will be tested below.

在标准光源 （AM1.5,100mW/cm2 ) 下， 对上述制备获得的太阳能电池 200进行性能测 试， 结果见图 7。 图 7显示了本实施例制备获得的太阳能电池 200在标准光源（AM1.5, 100 mW/cm2 )下测试的电流密度一电压曲线。 如图 7所示， 测得该太阳能电池 200的开路电压 为 1.3 V, 短路电流为 16.7 mA/cm2 , 光电转换效率为 7.0 %。 示例 1 The solar cell 200 obtained by the above preparation was subjected to performance test under a standard light source (AM 1.5, 100 mW/cm 2 ), and the results are shown in Fig. 7. Fig. 7 shows a current density-voltage curve of the solar cell 200 prepared in this example under standard light source (AM 1.5, 100 mW/cm 2 ). As shown in Fig. 7, the open circuit voltage of the solar cell 200 was measured to be 1.3 V, the short-circuit current was 16.7 mA/cm 2 , and the photoelectric conversion efficiency was 7.0%. Example 1

根据本发明的制备太阳能电池的方法， 按照以下步骤制备太阳能电池 200:  According to the method of producing a solar cell of the present invention, the solar cell 200 is prepared as follows:

1 )在玻璃透明衬底 5上蒸镀一层 100 nm厚的氧化铟锡透明导电薄膜层 4;  1) depositing a 100 nm thick indium tin oxide transparent conductive film layer 4 on the glass transparent substrate 5;

2 )在透明导电薄膜层 4上用等离子增强化学气相沉积方法依次沉积 500 nm厚的 N型 硅薄膜层、 10 nm厚 I型硅薄膜层和 1500 nm厚 P型硅薄膜层， 以便形成具有 PIN型三层硅 薄膜结构的硅薄膜层 32;  2) depositing a 500 nm thick N-type silicon film layer, a 10 nm thick I-type silicon film layer, and a 1500 nm thick P-type silicon film layer on the transparent conductive film layer 4 by plasma enhanced chemical vapor deposition to form a PIN a silicon film layer 32 of a three-layer silicon film structure;

3 )将厚度 200 nm的单壁碳纳米管薄膜层 2转移到 P型硅薄膜层 321上；  3) transferring the single-walled carbon nanotube film layer 2 having a thickness of 200 nm onto the P-type silicon film layer 321;

4 )在碳纳米管薄膜层 2上蒸镀 20 nm厚的铝电极作为背电极 1 , 并用导线引出。  4) A 20 nm thick aluminum electrode was vapor-deposited on the carbon nanotube film layer 2 as the back electrode 1 and led out by a wire.

由此， 制备获得如图 2所示的太阳能电池 200。  Thus, the solar cell 200 shown in Fig. 2 was prepared.

然后， 在扫描电镜下对制备获得的太阳能电池 200进行检测与分析， 观察碳纳米管转 移在硅薄膜上的状况并进行成像， 结果如图 6所示。 图 6显示了碳纳米管转移在硅薄膜层 上的扫描电镜照片示意图。 如图 6所示， 碳纳米管薄膜层 2与 P型硅薄膜层 321接触紧密。  Then, the prepared solar cell 200 was detected and analyzed under a scanning electron microscope, and the state of the carbon nanotube transfer on the silicon film was observed and imaged. The results are shown in Fig. 6. Figure 6 shows a scanning electron micrograph of carbon nanotubes transferred onto a thin film of silicon. As shown in Fig. 6, the carbon nanotube film layer 2 is in close contact with the P-type silicon film layer 321 .

下面将对通过上述工艺获得的太阳能电池 200的性能进行测试。  The performance of the solar cell 200 obtained by the above process will be tested below.

在标准光源（AM1.5, 100 mW/cm2 )下， 对上述制备获得的太阳能电池 200进行性能测 试， 结果见图 8。 图 8显示了本实施例制备获得的太阳能电池 200在标准光源（AM1.5, 100 mW/cm2 ) 下测试的电流密度一电压曲线。 如图 8所示， 测得该开路电压为 1.1 V, 短路电 流为 11.1 mA/cm2 , 光电转换效率为 3.8 %。 示例 3 根据本发明的制备太阳能电池的方法， 按照以下步骤制备太阳能电池 400:The solar cell 200 obtained by the above preparation was subjected to performance test under a standard light source (AM 1.5, 100 mW/cm 2 ), and the results are shown in Fig. 8. Fig. 8 shows a current density-voltage curve of the solar cell 200 prepared in the present example, which was tested under a standard light source (AM 1.5, 100 mW/cm 2 ). As shown in Fig. 8, the open circuit voltage was measured to be 1.1 V, the short-circuit current was 11.1 mA/cm 2 , and the photoelectric conversion efficiency was 3.8%. Example 3 According to the method of producing a solar cell of the present invention, the solar cell 400 is prepared as follows:

1 )在玻璃透明衬底 5上蒸镀一层 200 nm厚的氧化铟锡透明导电薄膜层 4, 并用导线引 出； 1) depositing a 200 nm thick indium tin oxide transparent conductive film layer 4 on the glass transparent substrate 5, and drawing it with a wire;

2 )在透明导电薄膜层 4上用等离子增强化学气相沉积方法依次沉积 100 nm厚的 N型 非晶硅层， 8 nm厚的 I型非晶硅层， 100 nm厚的 P型非晶硅层和 50 nm厚的 N型非晶硅层， 以便形成具有 NPIN型四层硅薄膜结构的硅薄膜层 34;  2) On the transparent conductive film layer 4, a 100 nm thick N-type amorphous silicon layer, an 8 nm thick I-type amorphous silicon layer, and a 100 nm thick P-type amorphous silicon layer are sequentially deposited by plasma enhanced chemical vapor deposition. And a 50 nm thick N-type amorphous silicon layer to form a silicon thin film layer 34 having a NPIN type four-layer silicon film structure;

3 )将厚度 300 nm的单壁碳纳米管薄膜层 2铺展到 N型非晶硅层上， 并使碳纳米管薄 膜层 2与硅薄膜层 34紧密接触；  3) Spreading the single-walled carbon nanotube film layer 2 having a thickness of 300 nm onto the N-type amorphous silicon layer, and bringing the carbon nanotube film layer 2 into close contact with the silicon film layer 34;

4 )在碳纳米管薄膜层 2上蒸镀 50 nm厚的铝电极作为背电极 1 , 并用导线引出。  4) A 50 nm thick aluminum electrode was vapor-deposited on the carbon nanotube film layer 2 as the back electrode 1 and led out by a wire.

由此， 制备获得如图 4所示的太阳能电池 400。  Thus, a solar cell 400 as shown in Fig. 4 was prepared.

下面将对通过上述工艺获得的太阳能电池 400的性能进行测试。  The performance of the solar cell 400 obtained by the above process will be tested below.

在标准光源 （AMI .5 , lOOmW/cm2 ) 下， 对上述制备获得的太阳能电池 400进行性能 测试，结果见图 9。图 9显示了本实施例制备获得的太阳能电池 400在标准光源（AM1.5, 100 mW/cm2 ) 下测试的电流密度一电压曲线。 如图 9所示， 测得开路电压为 1.6 V, 短路电流 为 4.6 mA/cm2 , 转换效率为 5.7 %。 工业实用性 The solar cell 400 obtained by the above preparation was subjected to performance test under a standard light source (AMI .5 , lOOmW/cm 2 ), and the results are shown in FIG. Fig. 9 shows a current density-voltage curve of the solar cell 400 prepared in the present example, which was tested under a standard light source (AM 1.5, 100 mW/cm 2 ). As shown in Fig. 9, the open circuit voltage was measured to be 1.6 V, the short-circuit current was 4.6 mA/cm 2 , and the conversion efficiency was 5.7%. Industrial applicability

本发明的制备太阳能电池的方法， 可以与传统的硅薄膜太阳电池工艺相结合， 工艺筒 单、 生产成本低， 适于进行大规模推广应用。 并且制备获得的太阳能电池开路电压及转换 效率高、 成本低廉。 在本说明书的描述中， 参考术语 "一个实施例"、 "一些实施例"、 "示意性实施例"、 "示 例"、 "具体示例"、 或 "一些示例" 等的描述意指结合该实施例或示例描述的具体特征、 结 构、 材料或者特点包含于本发明的至少一个实施例或示例中。 在本说明书中， 对上述术语 的示意性表述不一定指的是相同的实施例或示例。 而且， 描述的具体特征、 结构、 材料或 者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。  The method for preparing a solar cell of the invention can be combined with the traditional silicon thin film solar cell process, the process tube is simple, the production cost is low, and the method is suitable for large-scale popularization and application. Moreover, the solar cell obtained by the preparation has high open circuit voltage and high conversion efficiency, and low cost. In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "illustrative embodiment", "example", "specific example", or "some examples", etc. Particular features, structures, materials or features described in the examples or examples are included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

尽管已经示出和描述了本发明的实施例， 本领域的普通技术人员可以理解： 在不脱离 本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、 修改、 替换和变型， 本发 明的范围由权利要求及其等同物限定。  While the embodiments of the present invention have been shown and described, the embodiments of the invention may The scope of the invention is defined by the claims and their equivalents.

Claims

权利要求书 Claim 1、 一种太阳能电池， 包括： 1. A solar cell comprising: 透明衬底；  Transparent substrate 透明导电薄膜层， 所述透明导电薄膜层层叠在所述透明衬底上；  a transparent conductive film layer, the transparent conductive film layer being laminated on the transparent substrate; 硅薄膜层， 所述硅薄膜层层叠在所述透明导电薄膜层上；  a silicon thin film layer, the silicon thin film layer is laminated on the transparent conductive thin film layer; 碳纳米管 （CNT ) 薄膜层， 所述碳纳米管薄膜层层叠在所述硅薄膜层上； 以及 背电极， 所述背电极层叠在所述碳纳米管薄膜层上， 其中  a carbon nanotube (CNT) thin film layer laminated on the silicon thin film layer; and a back electrode, wherein the back electrode is laminated on the carbon nanotube thin film layer, wherein 所述硅薄膜层包括至少两层硅薄膜， 且所述硅薄膜层中的硅为非晶硅或微晶硅， 所述 硅薄膜层与所述碳纳米管薄膜层构成异质结。  The silicon thin film layer includes at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon, and the silicon thin film layer and the carbon nanotube thin film layer form a heterojunction. 2、 根据权利要求 1所述的太阳能电池， 其特征在于， 所述硅薄膜层为选自由 PN型双 层硅薄膜、 PIN型三层硅薄膜、 NPN型三层硅薄膜和 NPIN型四层硅薄膜组成的组的至少一 种。  2. The solar cell according to claim 1, wherein the silicon thin film layer is selected from the group consisting of a PN type double layer silicon film, a PIN type three layer silicon film, an NPN type three layer silicon film, and an NPIN type four layer silicon. At least one of the group consisting of films. 3、根据权利要求 1所述的太阳能电池， 其特征在于， 所述硅薄膜层的厚度为 0.2 ~ 2 μ m或者 0.1~2 μ ηι。  The solar cell according to claim 1, wherein the thickness of the silicon thin film layer is 0.2 to 2 μm or 0.1 to 2 μm. 4、 根据权利要求 2所述的太阳能电池， 其特征在于， 所述硅薄膜层为 ΡΝ型双层硅薄 膜， 所述 ΡΝ型双层硅薄膜与所述碳纳米管薄膜层形成 CNT/P+-P/N结构， 其中所述 ΡΝ型 双层硅薄膜中的 Ρ层与所述碳纳米管薄膜层结合。  The solar cell according to claim 2, wherein the silicon thin film layer is a bismuth double-layer silicon thin film, and the bismuth double-layer silicon thin film and the carbon nanotube thin film layer form CNT/P+- A P/N structure in which a germanium layer in the germanium double-layer silicon film is bonded to the carbon nanotube film layer. 5、 根据权利要求 2所述的太阳能电池， 其特征在于， 所述硅薄膜层为 PIN型三层硅薄 膜， 所述 PIN型三层硅薄膜与所述碳纳米管薄膜层形成 CNT/P+-P/I/N结构， 其中所述 PIN 型三层硅薄膜中的 P层与所述碳纳米管薄膜层结合。  The solar cell according to claim 2, wherein the silicon thin film layer is a PIN type three-layer silicon thin film, and the PIN type three-layer silicon thin film forms a CNT/P+- with the carbon nanotube thin film layer. A P/I/N structure in which a P layer in the PIN type three-layer silicon film is bonded to the carbon nanotube film layer. 6、 根据权利要求 2所述的太阳能电池， 其特征在于， 所述硅薄膜层为 NPN型三层硅 薄膜， 所述 NPN型三层硅薄膜与所述碳纳米管薄膜层形成 CNT/P+-N/P/N结构， 其中所述 NPN型三层硅薄膜中的 N层与所述碳纳米管薄膜层结合。  The solar cell according to claim 2, wherein the silicon thin film layer is an NPN-type three-layer silicon thin film, and the NPN-type three-layer silicon thin film and the carbon nanotube thin film layer form CNT/P+- An N/P/N structure in which an N layer in the NPN-type three-layer silicon film is bonded to the carbon nanotube film layer. 7、 根据权利要求 2所述的太阳能电池， 其特征在于， 所述硅薄膜层为 NPIN型四层硅 薄膜， 所述 NPIN型四层硅薄膜与所述碳纳米管薄膜层形成 CNT/P+-N/P/I/N结构， 其中所 述 NPIN型四层硅薄膜中的 N层与所述碳纳米管薄膜层结合。  The solar cell according to claim 2, wherein the silicon thin film layer is a NPIN type four-layer silicon thin film, and the NPIN type four-layer silicon thin film forms a CNT/P+- with the carbon nanotube thin film layer. An N/P/I/N structure in which an N layer in the NPIN type four-layer silicon film is bonded to the carbon nanotube film layer. 8、 根据权利要求 1-7中任一项所述的太阳能电池， 其特征在于， 所述碳纳米管薄膜层 为单壁碳纳米管薄膜层、 双壁碳纳米管薄膜层或者多壁碳纳米管薄膜层。  The solar cell according to any one of claims 1 to 7, wherein the carbon nanotube film layer is a single-walled carbon nanotube film layer, a double-walled carbon nanotube film layer or a multi-wall carbon nanometer. Tube film layer. 9、 根据权利要求 8 所述的太阳能电池， 其特征在于， 所述碳纳米管薄膜层的厚度为 The solar cell according to claim 8, wherein the thickness of the carbon nanotube film layer is 0.05 ~ 2 μ ηι。 0.05 ~ 2 μ ηι. 10、根据权利要求 1-7中任一项所述的太阳能电池， 其特征在于， 所述透明导电薄膜层 为氧化铟锡薄膜、 氧化锌铝薄膜、 掺氟氧化锡薄膜或石墨烯薄膜。 The solar cell according to any one of claims 1 to 7, wherein the transparent conductive film layer It is an indium tin oxide film, a zinc oxide aluminum film, a fluorine-doped tin oxide film or a graphene film. 11、 根据权利要求 10所述的太阳能电池， 其特征在于， 所述透明导电薄膜层的厚度为 0.1 ~ 2 μ ηι。  The solar cell according to claim 10, wherein the transparent conductive film layer has a thickness of 0.1 to 2 μm. 12、根据权利要求 1-7中任一项所述的太阳能电池， 其特征在于， 所述透明衬底由刚性 材料或柔性材料制成； 以及  The solar cell according to any one of claims 1 to 7, wherein the transparent substrate is made of a rigid material or a flexible material; 所述背电极由 Al、 Mo、 Ag、 Au或石墨烯制成。  The back electrode is made of Al, Mo, Ag, Au or graphene. 13、 一种制备太阳能电池的方法， 包括下述步骤：  13. A method of preparing a solar cell, comprising the steps of: 在透明衬底上形成透明导电薄膜层；  Forming a transparent conductive film layer on the transparent substrate; 在所述透明导电薄膜层上形成硅薄膜层；  Forming a silicon thin film layer on the transparent conductive film layer; 在所述硅薄膜层上形成碳纳米管薄膜层； 以及  Forming a carbon nanotube film layer on the silicon thin film layer; 在所述碳纳米管薄膜层上形成背电极， 以获得所述太阳能电池。  A back electrode is formed on the carbon nanotube film layer to obtain the solar cell. 14、 根据权利要求 13所述的方法， 其特征在于， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上依次沉积 N型硅薄膜、 P型硅薄膜，以形成 PN型双层硅薄膜。 The method according to claim 13, wherein the forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film and a P-type silicon film on the transparent conductive film layer to form a PN type double Layer of silicon film. 15、 根据权利要求 13所述的方法， 其特征在于， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜， 以形成 PIN 型三层硅薄膜。 The method according to claim 13, wherein the forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, an I-type silicon film, and a P-type silicon film on the transparent conductive film layer, To form a PIN type three-layer silicon film. 16、 根据权利要求 13所述的方法， 其特征在于， 形成所述硅薄膜层的步骤包括： 在在所述透明导电薄膜层上依次沉积 N型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPN型三层硅薄膜。  16. The method according to claim 13, wherein the forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a P-type silicon film, and an N-type silicon film on the transparent conductive film layer. To form an NPN type three-layer silicon film. 17、 根据权利要求 14所述的方法， 其特征在于， 形成所述硅薄膜层的步骤包括： 在所述透明导电薄膜层上依次沉积 N型硅薄膜、 I型硅薄膜、 P型硅薄膜、 N型硅薄膜， 以形成 NPIN型四层硅薄膜。  The method according to claim 14, wherein the forming the silicon thin film layer comprises: sequentially depositing an N-type silicon film, a type I silicon film, a P-type silicon film on the transparent conductive film layer, An N-type silicon film is formed to form a NPIN type four-layer silicon film. 18、 根据权利要求 13所述的方法， 其特征在于， 所述透明导电薄膜层被蒸镀在所述透 明衬底上， 且用导线引出。  18. The method according to claim 13, wherein the transparent conductive film layer is evaporated on the transparent substrate and drawn out by a wire. 19、 一种碳纳米管 -硅薄膜叠层太阳能电池， 其包括依序层叠的： 透明衬底、 透明导电 薄膜、 硅薄膜层、 碳纳米管薄膜和背电极， 其特征在于： 所述硅薄膜层由至少两层硅薄膜 组成， 所述硅薄膜层中的硅为非晶硅或微晶硅； 所述硅薄膜层与所述碳纳米管薄膜构成异 质结。  19. A carbon nanotube-silicon thin film stacked solar cell comprising: a transparent substrate, a transparent conductive film, a silicon thin film layer, a carbon nanotube film, and a back electrode, wherein: the silicon film The layer is composed of at least two silicon thin films, and the silicon in the silicon thin film layer is amorphous silicon or microcrystalline silicon; and the silicon thin film layer and the carbon nanotube thin film form a heterojunction.
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