WO2023115870A1 - Pn heterojunction antimony selenide/perovskite solar cell, and preparation method therefor - Google Patents

Pn heterojunction antimony selenide/perovskite solar cell, and preparation method therefor Download PDF

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WO2023115870A1
WO2023115870A1 PCT/CN2022/101422 CN2022101422W WO2023115870A1 WO 2023115870 A1 WO2023115870 A1 WO 2023115870A1 CN 2022101422 W CN2022101422 W CN 2022101422W WO 2023115870 A1 WO2023115870 A1 WO 2023115870A1
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perovskite
layer
antimony selenide
heterojunction
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Chinese (zh)
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李梦洁
赵志国
赵东明
秦校军
丁坤
刘家梁
熊继光
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中国华能集团清洁能源技术研究院有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • 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
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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

Definitions

  • the invention belongs to the technical field of solar cells, in particular to a PN heterojunction antimony selenide/perovskite solar cell and a preparation method thereof.
  • Solar cells can convert solar energy into electrical energy through photoelectric conversion, which can be directly used by people and has attracted much attention. According to the development of solar cells and the light-absorbing layer materials used, solar cells can be divided into three categories.
  • the first type is silicon-based solar cells, including monocrystalline silicon, polycrystalline silicon solar cells, amorphous silicon thin-film solar cells, and silicon stacked solar cells;
  • the second type is compound solar cells, including copper indium gallium selenide (CIGS), tellurium Cadmium (CdTe), gallium arsenide (GaAs) and perovskite solar cells;
  • the third category is new solar cells, including dye-sensitized solar cells, organic solar cells and quantum dot solar cells.
  • perovskite solar cells are solar cells that use perovskite-type organometallic halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and are also called new concept solar cells.
  • Perovskite solar cells which use organic-inorganic hybrid metal halides with a perovskite crystal structure as the light-absorbing layer, have attracted much attention since 2009 because of their simple preparation methods, low production costs, and excellent photoelectric performance. Photoelectric conversion The efficiency has risen rapidly from 3.8% to 25%, becoming the fastest growing photovoltaic technology and the most watched emerging photovoltaic technology in the world.
  • Single-junction solar cells have the Shockley-Queisser efficiency limit because they can only absorb photons within a specific range. Combining multiple light absorbers with different band gaps into multi-junction solar cells can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers.
  • perovskite is mainly stacked with crystalline silicon, copper indium gallium selenide, perovskite, etc. to form double-junction or multi-junction battery devices.
  • the double-junction perovskite stack cell is prepared by processes such as electron transport layer, wide band gap absorption layer, hole transport layer and intermediate tunneling layer, as well as hole transport layer, narrow band gap absorption layer, and electron transport layer. The structure is complex.
  • the Chinese patent with the publication number CN111244220A discloses an all-inorganic P/N heterojunction antimony selenide/perovskite solar cell and its preparation method.
  • the structure of the solar cell is FTO conductive from bottom to top.
  • Glass substrate titanium dioxide (TiO 2 ) layer
  • inorganic CsPbBrI 2 perovskite layer selenized Sb 2 Se 3 layer and metal counter electrode layer.
  • the inorganic perovskite layer has not been N-type treated and still needs electron Preparation of transport layer TiO2 .
  • the technical problem to be solved by the present invention is to provide a PN heterojunction antimony selenide/perovskite solar cell with a broad absorption spectrum and a simple structure and a preparation method thereof.
  • the invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
  • the substrate is a flexible metal substrate; the thickness of the substrate is 0.1-0.3mm.
  • the material of the metal back electrode is metal molybdenum; the thickness of the metal back electrode is 800-1000mm.
  • the thickness of the P-type antimony selenide layer is 50-300 nm.
  • the thickness of the N-type perovskite absorbing layer is 100-200 mm.
  • the material of the N-type perovskite absorbing layer is ABX 3 doped with N-type materials; wherein, A is one or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; the N-type materials include Bi 3+ , One or more of Sb 3+ , Fe 3+ and Al 3+ .
  • the molar ratio of N-type material to B in the N-type perovskite absorbing layer is (0.01-0.05): (0.95-0.99).
  • the present invention also provides a preparation method of a PN heterojunction antimony selenide/perovskite solar cell, comprising:
  • the vapor deposition in the step S2) is vacuum vapor deposition; the vacuum degree of the vapor deposition is less than 4 ⁇ 10 -4 Pa; the temperature of the vapor deposition is 300°C-600°C; the vapor deposition The rate is 0.3-1.5 angstroms/second; the raw materials for the vapor deposition are Se and Sb 2 Se 3 .
  • the N-type perovskite precursor solution includes AX, BX 2 and N-type dopant materials;
  • A is one or more of MA, FA, Cs and PEA;
  • MA is CH 3 NH 3 ;
  • FA is NH 2 CHNH 2 ;
  • PEA is C 8 H 9 NH 3 ;
  • B is Pb and/or Sn;
  • X is one or more of Cl, Br and I;
  • the N-type dopant material includes Bi 3+ , One or more of Sb 3+ , Fe 3+ and Al 3+ ;
  • the annealing temperature is 70°C-150°C;
  • the annealing time is 10-60min.
  • the invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
  • the present invention composes multiple light absorbers with different band gaps into a multi-junction solar cell, which can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers and improve photoelectric conversion efficiency; and the present invention uses a PN heterojunction Sb 2 Se 3 perovskite absorber layer, without the need for an electron transport layer and a hole transport layer, etc., reducing process preparation steps and costs, and improving battery stability at the same time.
  • the present invention does not need the preparation of the electron and/or hole transport layer and the intermediate composite layer, and directly prepares the mixed antimony selenide layer on the 1.1-1.3eV narrow bandgap P-type antimony selenide layer.
  • the 1.4-2.0eV wide-bandgap N-type perovskite cell with heterometallic ions can form a PN heterojunction structure with different bandgap, and at the same time, the doping of strong N-type ions through the perovskite layer does not require an electron transport layer and/or Or the preparation of the electron transport layer has the advantages of simple process, low cost and wide light absorption range, which reduces the technical difficulty of battery design and preparation.
  • Fig. 1 is the structural representation of the PN heterojunction antimony selenide/perovskite solar cell provided by the present invention
  • Fig. 2 is a schematic structural diagram of the antimony selenide evaporation equipment used in the embodiment of the present invention.
  • the invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
  • Fig. 1 is the structural representation of the PN heterojunction antimony selenide/perovskite solar cell provided by the present invention; wherein 1 is a substrate, 2 is a metal back electrode, 3 is a P-type antimony selenide layer, 4 5 is an N-type perovskite absorption layer, and 5 is a conductive electrode.
  • the substrate can be a substrate well-known to those skilled in the art, and there is no special limitation.
  • it is preferably metal foil, more preferably stainless steel foil; the thickness of the substrate is preferably 0.1-0.3mm .
  • the substrate is provided with a metal back electrode;
  • the metal back electrode is a metal back electrode well known to those skilled in the art, and is not particularly limited, and is preferably metal molybdenum in the present invention;
  • the thickness of the back electrode is preferably 800 ⁇ 1000nm.
  • a P-type antimony selenide layer is arranged on the metal back electrode; the thickness of the P-type antimony selenide layer is preferably 50-300 nm.
  • N-type perovskite absorbing layer is arranged on the P-type antimony selenide layer; the thickness of the N-type perovskite absorbing layer is preferably 100-200 mm, more preferably 120-150 nm, and more preferably 130-150 nm, The most preferred is 150 mm; the material of the N-type perovskite absorbing layer is preferably ABX 3 doped with N-type materials; wherein, A is one or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; the examples provided in the present invention Among them, A is specifically MA and/or Cs and FA; the molar ratio of MA and/or Cs and FA is preferably (0.1 ⁇ 0.2):(0.8 ⁇ 0.9), more preferably 0.15:0.85; the N type The material includes one or more of Bi 3
  • the N-type perovskite absorption layer is provided with a conductive electrode; the conductive electrode is preferably a transparent electrode, more preferably one or more of ITO, zinc oxide and aluminum-doped zinc oxide; the thickness of the conductive electrode Preferably it is 100 to 1000 nm.
  • a plurality of light absorbers with different band gaps are used to form a multi-junction solar cell, which can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers and improve the photoelectric conversion efficiency; and the present invention adopts PN
  • the heterojunction Sb 2 Se 3 perovskite absorber layer does not require an electron transport layer and a hole transport layer, etc., reducing process preparation steps and costs, while improving battery stability.
  • the present invention also provides a method for preparing the above-mentioned PN heterojunction antimony selenide/perovskite solar cell, comprising: S1) depositing a metal back electrode on a substrate to obtain a substrate of a composite metal back electrode; S2) A P-type antimony selenide layer is vapor-deposited on the substrate of the composite metal back electrode to obtain the substrate of the composite P-type antimony selenide layer; S3) coating the N-type perovskite precursor solution on the composite P-type antimony selenide layer The substrate surface of the antimony layer is annealed to obtain the substrate of the composite N-type perovskite absorbing layer; S4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorbing layer to obtain a PN heterojunction Antimony selenide/perovskite solar cells.
  • the present invention has no special restrictions on the source of all raw materials, which can be commercially available; the substrate, metal back electrode, P-type antimony selenide layer, N-type perovskite absorption layer and conductive electrode are all the same as above. , and will not be repeated here.
  • the substrate is preferably pretreated first; since the substrate in the present invention is preferably a metal foil, the pretreatment preferably includes grinding and polishing, followed by deionized water, absolute ethanol Ultrasonic cleaning with acetone and drying.
  • the method for depositing the metal back electrode is a method well known to those skilled in the art, and there is no special limitation.
  • Preference is given to using magnetron sputtering.
  • the evaporation is preferably carried out under the condition that the degree of vacuum is less than 4 ⁇ 10 -4 ; the temperature of the evaporation is preferably 300°C to 600°C; the evaporation The rate is preferably 0.1-1.5 angstroms/second; the raw materials for the evaporation are preferably Se and Sb 2 Se 3 ; the ratio of the evaporation rate of Se and Sb 2 Se 3 is 1: (10-15), more preferably 1: (10 ⁇ 12).
  • the N-type perovskite precursor solution is coated on the substrate surface of the composite P-type antimony selenide layer, and after annealing treatment, the substrate of the composite N-type perovskite absorption layer is obtained; the N-type perovskite precursor
  • the solution preferably includes AX, BX 2 and N-type materials;
  • A is one or more of MA, FA, Cs and PEA, more preferably one or both of Cs and MA and FA; the Cs and MA
  • the molar ratio of one or both of them to FA is preferably (0.05-0.5): (0.7-0.95), more preferably (0.1-0.5): (0.7-0.9), and more preferably (0.15-0.5): 0.85;
  • MA is CH 3 NH 3 ;
  • FA is NH 2 CHNH 2 ;
  • PEA is C 8 H 9 NH 3 ;
  • B is Pb and/or Sn;
  • X is one or more of Cl, Br and I;
  • the N-type material preferably includes
  • a conductive electrode on the substrate of the composite N-type perovskite absorber layer to obtain a PN heterojunction antimony selenide/perovskite solar cell; the method for depositing a conductive electrode is a method well known to those skilled in the art. Yes, there is no special limitation, vacuum evaporation or magnetron sputtering is preferred in the present invention.
  • PN heterojunction antimony selenide/perovskite solar cell provided by the present invention and a preparation method thereof are described in detail below in conjunction with examples.
  • a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 ⁇ 4 Pa.
  • the evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstroms/second, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstroms/second.
  • FIG. 2 The schematic diagram of the evaporation equipment structure is shown in Figure 2; 2-1 is the heat insulation layer, 2-2 is the Se evaporation source, 2-3 is the bottom heater, 2-4 is the Sb 2 Se 3 evaporation source, 2-5 is the Top heater, 2-6 are distributors.
  • N-type perovskite absorbing layer (4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , MAI, and FAI, and the molar ratio of MAI to FAI is 0.15:0.85. The molar ratio of PbI 2 to (MAI+FAI) is 1:1.
  • Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.05:0.95, and the solvents are DMF and DMSO, wherein the volume ratio of DMF to DMSO is 6:4, forming a concentration of It is a perovskite precursor solution doped with N-type material at 1mol/mL; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 12mm/s, and the coating injection volume is 170uL, and then annealed at 120°C for 20min to form an N-type perovskite material layer with a thickness of about 120nm;
  • a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 ⁇ 4 Pa.
  • the evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstrom/second, and the evaporation rate of Sb 2 Se 3 powder is 1 angstrom/second.
  • the schematic diagram of the evaporation equipment structure is shown in Figure 2.
  • N-type perovskite absorbing layer (4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , CsBr, and FAI, and the molar ratio of CsBr to FAI is 0.15:0.85. The molar ratio of PbI 2 to (CsBr+FAI) is 1:1.
  • Sb 3+ is selected as the N-type dopant material, wherein the molar ratio of SbI 3 to PbI 2 is 0.03:0.97, the solvent is DMF, DMSO, 2ME, and the volume ratio is 6:2:2, forming a concentration of It is a perovskite precursor solution doped with an N-type material of 1mol/ml; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 11mm/s, and the coating injection volume is 170uL, and then annealed at 120°C for 20min to form an N-type perovskite material layer with a thickness of about 110nm;
  • a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 ⁇ 4 Pa.
  • the evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstrom/sec, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstrom/sec.
  • the schematic diagram of the evaporation equipment structure is shown in Figure 2.
  • N-type perovskite absorbing layer (4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , CsBr, FAI, MACl, and the molar ratio of CsBr to FAI is 0.15:0.85. The molar ratio of PbI 2 to (CsBr+FAI) is 1:1, and the molar ratio of MACl to (CsBr+FAI) is 0.35:1.
  • Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.03:0.97, the solvent is DMF, 2ME and NMP, and the volume ratio is 7:3:0.25, forming a concentration of It is a perovskite precursor solution doped with an N-type material at 1mol/ml; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 15mm/s, and the coating injection volume 170uL, and then annealed at 130°C for 20min to form an N-type perovskite material layer with a thickness of about 150nm.
  • a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 ⁇ 4 Pa.
  • the evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstroms/second, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstroms/second.
  • the schematic diagram of the evaporation equipment structure is shown in Figure 2.
  • N-type perovskite absorbing layer (4) Prepare N-type perovskite material solution, wherein the solutes are PbI 2 , MAI, FAI, and CsBr, and the molar ratio of MAI, FAI, and CsBr is 0.10:0.85: 0.05. The molar ratio of PbI 2 to (MAI+FAI+CsBr) is 1:1.
  • Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.03:0.97, and the solvent is DMF, NMP and 2ME, wherein the volume ratio of DMF, 2ME and NMP is 8: 2: 0.25, forming a perovskite precursor solution doped with N-type material at a concentration of 1.03mol/ml; then coating the N-type perovskite material solution to form a film by wet method, and the coating speed is 13mm/s , the coating injection volume is 170uL, and then annealed at 130°C for 20min to form an N-type perovskite material layer with a thickness of about 130nm;
  • I-V efficiency test The I-V curve and steady-state Jsc are tested by a solar simulator (7SS1503A, Beijing simulates AM1.5G sunlight, the light intensity is 100mW/cm2, using a digital source meter 2400 Keithley Instruments Inc) to record data.
  • the incident light intensity was calibrated with NREL calibrated silicon solar cells (Newport Stratford Inc 91150V).
  • the scan rate is 50mV/s, and the delay time is 0.1s.
  • the reverse scan is from 1.2V to 0.05V, while the forward scan is from 0.05V to 1.2V.

Abstract

Provided in the present invention is a PN heterojunction antimony selenide/perovskite solar cell. The solar cell comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode, which are sequentially arranged. Compared with the prior art, the present invention can not only broaden the utilization range of a solar spectrum but can also reduce the thermal relaxation loss of photon-generated carriers by means of forming a multi-junction solar cell by a plurality of light absorbers that have different band gaps, thereby improving the photoelectric conversion efficiency; in addition, the present invention reduces the process preparation steps and cost and also improves the battery stability by means of a PN heterojunction Sb2Se3/perovskite absorption layer, without an electron transport layer, a hole transport layer, etc.

Description

一种PN异质结硒化锑/钙钛矿太阳能电池及其制备方法A kind of PN heterojunction antimony selenide/perovskite solar cell and its preparation method
本申请要求于2021年12月23日提交中国专利局、申请号为202111595116.0、发明名称为“一种PN异质结硒化锑/钙钛矿太阳能电池及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 23, 2021, the application number is 202111595116.0, and the invention title is "A PN heterojunction antimony selenide/perovskite solar cell and its preparation method" rights, the entire contents of which are incorporated in this application by reference.
技术领域technical field
本发明属于太阳能电池技术领域，尤其涉及一种PN异质结硒化锑/钙钛矿太阳能电池及其制备方法。The invention belongs to the technical field of solar cells, in particular to a PN heterojunction antimony selenide/perovskite solar cell and a preparation method thereof.
背景技术Background technique
太阳能电池可以通过光电转换将太阳能转化为电能被人们直接使用而备受关注。根据太阳能电池的发展和所用的光吸收层材料，可将太阳能电池分为三类。第一类是硅基太阳能电池，包括单晶硅、多晶硅太阳能电池、非晶硅薄膜太阳能电池以及硅的叠层太阳能电池；第二类是化合物太阳能电池，包括铜铟镓硒(CIGS)、碲化镉(CdTe)、砷化镓(GaAs)和钙钛矿等太阳能电池；第三类是新型太阳能电池，包括染料敏化太阳能电池、有机太阳能电池和量子点太阳能电池等。Solar cells can convert solar energy into electrical energy through photoelectric conversion, which can be directly used by people and has attracted much attention. According to the development of solar cells and the light-absorbing layer materials used, solar cells can be divided into three categories. The first type is silicon-based solar cells, including monocrystalline silicon, polycrystalline silicon solar cells, amorphous silicon thin-film solar cells, and silicon stacked solar cells; the second type is compound solar cells, including copper indium gallium selenide (CIGS), tellurium Cadmium (CdTe), gallium arsenide (GaAs) and perovskite solar cells; the third category is new solar cells, including dye-sensitized solar cells, organic solar cells and quantum dot solar cells.
其中，钙钛矿型太阳能电池(perovskite solar cells)，是利用钙钛矿型的有机金属卤化物半导体作为吸光材料的太阳能电池，属于第三代太阳能电池，也称作新概念太阳能电池。Among them, perovskite solar cells (perovskite solar cells) are solar cells that use perovskite-type organometallic halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and are also called new concept solar cells.
钙钛矿太阳能电池，采用具有钙钛矿晶体结构的有机无机杂化的金属卤化物作为吸光层，自2009年以来，因制备方式简单、生产成本低廉和光电性能优异而备受关注，光电转换效率由3.8％迅速升至25％，成为当前发展最快的光伏技术，是全世界最受瞩目的新兴光伏技术。Perovskite solar cells, which use organic-inorganic hybrid metal halides with a perovskite crystal structure as the light-absorbing layer, have attracted much attention since 2009 because of their simple preparation methods, low production costs, and excellent photoelectric performance. Photoelectric conversion The efficiency has risen rapidly from 3.8% to 25%, becoming the fastest growing photovoltaic technology and the most watched emerging photovoltaic technology in the world.
单结太阳能电池由于只能吸收特定范围内的光子，使其具有肖克利-奎伊瑟(Shockley-Queisser)效率极限。将多个带隙不同的光吸收剂组成多结太阳能电池，不仅可以拓宽太阳光谱的利用范围，同时可以降低光生载流子的热驰豫损失。目前钙钛矿主要与晶硅、铜铟镓硒、钙钛矿等叠加形成双结或多结电池器件。但双结钙钛矿叠层电池是由电子传输层、宽带隙吸收层、空穴传输层和中间隧穿层、以及空穴传输层、窄带隙吸收层、电子传输层等工序制备而成，结构复杂，如公开号为CN111244220A的中国专利公开了一种全无机P/N异质结硒化锑/钙钛矿太阳能电池及其制备方法，所述太阳能电池的结构从下至上 依次为FTO导电玻璃基底、二氧化钛(TiO 2)层、无机CsPbBrI 2钙钛矿层、硒化处理的Sb 2Se 3层以及金属对电极层，在此专利中无机钙钛矿层并未进行N型处理，仍需电子传输层TiO 2的制备。 Single-junction solar cells have the Shockley-Queisser efficiency limit because they can only absorb photons within a specific range. Combining multiple light absorbers with different band gaps into multi-junction solar cells can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers. At present, perovskite is mainly stacked with crystalline silicon, copper indium gallium selenide, perovskite, etc. to form double-junction or multi-junction battery devices. However, the double-junction perovskite stack cell is prepared by processes such as electron transport layer, wide band gap absorption layer, hole transport layer and intermediate tunneling layer, as well as hole transport layer, narrow band gap absorption layer, and electron transport layer. The structure is complex. For example, the Chinese patent with the publication number CN111244220A discloses an all-inorganic P/N heterojunction antimony selenide/perovskite solar cell and its preparation method. The structure of the solar cell is FTO conductive from bottom to top. Glass substrate, titanium dioxide (TiO 2 ) layer, inorganic CsPbBrI 2 perovskite layer, selenized Sb 2 Se 3 layer and metal counter electrode layer. In this patent, the inorganic perovskite layer has not been N-type treated and still needs electron Preparation of transport layer TiO2 .
发明内容Contents of the invention
有鉴于此，本发明要解决的技术问题在于提供一种具有较宽吸收光谱和结构简单的PN异质结硒化锑/钙钛矿太阳能电池及其制备方法。In view of this, the technical problem to be solved by the present invention is to provide a PN heterojunction antimony selenide/perovskite solar cell with a broad absorption spectrum and a simple structure and a preparation method thereof.
本发明提供了一种PN异质结硒化锑/钙钛矿太阳能电池，包括依次设置的衬底、金属背电极、P型硒化锑层、N型钙钛矿吸收层与导电电极。The invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
优选的，所述衬底为柔性金属衬底；所述衬底的厚度为0.1～0.3mm。Preferably, the substrate is a flexible metal substrate; the thickness of the substrate is 0.1-0.3mm.
优选的，所述金属背电极的材料为金属钼；所述金属背电极的厚度为800～1000mm。Preferably, the material of the metal back electrode is metal molybdenum; the thickness of the metal back electrode is 800-1000mm.
优选的，所述P型硒化锑层的厚度为50～300nm。Preferably, the thickness of the P-type antimony selenide layer is 50-300 nm.
优选的，所述N型钙钛矿吸收层的厚度为100～200mm。Preferably, the thickness of the N-type perovskite absorbing layer is 100-200 mm.
优选的，所述N型钙钛矿吸收层的材料为掺杂有N型材料的ABX 3；其中，A为MA、FA、Cs与PEA中的一种或多种；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；所述N型材料包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种。 Preferably, the material of the N-type perovskite absorbing layer is ABX 3 doped with N-type materials; wherein, A is one or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; the N-type materials include Bi 3+ , One or more of Sb 3+ , Fe 3+ and Al 3+ .
优选的，所述N型钙钛矿吸收层中N型材料与B的摩尔比为(0.01～0.05)：(0.95～0.99)。Preferably, the molar ratio of N-type material to B in the N-type perovskite absorbing layer is (0.01-0.05): (0.95-0.99).
本发明还提供了一种PN异质结硒化锑/钙钛矿太阳能电池的制备方法，包括：The present invention also provides a preparation method of a PN heterojunction antimony selenide/perovskite solar cell, comprising:
S1)在衬底上沉积金属背电极，得到复合金属背电极的衬底；S1) Depositing a metal back electrode on the substrate to obtain a composite metal back electrode substrate;
S2)在所述复合金属背电极的衬底上蒸镀P型硒化锑层，得到复合P型硒化锑层的衬底；S2) Evaporating a P-type antimony selenide layer on the substrate of the composite metal back electrode to obtain a composite P-type antimony selenide layer substrate;
S3)将N型钙钛矿前驱体溶液涂覆在复合P型硒化锑层的衬底表面，退火处理后，得到复合N型钙钛矿吸收层的衬底；S3) coating the N-type perovskite precursor solution on the substrate surface of the composite P-type antimony selenide layer, and after annealing treatment, the substrate of the composite N-type perovskite absorption layer is obtained;
S4)在所述复合N型钙钛矿吸收层的衬底上沉积导电电极，得到PN异质结硒化锑/钙钛矿太阳能电池。S4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorbing layer to obtain a PN heterojunction antimony selenide/perovskite solar cell.
优选的，所述步骤S2)中的蒸镀为真空蒸镀；所述蒸镀的真空度小于4×10 -4Pa；所述蒸镀的温度为300℃～600℃；所述蒸镀的速率为0.3～1.5埃/秒；所述 蒸镀的原料为Se与Sb 2Se 3。 Preferably, the vapor deposition in the step S2) is vacuum vapor deposition; the vacuum degree of the vapor deposition is less than 4×10 -4 Pa; the temperature of the vapor deposition is 300°C-600°C; the vapor deposition The rate is 0.3-1.5 angstroms/second; the raw materials for the vapor deposition are Se and Sb 2 Se 3 .
优选的，所述N型钙钛矿前驱体溶液包括AX、BX 2与N型掺杂材料；A为MA、FA、Cs与PEA中的一种或多种；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；所述N型掺杂材料包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种；所述退火的温度为70℃～150℃；所述退火的时间为10～60min。 Preferably, the N-type perovskite precursor solution includes AX, BX 2 and N-type dopant materials; A is one or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; the N-type dopant material includes Bi 3+ , One or more of Sb 3+ , Fe 3+ and Al 3+ ; the annealing temperature is 70°C-150°C; the annealing time is 10-60min.
本发明提供一种PN异质结硒化锑/钙钛矿太阳能电池，包括依次设置的衬底、金属背电极、P型硒化锑层、N型钙钛矿吸收层与导电电极。与现有技术相比，本发明将多个带隙不同的光吸收剂组成多结太阳能电池，不仅可以拓宽太阳光谱的利用范围，同时可以降低光生载流子的热驰豫损失，提高光电转换效率；并且本发明通过PN异质结Sb 2Se 3钙钛矿吸收层，无需电子传输层与空穴传输层等，减少工艺制备步骤和成本，同时提高了电池稳定性。 The invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence. Compared with the prior art, the present invention composes multiple light absorbers with different band gaps into a multi-junction solar cell, which can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers and improve photoelectric conversion efficiency; and the present invention uses a PN heterojunction Sb 2 Se 3 perovskite absorber layer, without the need for an electron transport layer and a hole transport layer, etc., reducing process preparation steps and costs, and improving battery stability at the same time.
与双结钙钛矿叠层电池相比，本发明无需电子和/或空穴传输层以及中间复合层的制备，直接在1.1～1.3eV窄带隙的P型硒化锑层上刮涂制备掺杂金属离子的1.4～2.0eV的宽带隙N型钙钛矿电池，即可形成带隙不同的PN异质结结构，同时通过钙钛矿层强N型离子的掺杂也无需电子传输层和/或电子传输层的制备，具有工序简单、成本低、吸光范围广等优势，降低了电池设计和制备的技术难度。Compared with the double-junction perovskite laminated battery, the present invention does not need the preparation of the electron and/or hole transport layer and the intermediate composite layer, and directly prepares the mixed antimony selenide layer on the 1.1-1.3eV narrow bandgap P-type antimony selenide layer. The 1.4-2.0eV wide-bandgap N-type perovskite cell with heterometallic ions can form a PN heterojunction structure with different bandgap, and at the same time, the doping of strong N-type ions through the perovskite layer does not require an electron transport layer and/or Or the preparation of the electron transport layer has the advantages of simple process, low cost and wide light absorption range, which reduces the technical difficulty of battery design and preparation.
实验表明，本发明制备的PN异质结硒化锑/钙钛矿太阳能电池光电转换效率可达17.5％。Experiments show that the photoelectric conversion efficiency of the PN heterojunction antimony selenide/perovskite solar cell prepared by the invention can reach 17.5%.
附图说明Description of drawings
图1为本发明提供的PN异质结硒化锑/钙钛矿太阳能电池的结构示意图；Fig. 1 is the structural representation of the PN heterojunction antimony selenide/perovskite solar cell provided by the present invention;
图2为为本发明实施例中所用蒸发硒化锑设备的结构示意图。Fig. 2 is a schematic structural diagram of the antimony selenide evaporation equipment used in the embodiment of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提供了一种PN异质结硒化锑/钙钛矿太阳能电池，包括依次设置的衬底、金属背电极、P型硒化锑层、N型钙钛矿吸收层与导电电极。The invention provides a PN heterojunction antimony selenide/perovskite solar cell, which comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
参见图1，图1为本发明提供的PN异质结硒化锑/钙钛矿太阳能电池的结构示意图；其中1为衬底，2为金属背电极，3为P型硒化锑层，4为N型钙钛矿吸收层，5为导电电极。Referring to Fig. 1, Fig. 1 is the structural representation of the PN heterojunction antimony selenide/perovskite solar cell provided by the present invention; wherein 1 is a substrate, 2 is a metal back electrode, 3 is a P-type antimony selenide layer, 4 5 is an N-type perovskite absorption layer, and 5 is a conductive electrode.
其中，所述衬底为本领域技术人员熟知的衬底即可，并无特殊的限制，本发明中优选为金属箔，更优选为不锈钢箔；所述衬底的厚度优选为0.1～0.3mm。Wherein, the substrate can be a substrate well-known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably metal foil, more preferably stainless steel foil; the thickness of the substrate is preferably 0.1-0.3mm .
所述衬底上设置有金属背电极；所述金属背电极为技术人员熟知的金属背电极即可，并无特殊的限制，在本发明中优选为金属钼；所述背电极的厚度优选为800～1000nm。The substrate is provided with a metal back electrode; the metal back electrode is a metal back electrode well known to those skilled in the art, and is not particularly limited, and is preferably metal molybdenum in the present invention; the thickness of the back electrode is preferably 800~1000nm.
所述金属背电极上设置有P型硒化锑层；所述P型硒化锑层的厚度优选为50～300nm。A P-type antimony selenide layer is arranged on the metal back electrode; the thickness of the P-type antimony selenide layer is preferably 50-300 nm.
所述P型硒化锑层上设置有N型钙钛矿吸收层；所述N型钙钛矿吸收层的厚度优选为100～200mm，更优选为120～150nm，再优选为130～150nm，最优选为150mm；所述N型钙钛矿吸收层的材料优选为掺杂有N型材料的ABX 3；其中，A为MA、FA、Cs与PEA中的一种或多种；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；在本发明提供的实施例中，A具体为MA和/或Cs与FA；所述MA和/或Cs与FA的摩尔比优选为(0.1～0.2)：(0.8～0.9)，更优选为0.15：0.85；所述N型材料包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种；所述N型钙钛矿吸收层中N型材料与B的摩尔比优选为(0.01～0.05)：(0.95～0.99)，更优选为(0.03～0.05)：(0.95～0.97)。 An N-type perovskite absorbing layer is arranged on the P-type antimony selenide layer; the thickness of the N-type perovskite absorbing layer is preferably 100-200 mm, more preferably 120-150 nm, and more preferably 130-150 nm, The most preferred is 150 mm; the material of the N-type perovskite absorbing layer is preferably ABX 3 doped with N-type materials; wherein, A is one or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; the examples provided in the present invention Among them, A is specifically MA and/or Cs and FA; the molar ratio of MA and/or Cs and FA is preferably (0.1～0.2):(0.8～0.9), more preferably 0.15:0.85; the N type The material includes one or more of Bi 3+ , Sb 3+ , Fe 3+ and Al 3+ ; the molar ratio of N-type material to B in the N-type perovskite absorber layer is preferably (0.01-0.05) : (0.95-0.99), more preferably (0.03-0.05): (0.95-0.97).
所述N型钙钛矿吸收层上设置有导电电极；所述导电电极优选为透明电极，更优选为ITO、氧化锌与掺铝氧化锌中的一种或多种；所述导电电极的厚度优选为100～1000nm。The N-type perovskite absorption layer is provided with a conductive electrode; the conductive electrode is preferably a transparent electrode, more preferably one or more of ITO, zinc oxide and aluminum-doped zinc oxide; the thickness of the conductive electrode Preferably it is 100 to 1000 nm.
本发明将多个带隙不同的光吸收剂组成多结太阳能电池，不仅可以拓宽太阳光谱的利用范围，同时可以降低光生载流子的热驰豫损失，提高光电转换效率；并且本发明通过PN异质结Sb 2Se 3钙钛矿吸收层，无需电子传输层与空穴传输层等，减少工艺制备步骤和成本，同时提高了电池稳定性。 In the present invention, a plurality of light absorbers with different band gaps are used to form a multi-junction solar cell, which can not only broaden the utilization range of the solar spectrum, but also reduce the thermal relaxation loss of photogenerated carriers and improve the photoelectric conversion efficiency; and the present invention adopts PN The heterojunction Sb 2 Se 3 perovskite absorber layer does not require an electron transport layer and a hole transport layer, etc., reducing process preparation steps and costs, while improving battery stability.
本发明还提供了一种上述PN异质结硒化锑/钙钛矿太阳能电池的制备方法，包括：S1)在衬底上沉积金属背电极，得到复合金属背电极的衬底；S2)在所述复合金属背电极的衬底上蒸镀P型硒化锑层，得到复合P型硒化锑层的 衬底；S3)将N型钙钛矿前驱体溶液涂覆在复合P型硒化锑层的衬底表面，退火处理后，得到复合N型钙钛矿吸收层的衬底；S4)在所述复合N型钙钛矿吸收层的衬底上沉积导电电极，得到PN异质结硒化锑/钙钛矿太阳能电池。The present invention also provides a method for preparing the above-mentioned PN heterojunction antimony selenide/perovskite solar cell, comprising: S1) depositing a metal back electrode on a substrate to obtain a substrate of a composite metal back electrode; S2) A P-type antimony selenide layer is vapor-deposited on the substrate of the composite metal back electrode to obtain the substrate of the composite P-type antimony selenide layer; S3) coating the N-type perovskite precursor solution on the composite P-type antimony selenide layer The substrate surface of the antimony layer is annealed to obtain the substrate of the composite N-type perovskite absorbing layer; S4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorbing layer to obtain a PN heterojunction Antimony selenide/perovskite solar cells.
其中，本发明对所有原料的来源并没有特殊的限制，为市售即可；所述衬底、金属背电极、P型硒化锑层、N型钙钛矿吸收层与导电电极均同上所述，在此不再赘述。Among them, the present invention has no special restrictions on the source of all raw materials, which can be commercially available; the substrate, metal back electrode, P-type antimony selenide layer, N-type perovskite absorption layer and conductive electrode are all the same as above. , and will not be repeated here.
在本发明中，优选先将所述衬底进行预处理；由于本发明中所述衬底优选为金属箔，因此所述预处理优选包括打磨、抛光，然后依次用去离子水、无水乙醇与丙酮进行超声清洗，烘干。In the present invention, the substrate is preferably pretreated first; since the substrate in the present invention is preferably a metal foil, the pretreatment preferably includes grinding and polishing, followed by deionized water, absolute ethanol Ultrasonic cleaning with acetone and drying.
在预处理后的衬底上沉积金属背电极，得到复合金属背电极的衬底；所述沉积金属背电极的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明中优选采用磁控溅射。Deposit the metal back electrode on the pretreated substrate to obtain the substrate of the composite metal back electrode; the method for depositing the metal back electrode is a method well known to those skilled in the art, and there is no special limitation. In the present invention Preference is given to using magnetron sputtering.
在所述复合背电极的衬底上蒸镀P型硒化锑层，得到P型硒化锑层的衬底；所述蒸镀的方法优选为本领域技术人员熟知的方法即可并无特殊的限制，本发明中优选为真空蒸镀；所述蒸镀优选在真空度小于4×10 -4的条件下进行；所述蒸镀的温度优选为300℃～600℃；所述蒸镀的速率优选为0.1～1.5埃/秒；所述蒸镀的原料优选为Se与Sb 2Se 3；所述Se与Sb 2Se 3的蒸发速率之比为1：(10～15)，更优选为1：(10～12)。 Evaporate a P-type antimony selenide layer on the substrate of the composite back electrode to obtain the substrate of the P-type antimony selenide layer; In the present invention, vacuum evaporation is preferred; the evaporation is preferably carried out under the condition that the degree of vacuum is less than 4×10 -4 ; the temperature of the evaporation is preferably 300°C to 600°C; the evaporation The rate is preferably 0.1-1.5 angstroms/second; the raw materials for the evaporation are preferably Se and Sb 2 Se 3 ; the ratio of the evaporation rate of Se and Sb 2 Se 3 is 1: (10-15), more preferably 1: (10~12).
将N型钙钛矿前驱体溶液涂覆在复合P型硒化锑层的衬底表面，退火处理后，得到复合N型钙钛矿吸收层的衬底；所述N型钙钛矿前驱体溶液优选包括AX、BX 2与N型材料；A为MA、FA、Cs与PEA中的一种或多种，更优选为Cs与MA中的一种或两种与FA；所述Cs与MA中的一种或两种与FA的摩尔比优选为(0.05～0.5)：(0.7～0.95)，更优选为(0.1～0.5)：(0.7～0.9)，再优选为(0.15～0.5)：0.85；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；所述N型材料优选包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种；所述N型钙钛矿前驱体溶液的溶剂优选为DMF、NMP、2ME、DMSO、DMPU、乙腈与甲胺醇中的一种或多种，更优选为NMP、2ME、DMSO、DMPU、乙腈与甲胺醇中的一种或多种与DMF；NMP、2ME、DMSO、DMPU、乙腈与甲胺醇中的一种或多种与DMF的体积比优选为(2～4)：(6～8)；在本发明提供的实施例中，所述N型钙钛矿前驱体 溶液的溶剂具体为体积比为6：4的DMF与DMSO的混合溶液、体积比为6：2：2的DMF与DMSO及2ME的混合溶液、体积比为7：3：0.25的DMF和2ME及NMP的混合溶液或体积比为8：2：0.25的DMF和2ME及NMP的混合溶液；所述N型钙钛矿前驱体溶液中ABX 3的浓度优选为0.1～1.5mol/mL；通过涂覆使N型钙钛矿前驱体溶液湿法成膜，其中涂覆的方法可为涂布、喷涂或旋涂等，并无特殊的限制；所述退火的温度优选为70℃～150℃；所述退火的时间优选为10～60min。 The N-type perovskite precursor solution is coated on the substrate surface of the composite P-type antimony selenide layer, and after annealing treatment, the substrate of the composite N-type perovskite absorption layer is obtained; the N-type perovskite precursor The solution preferably includes AX, BX 2 and N-type materials; A is one or more of MA, FA, Cs and PEA, more preferably one or both of Cs and MA and FA; the Cs and MA The molar ratio of one or both of them to FA is preferably (0.05-0.5): (0.7-0.95), more preferably (0.1-0.5): (0.7-0.9), and more preferably (0.15-0.5): 0.85; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; The N-type material preferably includes one or more of Bi 3+ , Sb 3+ , Fe 3+ and Al 3+ ; the solvent of the N-type perovskite precursor solution is preferably DMF, NMP, 2ME, DMSO, One or more of DMPU, acetonitrile and methylamino alcohol, more preferably one or more of NMP, 2ME, DMSO, DMPU, acetonitrile and methylamino alcohol and DMF; NMP, 2ME, DMSO, DMPU, acetonitrile The volume ratio of one or more of methanol and DMF is preferably (2-4): (6-8); in the embodiments provided by the invention, the N-type perovskite precursor solution The solvent is specifically a mixed solution of DMF and DMSO with a volume ratio of 6:4, a mixed solution of DMF, DMSO and 2ME with a volume ratio of 6:2:2, and a mixture of DMF, 2ME and NMP with a volume ratio of 7:3:0.25. A mixed solution or a mixed solution of DMF, 2ME and NMP with a volume ratio of 8:2:0.25; the concentration of ABX 3 in the N-type perovskite precursor solution is preferably 0.1 to 1.5mol/mL; N Type perovskite precursor solution wet method film formation, wherein the method of coating can be coating, spray coating or spin coating, etc., there is no special limitation; the temperature of the annealing is preferably 70 ℃ ~ 150 ℃; the annealing The time is preferably 10 to 60 minutes.
在所述复合N型钙钛矿吸收层的衬底上沉积导电电极，得到PN异质结硒化锑/钙钛矿太阳能电池；所述沉积导电电极的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明中优选为真空蒸镀或磁控溅射。Deposit a conductive electrode on the substrate of the composite N-type perovskite absorber layer to obtain a PN heterojunction antimony selenide/perovskite solar cell; the method for depositing a conductive electrode is a method well known to those skilled in the art. Yes, there is no special limitation, vacuum evaporation or magnetron sputtering is preferred in the present invention.
为了进一步说明本发明，以下结合实施例对本发明提供一种PN异质结硒化锑/钙钛矿太阳能电池及其制备方法进行详细描述。In order to further illustrate the present invention, a PN heterojunction antimony selenide/perovskite solar cell provided by the present invention and a preparation method thereof are described in detail below in conjunction with examples.
以下实施例中所用的试剂均为市售。The reagents used in the following examples are all commercially available.
实施例1Example 1
1)选择厚度为0.2mm的不锈钢箔(1)，进行打磨和抛光，然后分别采用去离子水、无水乙醇和丙酮进行超声清洗30min，之后烘干；1) Select a stainless steel foil (1) with a thickness of 0.2 mm, grind and polish it, then use deionized water, absolute ethanol and acetone to perform ultrasonic cleaning for 30 minutes, and then dry it;
2)金属背电极(2)的制备：采用磁控溅射将Mo沉积在不锈钢箔(1)上作为电池的背电极，沉积厚度800nm；2) Preparation of the metal back electrode (2): Deposit Mo on the stainless steel foil (1) as the back electrode of the battery by magnetron sputtering, with a deposition thickness of 800 nm;
3)Sb 2Se 3吸收层(3)的制备：在真空度小于4*10 -4Pa下，在350℃范围内采用真空蒸镀法进行蒸镀一层300nm厚度的Sb 2Se 3层。其中蒸镀原物料为Se和Sb 2Se 3粉，Se粉的蒸发速率为0.1埃/秒，Sb 2Se 3粉的蒸发速率为1.2埃/秒。蒸发设备结构示意图如图2所示；其中2-1为隔热层，2-2为Se蒸发源，2-3为底部加热器，2-4为Sb 2Se 3蒸发源，2-5为顶部加热器，2-6为分配器。 3) Preparation of the Sb 2 Se 3 absorbing layer (3): a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 −4 Pa. The evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstroms/second, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstroms/second. The schematic diagram of the evaporation equipment structure is shown in Figure 2; 2-1 is the heat insulation layer, 2-2 is the Se evaporation source, 2-3 is the bottom heater, 2-4 is the Sb 2 Se 3 evaporation source, 2-5 is the Top heater, 2-6 are distributors.
4)N型钙钛矿吸收层(4)的制备：制备N型钙钛矿材料溶液，其中溶质为PbI 2、MAI、FAI，其中MAI与FAI的摩尔比为0.15：0.85。PbI 2与(MAI+FAI)的摩尔比为1：1。在本实施例中选择Bi 3+作为N型掺杂材料，其中BiI 3与PbI 2的摩尔比为0.05：0.95，溶剂为DMF和DMSO，其中DMF与DMSO的体积比为6：4，形成浓度为1mol/mL的掺杂有N型材料的钙钛矿前驱体溶液；之后将N型钙钛矿材料溶液涂布湿法成膜，其中涂布速度为12mm/s，涂布注液量为170uL，然后在120℃退火处理20min，形成N型钙钛矿材料层，厚度 大约为120nm； 4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , MAI, and FAI, and the molar ratio of MAI to FAI is 0.15:0.85. The molar ratio of PbI 2 to (MAI+FAI) is 1:1. In this embodiment, Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.05:0.95, and the solvents are DMF and DMSO, wherein the volume ratio of DMF to DMSO is 6:4, forming a concentration of It is a perovskite precursor solution doped with N-type material at 1mol/mL; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 12mm/s, and the coating injection volume is 170uL, and then annealed at 120°C for 20min to form an N-type perovskite material layer with a thickness of about 120nm;
5)对电极(5)的制备：在N型钙钛矿吸收层(4)上磁控溅射一层200nm的掺铟氧化锡。5) Preparation of the counter electrode (5): magnetron sputtering a layer of 200 nm indium-doped tin oxide on the N-type perovskite absorbing layer (4).
实施例2Example 2
1)选择厚度为0.2mm的不锈钢箔(1)，进行打磨和抛光，然后分别采用去离子水、无水乙醇和丙酮进行超声清洗30min，之后烘干；1) Select a stainless steel foil (1) with a thickness of 0.2 mm, grind and polish it, then use deionized water, absolute ethanol and acetone to perform ultrasonic cleaning for 30 minutes, and then dry it;
2)金属背电极(2)的制备：采用磁控溅射将Mo沉积在不锈钢箔(1)上作为电池的背电极，沉积厚度1000nm；2) Preparation of the metal back electrode (2): Deposit Mo on the stainless steel foil (1) as the back electrode of the battery by magnetron sputtering, with a deposition thickness of 1000 nm;
3)Sb 2Se 3吸收层(3)的制备：在真空度小于4*10 -4Pa下，在350℃范围内采用真空蒸镀法进行蒸镀一层300nm厚度的Sb 2Se 3层。其中蒸镀原物料为Se和Sb 2Se 3粉，Se粉的蒸发速率为0.1埃/秒，Sb 2Se 3粉的蒸发速率为1埃/秒。蒸发设备结构示意图如图2所示。 3) Preparation of the Sb 2 Se 3 absorbing layer (3): a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 −4 Pa. The evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstrom/second, and the evaporation rate of Sb 2 Se 3 powder is 1 angstrom/second. The schematic diagram of the evaporation equipment structure is shown in Figure 2.
4)N型钙钛矿吸收层(4)的制备：制备N型钙钛矿材料溶液，其中溶质为PbI 2、CsBr、FAI，其中CsBr与FAI的摩尔比为0.15：0.85。PbI 2与(CsBr+FAI)的摩尔比为1：1。在本实施例中选择Sb 3+作为N型掺杂材料，其中SbI 3与PbI 2的摩尔比为0.03：0.97，溶剂为DMF、DMSO、2ME，其体积比为6：2：2，形成浓度为1mol/ml的掺杂有N型材料的钙钛矿前驱体溶液；之后将N型钙钛矿材料溶液涂布湿法成膜，其中涂布速度为11mm/s，涂布注液量为170uL，然后在120℃退火处理20min，形成N型钙钛矿材料层，厚度大约为110nm； 4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , CsBr, and FAI, and the molar ratio of CsBr to FAI is 0.15:0.85. The molar ratio of PbI 2 to (CsBr+FAI) is 1:1. In this embodiment, Sb 3+ is selected as the N-type dopant material, wherein the molar ratio of SbI 3 to PbI 2 is 0.03:0.97, the solvent is DMF, DMSO, 2ME, and the volume ratio is 6:2:2, forming a concentration of It is a perovskite precursor solution doped with an N-type material of 1mol/ml; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 11mm/s, and the coating injection volume is 170uL, and then annealed at 120°C for 20min to form an N-type perovskite material layer with a thickness of about 110nm;
5)对电极(5)的制备：在N型钙钛矿吸收层(4)上磁控溅射一层300nm的掺铟氧化锡。5) Preparation of the counter electrode (5): magnetron sputtering a layer of 300 nm indium-doped tin oxide on the N-type perovskite absorbing layer (4).
实施例3Example 3
1)选择厚度为0.2mm的不锈钢箔(1)，进行打磨和抛光，然后分别采用去离子水、无水乙醇和丙酮进行超声清洗30min，之后烘干；1) Select a stainless steel foil (1) with a thickness of 0.2 mm, grind and polish it, then use deionized water, absolute ethanol and acetone to perform ultrasonic cleaning for 30 minutes, and then dry it;
2)金属背电极(2)的制备：采用磁控溅射将Mo沉积在不锈钢箔(1)上作为电池的背电极，沉积厚度800nm；2) Preparation of the metal back electrode (2): Deposit Mo on the stainless steel foil (1) as the back electrode of the battery by magnetron sputtering, with a deposition thickness of 800 nm;
3)Sb 2Se 3吸收层(3)的制备：在真空度小于4*10 -4Pa下，在350℃范围内采用真空蒸镀法进行蒸镀一层300nm厚度的Sb 2Se 3层。其中蒸镀原物料为Se和Sb 2Se 3粉，Se粉的蒸发速率为0.1埃/秒，Sb 2Se 3粉的蒸发速率为1.2埃/ 秒。蒸发设备结构示意图如图2所示。 3) Preparation of the Sb 2 Se 3 absorbing layer (3): a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 −4 Pa. The evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstrom/sec, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstrom/sec. The schematic diagram of the evaporation equipment structure is shown in Figure 2.
4)N型钙钛矿吸收层(4)的制备：制备N型钙钛矿材料溶液，其中溶质为PbI 2、CsBr、FAI、MACl，其中CsBr与FAI的摩尔比为0.15：0.85。PbI 2与(CsBr+FAI)的摩尔比为1：1，MACl与(CsBr+FAI)的摩尔比为0.35：1。在本实施例中选择Bi 3+作为N型掺杂材料，其中BiI 3与PbI 2的摩尔比为0.03：0.97，溶剂为DMF、2ME和NMP，其体积比为7：3：0.25，形成浓度为1mol/ml的掺杂有N型材料的钙钛矿前驱体溶液；之后将N型钙钛矿材料溶液进行涂布湿法成膜，其中涂布速度为15mm/s，涂布注液量为170uL，然后在130℃退火处理20min，形成N型钙钛矿材料层，厚度大约为150nm。 4) Preparation of N-type perovskite absorbing layer (4): prepare N-type perovskite material solution, wherein the solutes are PbI 2 , CsBr, FAI, MACl, and the molar ratio of CsBr to FAI is 0.15:0.85. The molar ratio of PbI 2 to (CsBr+FAI) is 1:1, and the molar ratio of MACl to (CsBr+FAI) is 0.35:1. In this embodiment, Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.03:0.97, the solvent is DMF, 2ME and NMP, and the volume ratio is 7:3:0.25, forming a concentration of It is a perovskite precursor solution doped with an N-type material at 1mol/ml; after that, the N-type perovskite material solution is coated with a wet method to form a film, wherein the coating speed is 15mm/s, and the coating injection volume 170uL, and then annealed at 130°C for 20min to form an N-type perovskite material layer with a thickness of about 150nm.
5)对电极(5)的制备：在N型钙钛矿吸收层(4)上磁控溅射一层300nm的掺铟氧化锡。5) Preparation of the counter electrode (5): magnetron sputtering a layer of 300 nm indium-doped tin oxide on the N-type perovskite absorbing layer (4).
实施例4Example 4
1)选择厚度为0.2mm的不锈钢箔(1)，进行打磨和抛光，然后分别采用去离子水、无水乙醇和丙酮进行超声清洗30min，之后烘干；1) Select a stainless steel foil (1) with a thickness of 0.2 mm, grind and polish it, then use deionized water, absolute ethanol and acetone to perform ultrasonic cleaning for 30 minutes, and then dry it;
2)金属背电极(2)的制备：采用磁控溅射将Mo沉积在不锈钢箔(1)上作为电池的背电极，沉积厚度1000nm；2) Preparation of the metal back electrode (2): Deposit Mo on the stainless steel foil (1) as the back electrode of the battery by magnetron sputtering, with a deposition thickness of 1000 nm;
3)Sb 2Se 3吸收层(3)的制备：在真空度小于4*10 -4Pa下，在350℃范围内采用真空蒸镀法进行蒸镀一层300nm厚度的Sb 2Se 3层。其中蒸镀原物料为Se和Sb 2Se 3粉，Se粉的蒸发速率为0.1埃/秒，Sb 2Se 3粉的蒸发速率为1.2埃/秒。蒸发设备结构示意图如图2所示。 3) Preparation of the Sb 2 Se 3 absorbing layer (3): a layer of Sb 2 Se 3 with a thickness of 300 nm was vapor-deposited by a vacuum evaporation method at 350° C. under a vacuum degree of less than 4*10 −4 Pa. The evaporation raw materials are Se and Sb 2 Se 3 powder, the evaporation rate of Se powder is 0.1 angstroms/second, and the evaporation rate of Sb 2 Se 3 powder is 1.2 angstroms/second. The schematic diagram of the evaporation equipment structure is shown in Figure 2.
4)N型钙钛矿吸收层(4)的制备：制备N型钙钛矿材料溶液，其中溶质为PbI 2、MAI、FAI、CsBr，其中MAI、FAI与CsBr的摩尔比为0.10：0.85：0.05。PbI 2与(MAI+FAI+CsBr)的摩尔比为1：1。在本实施例中选择Bi 3+作为N型掺杂材料，其中BiI 3与PbI 2的摩尔比为0.03：0.97，溶剂为DMF、NMP和2ME，其中DMF、2ME和NMP的体积比为8：2：0.25，形成浓度为1.03mol/ml的掺杂有N型材料的钙钛矿前驱体溶液；之后将N型钙钛矿材料溶液涂布湿法成膜，其中涂布速度为13mm/s，涂布注液量为170uL，然后在130℃退火处理20min，形成N型钙钛矿材料层，厚度大约为130nm； 4) Preparation of N-type perovskite absorbing layer (4): Prepare N-type perovskite material solution, wherein the solutes are PbI 2 , MAI, FAI, and CsBr, and the molar ratio of MAI, FAI, and CsBr is 0.10:0.85: 0.05. The molar ratio of PbI 2 to (MAI+FAI+CsBr) is 1:1. In this embodiment, Bi 3+ is selected as the N-type dopant material, wherein the molar ratio of BiI 3 to PbI 2 is 0.03:0.97, and the solvent is DMF, NMP and 2ME, wherein the volume ratio of DMF, 2ME and NMP is 8: 2: 0.25, forming a perovskite precursor solution doped with N-type material at a concentration of 1.03mol/ml; then coating the N-type perovskite material solution to form a film by wet method, and the coating speed is 13mm/s , the coating injection volume is 170uL, and then annealed at 130°C for 20min to form an N-type perovskite material layer with a thickness of about 130nm;
5)对电极(5)的制备：在N型钙钛矿吸收层(4)上磁控溅射一层300nm的掺铟氧化锡。5) Preparation of the counter electrode (5): magnetron sputtering a layer of 300 nm indium-doped tin oxide on the N-type perovskite absorbing layer (4).
对实施例1～4中得到的PN异质结硒化锑/钙钛矿太阳能电池的性能进行检测，得到结果如表1所示。检测方法如下。The performance of the PN heterojunction antimony selenide/perovskite solar cells obtained in Examples 1-4 was tested, and the results are shown in Table 1. The detection method is as follows.
I-V效率测试：测试I-V曲线和稳态Jsc是通过太阳光模拟器(7SS1503A，北京模拟AM1.5G的太阳光，光强为100mW/cm2，使用数字源表2400 Keithley Instruments Inc)记录数据。用NREL校准的硅太阳能电池(Newport Stratford Inc 91150V)校准入射光强度。扫描速率为50mV/s，延迟时间为0.1s。反向扫描是从1.2V到0.05V，而正向扫描是从0.05V到1.2V。I-V efficiency test: The I-V curve and steady-state Jsc are tested by a solar simulator (7SS1503A, Beijing simulates AM1.5G sunlight, the light intensity is 100mW/cm2, using a digital source meter 2400 Keithley Instruments Inc) to record data. The incident light intensity was calibrated with NREL calibrated silicon solar cells (Newport Stratford Inc 91150V). The scan rate is 50mV/s, and the delay time is 0.1s. The reverse scan is from 1.2V to 0.05V, while the forward scan is from 0.05V to 1.2V.
表1 不同N型掺杂及溶剂的比例对电池性能的影响Table 1 Effect of different N-type doping and solvent ratios on battery performance
Figure PCTCN2022101422-appb-000001
Figure PCTCN2022101422-appb-000001

Claims (10)

  1. 一种PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，包括依次设置的衬底、金属背电极、P型硒化锑层、N型钙钛矿吸收层与导电电极。A PN heterojunction antimony selenide/perovskite solar cell is characterized in that it comprises a substrate, a metal back electrode, a P-type antimony selenide layer, an N-type perovskite absorption layer and a conductive electrode arranged in sequence.
  2. 根据权利要求1所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述衬底为柔性金属衬底；所述衬底的厚度为0.1～0.3mm。The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the substrate is a flexible metal substrate; the thickness of the substrate is 0.1-0.3 mm.
  3. 根据权利要求1所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述金属背电极的材料为金属钼；所述金属背电极的厚度为800～1000mm。The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the material of the metal back electrode is metal molybdenum; the thickness of the metal back electrode is 800-1000mm.
  4. 根据权利要求1所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述P型硒化锑层的厚度为50～300nm。The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the thickness of the P-type antimony selenide layer is 50-300 nm.
  5. 根据权利要求1所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述N型钙钛矿吸收层的厚度为100～200mm。The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the thickness of the N-type perovskite absorbing layer is 100-200 mm.
  6. 根据权利要求1所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述N型钙钛矿吸收层的材料为掺杂有N型材料的ABX 3；其中，A为MA、FA、Cs与PEA中的一种或多种；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；所述N型材料包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种。 The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the material of the N-type perovskite absorber layer is ABX 3 doped with N-type materials; wherein, A One or more of MA, FA, Cs and PEA; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is Cl , one or more of Br and I; the N-type material includes one or more of Bi 3+ , Sb 3+ , Fe 3+ and Al 3+ .
  7. 根据权利要求6所述的PN异质结硒化锑/钙钛矿太阳能电池，其特征在于，所述N型钙钛矿吸收层中N型材料与B的摩尔比为(0.01～0.05)：(0.95～0.99)。The PN heterojunction antimony selenide/perovskite solar cell according to claim 6, wherein the molar ratio of the N-type material to B in the N-type perovskite absorbing layer is (0.01-0.05): (0.95～0.99).
  8. 一种PN异质结硒化锑/钙钛矿太阳能电池的制备方法，其特征在于，包括：A method for preparing a PN heterojunction antimony selenide/perovskite solar cell, characterized in that it comprises:
    S1)在衬底上沉积金属背电极，得到复合金属背电极的衬底；S1) Depositing a metal back electrode on the substrate to obtain a composite metal back electrode substrate;
    S2)在所述复合金属背电极的衬底上蒸镀P型硒化锑层，得到复合P型硒化锑层的衬底；S2) Evaporating a P-type antimony selenide layer on the substrate of the composite metal back electrode to obtain a composite P-type antimony selenide layer substrate;
    S3)将N型钙钛矿前驱体溶液涂覆在复合P型硒化锑层的衬底表面，退火处理后，得到复合N型钙钛矿吸收层的衬底；S3) coating the N-type perovskite precursor solution on the substrate surface of the composite P-type antimony selenide layer, and after annealing treatment, the substrate of the composite N-type perovskite absorption layer is obtained;
    S4)在所述复合N型钙钛矿吸收层的衬底上沉积导电电极，得到PN异质结硒化锑/钙钛矿太阳能电池。S4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorbing layer to obtain a PN heterojunction antimony selenide/perovskite solar cell.
  9. 根据权利要求8所述的制备方法，其特征在于，所述步骤S2)中的蒸镀为真空蒸镀；所述蒸镀的真空度小于4×10 -4Pa；所述蒸镀的温度为300℃～600℃；所述蒸镀的速率为0.3～1.5埃/秒；所述蒸镀的原料为Se与Sb 2Se 3。 The preparation method according to claim 8, characterized in that, the evaporation in the step S2) is vacuum evaporation; the vacuum degree of the evaporation is less than 4×10 -4 Pa; the temperature of the evaporation is 300°C-600°C; the evaporation rate is 0.3-1.5 angstroms/second; the raw materials for the evaporation are Se and Sb 2 Se 3 .
  10. 根据权利要求8所述的制备方法，其特征在于，所述N型钙钛矿前驱体溶液包括AX、BX 2与N型掺杂材料；A为MA、FA、Cs与PEA中的一种或多种；MA为CH 3NH 3；FA为NH 2CHNH 2；PEA为C 8H 9NH 3；B为Pb和/或Sn；X为Cl、Br与I中的一种或多种；所述N型掺杂材料包括Bi 3+、Sb 3+、Fe 3+与Al 3+中的一种或多种；所述退火的温度为70℃～150℃；所述退火的时间为10～60min。 The preparation method according to claim 8, wherein the N-type perovskite precursor solution includes AX, BX 2 and N-type dopant materials; A is one or more of MA, FA, Cs and PEA Multiple; MA is CH 3 NH 3 ; FA is NH 2 CHNH 2 ; PEA is C 8 H 9 NH 3 ; B is Pb and/or Sn; X is one or more of Cl, Br and I; The N-type dopant material includes one or more of Bi 3+ , Sb 3+ , Fe 3+ and Al 3+ ; the annealing temperature is 70°C-150°C; the annealing time is 10-100°C. 60min.
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