WO2023185464A1 - 一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 - Google Patents

一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 Download PDF

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WO2023185464A1
WO2023185464A1 PCT/CN2023/081524 CN2023081524W WO2023185464A1 WO 2023185464 A1 WO2023185464 A1 WO 2023185464A1 CN 2023081524 W CN2023081524 W CN 2023081524W WO 2023185464 A1 WO2023185464 A1 WO 2023185464A1
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layer
amorphous silicon
perovskite
transport layer
silicon layer
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毕恩兵
郭铁
巴前凯
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Advanced Solar Technology Institute Xuancheng
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Advanced Solar Technology Institute Xuancheng
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Publication of WO2023185464A1 publication Critical patent/WO2023185464A1/zh
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
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    • 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
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H10F10/165—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells
    • H10F10/166—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells the Group IV-IV heterojunctions being heterojunctions of crystalline and amorphous materials, e.g. silicon heterojunction [SHJ] photovoltaic cells
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    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/19—Photovoltaic cells having multiple potential barriers of different types, e.g. tandem cells having both PN and PIN junctions
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    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material 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
    • H—ELECTRICITY
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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • 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 present invention relates to the technical field of solar cells, and in particular to a perovskite/silicon heterojunction stacked solar cell and a preparation method thereof.
  • Perovskite solar cells have the advantages of high absorption coefficient (10 5 cm -1 ), high open circuit voltage (>1.2eV), adjustable band gap (1.2 ⁇ 2.3eV), lamination application, and solution preparation. Perovskite solar cells started in 2009. After more than ten years of research and development, the efficiency of a single cell has continued to set new records, increasing from 3.8% to 25.5%. The stability lasted from a few minutes to 10,000 hours. Silicon-based heterojunction solar cells have the characteristics of high conversion efficiency and high long-wave spectral response, and the efficiency has now reached more than 25%.
  • any solar cell uses a single photoelectric conversion material, and the theoretical efficiency is determined by its bandgap width, and there is a theoretical limit of efficiency.
  • the theoretical efficiency limit of single-cell perovskite is 33%, and the theoretical efficiency limit of heterogeneous crystalline silicon solar cells is 29%. This is due to the broad energy distribution in the solar spectrum, and any existing material can only absorb photons with energy higher than its energy band value.
  • the photons with smaller energy in the sunlight will pass through the battery, be absorbed by the back electrode metal, and be converted into heat energy; while the excess energy of the other high-energy photons exceeding the forbidden band width will excite phonons and become heat losses, that is, high-energy Photons cannot be fully utilized. These energy losses limit the efficiency of solar cells.
  • the tunnel junction 108 is made of ITO, IZO, AZO, IWO, ICO or other transparent materials.
  • Thin film material patent CN 213150795 U, uses a transparent conductive layer and a heavily doped silicon layer as the intermediate composite layer.
  • this will increase the preparation and equipment costs.
  • metal oxide has a relatively large absorption of the near-infrared spectrum, which will affect Photocurrent of silicon cells. Therefore, it is necessary to develop new composite layers to improve the photocurrent of tandem cells to solve the above technical problems existing in the existing technology.
  • the purpose of the present invention is to propose a perovskite/silicon heterojunction tandem solar cell and a preparation method thereof, so as to solve the problem of low photoelectric conversion efficiency of the perovskite tandem solar cell.
  • the present invention provides a perovskite/silicon heterojunction tandem solar cell, including a silicon-based sub-cell and a perovskite sub-cell stacked on the silicon-based sub-cell.
  • the silicon-based sub-cell and the perovskite sub-cell are There is an intermediate layer or composite junction formed between the p-type heavily doped amorphous silicon layer and the n-type heavily doped amorphous silicon layer between the mineral cells.
  • the p-type heavily doped amorphous silicon layer has a thickness of 1 to 30 nm, and the doping concentration is 10 18 –10 20 cm -3 ;
  • the n-type heavily doped amorphous silicon layer has a thickness of 1 to 30 nm, and the doping concentration is 1 to 30 nm.
  • the impurity concentration is 10 18 –10 20 cm -3 .
  • the stacked solar cell has a formal stacked structure
  • the silicon-based sub-cell includes a first metal electrode, a first transparent conductive layer, an n-type doped amorphous silicon layer, and a first intrinsic layer that are stacked sequentially from bottom to top.
  • the perovskite sub-cell includes a first electron transport layer, a second electron transport layer, a calcium
  • the titanium light-absorbing layer, the first hole transport layer, the second hole transport layer, the second transparent conductive layer and the second metal electrode layer, the intermediate layer or composite junction is stacked sequentially from bottom to top and is arranged on the second base layer.
  • the laminated solar cell is a reverse stacked structure, and the silicon-based sub-cell includes from bottom to top
  • the first metal electrode, the first transparent conductive layer, the p-type doped amorphous silicon layer, the first intrinsic amorphous silicon layer, the N-type single crystal silicon layer and the second intrinsic amorphous silicon layer are stacked in sequence, so
  • the perovskite sub-cell includes a first hole transport layer, a second hole transport layer, a perovskite light-absorbing layer, a first electron transport layer, a second electron transport layer, and a second transparent layer that are stacked sequentially from bottom to top.
  • the conductive layer and the second metal electrode layer, the intermediate layer or composite junction is an n-type heavily doped amorphous layer that is stacked from bottom to top and is arranged between the second intrinsic amorphous silicon layer and the first hole transport layer. Silicon layer and p-type heavily doped amorphous silicon layer.
  • the first transparent conductive layer and the second transparent conductive layer are preferably transparent metal oxide conductive layers.
  • the first metal electrode and the second metal electrode are made of one or more materials selected from silver, copper, gold, aluminum, palladium, titanium, chromium, or nickel; the first transparent conductive layer and the second transparent conductive layer are The conductive layers are all transparent metal oxide conductive layers.
  • the transparent metal oxide conductive layers are made of indium tin oxide (ITO), indium tungsten oxide (IWO), fluorine-doped tin oxide (FTO), indium zinc oxide (IZO) or aluminum-doped oxide. Made of one or more materials in zinc (AZO).
  • the first hole transport layer and/or the second hole transport layer are made of p-type semiconductor material; the first electron transport layer and/or the second electron transport layer are made of n-type semiconductor material.
  • the first hole transport layer and/or the second hole transport layer are made of nickel oxide, molybdenum oxide, cuprous oxide, copper iodide, copper phthalocyanine, cuprous thiocyanate, redox graphene, polyethylene oxide, etc.
  • the first electron transport layer and/or the second electron transport layer are made of titanium oxide (TiO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), and zinc tin oxide (Zn 2 SnO 4 ).
  • TiO 2 titanium oxide
  • SnO 2 tin oxide
  • ZnO zinc oxide
  • Zn 2 SnO 4 zinc tin oxide
  • C60 fullerene
  • graphene or fullerene derivatives made of one or more materials from fullerene (C60), graphene or fullerene derivatives.
  • the material of the perovskite light-absorbing layer is an ABX 3 structure.
  • the ABX 3 structure is composed of corner-sharing BX 6 octahedrons and A cations located in its gaps, where A is a monovalent cation; B is a divalent cation; X is a halogen anions.
  • A is preferably one or more of MA, FA, Cs or Rb, B is preferably Pb, and X is preferably one or more of I, Br, Cl halogen or pseudo-halogen such as SCN, BF 4 , PF 6, etc. kind; the band gap of the perovskite sub-cell ranges from 1.5eV to 1.85eV.
  • the present invention also provides a method for preparing the perovskite/silicon heterojunction tandem solar cell, including a preparation method for a formal stacked structure and a preparation method for a reverse stacked structure, wherein the preparation method for the formal stacked structure includes follow these steps:
  • the preparation method of the trans-laminated structure includes the following steps:
  • the preparation method of the first hole transport layer, the second hole transport layer, the first electron transport layer and the second electron transport layer is a physical deposition method or a chemical deposition method, wherein the physical deposition method includes vacuum evaporation method, sputtering method radiation, ion beam deposition and pulsed laser deposition methods; chemical deposition methods include chemical vapor deposition, atomic layer deposition, spin coating, slit coating and doctor blade methods.
  • the first transparent conductive layer and the second transparent conductive layer are prepared by vacuum evaporation, sputtering, ion beam deposition and pulse laser deposition.
  • the preparation method of the perovskite light-absorbing layer is a physical deposition method and/or a chemical deposition method, wherein the physical deposition method includes a vacuum evaporation method, and the chemical deposition method includes chemical vapor deposition, spin coating, slit coating and doctor blade method .
  • the perovskite/silicon heterojunction tandem solar cell of the present invention no longer uses a transparent conductive layer of metal oxide as the top perovskite solar cell and the bottom heterojunction silicon solar cell.
  • the intermediate layer (or composite layer or tunneling layer) uses a p-type heavily doped amorphous silicon layer and an n-type heavily doped amorphous silicon layer as carrier recombination junctions. On the one hand, it can greatly reduce preparation and equipment costs, and on the other hand, it can improve the photocurrent density and conversion efficiency of tandem cells.
  • Figure 1 is a schematic diagram of the formal stacked structure of the perovskite/silicon heterojunction tandem solar cell of the present invention
  • Figure 2 is a schematic diagram of the reverse stack structure of the perovskite/silicon heterojunction stack solar cell of the present invention.
  • First metal electrode 2. First transparent conductive layer; 3. n-type heavily doped amorphous silicon layer; 4. First intrinsic amorphous silicon layer; 5. N-type single crystal silicon layer; 6. n Type heavily doped amorphous silicon layer; 7. First hole transport layer; 8. Second hole transport layer; 9. Perovskite light absorbing layer; 10. First electron transport layer; 11. Second electron transport layer ; 12. Second intrinsic amorphous silicon layer; 13. Second transparent conductive layer; 14. Second metal electrode; 31. p-type doped amorphous silicon layer; 32. n-type doped amorphous silicon layer.
  • the invention relates to a perovskite/silicon heterojunction stacked solar cell, which includes a silicon-based sub-cell and a perovskite sub-cell stacked on the silicon-based sub-cell.
  • An intermediate layer or composite junction formed by a p-type heavily doped amorphous silicon layer and an n-type heavily doped amorphous silicon layer is provided.
  • a p-type doped amorphous silicon layer and an n-type doped amorphous silicon layer as carrier recombination junctions.
  • it can greatly reduce preparation and equipment costs, and on the other hand, it can improve the photocurrent density and conversion efficiency of tandem cells.
  • the perovskite/silicon heterojunction tandem solar cell has a formal stacked structure, including a first metal electrode, a first transparent conductive layer, and an n-type doped amorphous layer that are stacked sequentially from bottom to top.
  • Silicon layer first intrinsic amorphous silicon layer, N-type single crystal silicon layer, second intrinsic amorphous silicon layer, p-type heavily doped amorphous silicon layer, n-type heavily doped amorphous silicon layer, first An electron transport layer, a second electron transport layer, a perovskite light absorption layer, a first hole transport layer, a second hole transport layer, a second transparent conductive layer and a second metal electrode layer.
  • the preparation method of the formal laminated structure includes the following steps:
  • the perovskite/silicon heterojunction tandem solar cell has an inverse stacked structure, including a first metal electrode, a first transparent conductive layer, a p-type doped non-conductive layer, and a first metal electrode stacked sequentially from bottom to top.
  • the preparation method of the trans-laminated structure includes the following steps:
  • the above-mentioned first metal electrode and second metal electrode are the same Metal electrodes.
  • the first intrinsic amorphous silicon layer and the second intrinsic amorphous silicon layer are the same intrinsic amorphous silicon layer.
  • the first transparent conductive layer and the second transparent conductive layer are the same transparent metal oxide conductive layer.
  • the thickness of the p-type heavily doped amorphous silicon layer is 1 to 30 nm, and the doping concentration is 10 18 –10 20 cm -3 ; the thickness of the n-type heavily doped amorphous silicon layer is 1 to 30 nm, and the doping concentration is 1 to 30 nm.
  • the impurity concentration is 10 18 –10 20 cm -3 .
  • the metal electrode is made of one or more materials selected from silver, copper, gold, aluminum, palladium, titanium, chromium, or nickel.
  • the transparent metal oxide conductive layer uses one or more of indium tin oxide (ITO), indium tungsten oxide (IWO), fluorine-doped tin oxide (FTO), indium zinc oxide (IZO) or aluminum-doped zinc oxide (AZO). material.
  • the first hole transport layer and/or the second hole transport layer are made of p-type semiconductor material; the first electron transport layer and/or the second electron transport layer are made of n-type semiconductor material.
  • the first hole transport layer and/or the second hole transport layer are made of nickel oxide, molybdenum oxide, cuprous oxide, copper iodide, copper phthalocyanine, cuprous thiocyanate, redox graphene, polyethylene oxide, etc.
  • the first electron transport layer and/or the second electron transport layer are made of titanium oxide (TiO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), and zinc tin oxide (Zn 2 SnO 4 ).
  • TiO 2 titanium oxide
  • SnO 2 tin oxide
  • ZnO zinc oxide
  • Zn 2 SnO 4 zinc tin oxide
  • C60 fullerene
  • graphene or fullerene derivatives made of one or more materials from fullerene (C60), graphene or fullerene derivatives.
  • the material of the perovskite light-absorbing layer is an ABX 3 structure.
  • the ABX 3 structure is composed of corner-sharing BX 6 octahedrons and A cations located in its gaps.
  • A is a monovalent cation
  • B is a divalent cation
  • X is a halogen. anions.
  • A is preferably one or more of MA, FA, Cs or Rb, B is preferably Pb, and X is preferably one or more of I, Br, Cl halogen or pseudo-halogen such as SCN, BF 4 , PF 6, etc. kind; the band gap of the perovskite sub-cell ranges from 1.5eV to 1.85eV.
  • N-type silicon wafer is used, with a resistivity of 1-10 ⁇ .cm and a thickness of 150-200um.
  • the N-type silicon wafer undergoes polishing, texturing and cleaning processes in sequence, and PECVD is used to deposit intrinsic amorphous silicon passivation layers (thickness 5nm) on both sides of the silicon wafer, and doping is prepared on the back (doping concentration 10 19-20 cm -3 ) n-type heavily doped amorphous silicon (thickness 10nm), prepare doped (doping concentration 10 19-20 cm -3 ) p-type heavily doped amorphous silicon (thickness 10nm) on the front side of the silicon wafer It forms a tunnel junction with n-type heavily doped amorphous silicon (thickness 10nm).
  • n-type doped amorphous silicon is used to prepare ITO (100nm) by the PVD method.
  • the silicon base is
  • the perovskite layer (400nm) was prepared using spin coating method.
  • spin coating method For example, to prepare a MAPbI 3 film, first, dissolve PbI 2 and CH 3 NH 3 I in a solvent at a molar ratio of 1:1 to prepare a perovskite precursor solution.
  • the solvent is dimethyl sulfoxide (DMSO) mixed with DMF. solution, and the volume ratio of DMSO to DMF is 1:4; then, take the perovskite precursor solution and spin-coat it.
  • DMSO dimethyl sulfoxide
  • the spin-coating parameters are: the rotation speed is 5000rpm, the time is 30 seconds, and at the 10th s, 0.3ml of Antisolvent (chlorobenzene or diethyl ether); finally, place the substrate on a hot stage at 100°C and anneal for 10 minutes to prepare a perovskite light-absorbing layer with a thickness of 400 nanometers; use spin coating to prepare the hole transport layer PTAA, thickness 50nm.
  • ALD was used to prepare the NiO layer with a thickness of 10 nm.
  • the silver electrode was prepared using a high vacuum thermal evaporation process, and was evenly evaporated on the hole transport layer at a speed of 2 angstroms/second under the condition of substrate rotation, with a thickness of 200 nm.
  • N-type silicon wafer is used, with a resistivity of 1-10 ⁇ .cm and a thickness of 150-200um.
  • the N-type silicon wafer undergoes polishing, texturing and cleaning processes in sequence, and PECVD is used to deposit intrinsic amorphous silicon passivation layers (thickness 5nm) on both sides of the silicon wafer, and doping is prepared on the back (doping concentration 10 19-20 cm -3 ) p-type heavily doped amorphous silicon (thickness 10nm), prepare doped (doping concentration 10 19-20 cm -3 ) n-type heavily doped amorphous silicon (thickness 10nm) on the front side of the silicon wafer and p-type heavily doped amorphous silicon (thickness 10nm) to form a tunnel junction.
  • p-type doped amorphous silicon is used to prepare ITO (100nm) through the PVD method. Silicon is produced
  • the solvent is a mixed solution of dimethyl sulfoxide (DMSO) and DMF, and the volume ratio of DMSO to DMF is 1:5; then, take the perovskite precursor solution Spin coating, the spin coating parameters are: the rotation speed is 5000rpm, the time is 30 seconds, and 0.3ml of anti-solvent (chlorobenzene or ether) is added dropwise at the 10th second; finally, the substrate is placed on a hot stage at 100°C and annealed After processing for 30 minutes, a perovskite light-absorbing layer with a thickness of 500 nm is prepared; the electron transport layer C60 is prepared by evaporation method with a thickness of 30 nm.
  • DMSO dimethyl sulfoxide
  • DMF dimethyl sulfoxide
  • ALD was used to prepare the SnO2 layer with a thickness of 10nm.
  • the silver electrode was prepared using a high vacuum thermal evaporation process, and was evenly evaporated on the hole transport layer at a speed of 2 angstroms/second under the condition of substrate rotation, with a thickness of 200 nm.
  • Example 1 The difference between this embodiment and Example 1 is that the silver electrode in Example 1 is replaced by a nickel electrode, and the ITO is replaced by IZO, and the others remain unchanged.
  • Example 2 The difference between this embodiment and Example 2 is that the silver electrode in Example 2 is replaced by a chromium electrode, ITO Replace it with IWO and leave everything else unchanged.
  • N-type silicon wafer is used, with a resistivity of 1-10 ⁇ .cm and a thickness of 150-200um.
  • the N-type silicon wafer undergoes polishing, texturing and cleaning processes in sequence, and PECVD is used to deposit intrinsic amorphous silicon passivation layers (thickness 5nm) on both sides of the silicon wafer, and doped n-type doped amorphous silicon (thickness 5nm) is prepared on the back.
  • Thickness 10nm prepare doped p-type doped amorphous silicon (thickness 10nm) on the front side of the silicon wafer, prepare doped p-type doped amorphous silicon on the front side of the silicon wafer PVD coating ITO (100nm), through The above process produces a silicon-based heterojunction bottom battery.
  • the perovskite layer (400nm) was prepared using spin coating method.
  • spin coating method For example, to prepare a MAPbI 3 film, first, dissolve PbI 2 and CH 3 NH 3 I in a solvent at a molar ratio of 1:1 to prepare a perovskite precursor solution.
  • the solvent is dimethyl sulfoxide (DMSO) mixed with DMF. solution, and the volume ratio of DMSO to DMF is 1:4; then, take the perovskite precursor solution and spin-coat it.
  • DMSO dimethyl sulfoxide
  • the spin-coating parameters are: the rotation speed is 5000rpm, the time is 30 seconds, and at the 10th s, 0.3ml of Antisolvent (chlorobenzene or diethyl ether); finally, place the substrate on a hot stage at 100°C and anneal for 10 minutes to prepare a perovskite light-absorbing layer with a thickness of 400 nanometers; use spin coating to prepare the hole transport layer PTAA, thickness 50nm.
  • ALD was used to prepare the NiO layer with a thickness of 10 nm.
  • the silver electrode was prepared using a high vacuum thermal evaporation process, and was evenly evaporated on the hole transport layer at a speed of 2 angstroms/second under the condition of substrate rotation, with a thickness of 200 nm.
  • N-type silicon wafer is used, with a resistivity of 1-10 ⁇ .cm and a thickness of 150-200um.
  • the N-type silicon wafer undergoes polishing, texturing and cleaning processes in sequence, and is deposited on both sides of the silicon wafer using PECVD.
  • Intrinsic amorphous silicon passivation layer (thickness 5nm), doped p-type doped amorphous silicon (thickness 10nm) is prepared on the back side, and doped n-type doped amorphous silicon (thickness 10nm) is prepared on the front side of the silicon wafer ), PVD coating ITO (100nm) on n-type doped amorphous silicon prepared on the front side of the silicon wafer, and a silicon-based heterojunction bottom cell is produced through the above process.
  • the solvent is a mixed solution of dimethyl sulfoxide (DMSO) and DMF, and the volume ratio of DMSO to DMF is 1:5; then, take the perovskite precursor solution Spin coating, the spin coating parameters are: the rotation speed is 5000rpm, the time is 30 seconds, and 0.3ml of anti-solvent (chlorobenzene or ether) is added dropwise at the 10th second; finally, the substrate is placed on a hot stage at 100°C and annealed After processing for 30 minutes, a perovskite light-absorbing layer with a thickness of 500 nm is prepared; the electron transport layer C60 is prepared by evaporation method with a thickness of 30 nm.
  • DMSO dimethyl sulfoxide
  • DMF dimethyl sulfoxide
  • ALD was used to prepare the SnO2 layer with a thickness of 10nm.
  • the silver electrode was prepared using a high vacuum thermal evaporation process, and was evenly evaporated on the hole transport layer at a speed of 2 angstroms/second under the condition of substrate rotation, with a thickness of 200 nm.
  • test results show that the p-type heavily doped amorphous silicon layer and the n-type heavily doped amorphous silicon layer are used as current carriers. Sub-composite junctions can better improve the photocurrent density and conversion efficiency of stacked cells.

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Abstract

本发明涉及太阳能电池技术领域，具体涉及一种钙钛矿/硅异质结叠层太阳能电池及其制备方法，太阳能电池包括硅基子电池和层叠设于硅基子电池上的钙钛矿子电池，所述硅基子电池与钙钛矿子电池之间设有由p型重掺杂非晶硅层和n型重掺杂非晶硅层形成的中间层或复合结。本发明通过采用p型重掺杂非晶硅层和n型重掺杂非晶硅层作为载流子复合结。一方面大幅度减少制备和设备成本，另一方面可以提高叠层电池的光电流密度和转换效率。

Description

一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 技术领域
本发明涉及太阳能电池技术领域，尤其涉及一种钙钛矿/硅异质结叠层太阳能电池及其制备方法。
背景技术
钙钛矿太阳能电池具有高吸收系数(105cm-1)、高开路电压(>1.2eV)，带隙可调(1.2～2.3eV)，可叠层应用、可溶液法制备等优势。钙钛矿太阳能电池从2009年开始，经过十余年的研发，单节电池效率不断刷新记录，单节从3.8％增长到25.5％，稳定性从开始持续数分钟，发展至现在万小时。硅基异质结太阳能电池具有高转换效率、高长波光谱响应等特点，现在效率已经达到25％以上。
虽然单节太阳能电池已经达到了25％以上的效率，但是任何一种太阳能电池所使用的光电转化材料单一，理论效率由其禁带宽度决定，都有一个效率理论极限。单节钙钛矿理论效率极限在33％，异质结晶硅太阳能电池的理论效率极限在29％。这是由于太阳光光谱中的能量分布较宽，现有的任何一种材料都只能吸收能量比其能带值高的光子。因此，太阳光中能量较小的光子将透过电池，被背电极金属吸收，转变成热能；而另外一部分的高能光子超出禁带宽度的多余能量将激发声子成为热损耗，也就是说高能光子不能充分利用。这些能量损失限制了太阳能电池的效率。
然而，将不同带隙宽度的太阳能电池按照带隙宽度大小逻辑，从上到下串联起来构成多结叠层电池是克服低能和高能损耗的最佳技术方案，也是突破单节电池光电转化效率的最直接的手段。采用钙钛矿与硅基异质结叠层太阳能电池器件理论上可获得高于40％的高光电转换效率。通常的两端子的钙钛矿/异质结硅叠层太阳能电池一般使用透明导电层金属氧化物作为顶部的钙钛矿太阳电 池和底部的异质结硅太阳电池的中间层(或者复合层、隧穿层)，如中国专利CN 215680694 U中采用隧穿结108的材质为ITO、IZO、AZO、IWO、ICO或其他透明薄膜材料；专利CN 213150795 U，采用透明导电层和重掺杂硅层作为中间复合层，一方面这会增加制备和设备成本，另一方面金属氧化物对于近红外光谱的吸收比较大，会影响硅电池的光电流。因此，有必要开发新的复合层来提高叠层电池的光电流，以解决现有技术中存在的上述技术问题。
发明内容
有鉴于此，本发明的目的在于提出一种一种钙钛矿/硅异质结叠层太阳能电池及其制备方法，以解决钙钛矿叠层太阳能电池的光电转化效率不高的问题。
基于上述目的，本发明提供了一种钙钛矿/硅异质结叠层太阳能电池，包括硅基子电池和层叠设于硅基子电池上的钙钛矿子电池，所述硅基子电池与钙钛矿子电池之间设有由p型重掺杂非晶硅层和n型重掺杂非晶硅层形成的中间层或复合结。
所述p型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3；所述n型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3。
所述叠层太阳能电池为正式叠层结构，所述硅基子电池包括由下到上依次层叠设置的第一金属电极、第一透明导电层、n型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层和第二本征非晶硅层，所述钙钛矿子电池包括由下到上依次层叠设置的第一电子传输层、第二电子传输层、钙钛矿吸光层、第一空穴传输层、第二空穴传输层、第二透明导电层和第二金属电极层，所述中间层或复合结为由下到上依次层叠设置在第二本征非晶硅层与第一电子传输层之间的p型重掺杂非晶硅层和n型重掺杂非晶硅层。
所述叠层太阳能电池为反式叠层结构，所述所述硅基子电池包括由下到上 依次层叠设置的第一金属电极、第一透明导电层、p型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层和第二本征非晶硅层，所述钙钛矿子电池包括由下到上依次层叠设置的第一空穴传输层、第二空穴传输层、钙钛矿吸光层、第一电子传输层、第二电子传输层、第二透明导电层和第二金属电极层，所述中间层或复合结为由下到上依次层叠设置在第二本征非晶硅层与第一空穴传输层之间的n型重掺杂非晶硅层和p型重掺杂非晶硅层。
所述第一透明导电层和第二透明导电层优选为透明金属氧化物导电层。
所述第一金属电极和第二金属电极采用银、铜、金、铝、钯、钛、铬、或镍中的一种或几种材料制成；所述第一透明导电层和第二透明导电层均为透明金属氧化物导电层，透明金属氧化物导电层采用氧化铟锡(ITO)、氧化铟钨(IWO)、掺氟氧化锡(FTO)、氧化铟锌(IZO)或掺铝氧化锌(AZO)中的一种或几种材料制成。
所述第一空穴传输层和/或第二空穴传输层采用p型半导体材料制成；所述第一电子传输层和/或第二电子传输层采用n型半导体材料制成。
可选的，第一空穴传输层和/或第二空穴传输层采用氧化镍、氧化钼、氧化亚铜、碘化铜、酞菁铜、硫氰酸亚铜、氧化还原石墨烯、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9‘-螺二芴(Spiro-OMeTAD)、聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)、聚(3-己基噻吩-2,5-二基)(P3HT)、N2,N2,N2’,N2‘,N7,N7,N7’,N7‘-八(4-甲氧基苯基)螺[芴-9,9’-氧杂蒽]-2,2‘,7,7’-四胺(X60)、N2,N7-二(4-甲氧基苯基)-N2,N7-二(2-螺[芴-9,9‘-氧杂蒽])-螺[芴-9,9’-氧杂蒽]-2,7-二胺(X55)、聚(3,4-乙烯二氧噻吩)-聚(苯乙烯磺酸酯)(PEDOT:PSS)、2,2,7,7-四(N,N-二对甲苯基)氨基-9,9-螺二芴(Spiro-TTB)、聚乙烯基咔唑(PVK)中的一种或几种材料制成。
可选的，所述第一电子传输层和/或第二电子传输层采用氧化钛(TiO2)、氧化锡(SnO2)、氧化锌(ZnO)和氧化锌锡(Zn2SnO4)、富勒烯(C60)、石墨烯或富勒烯衍生物中的一种或几种材料制成。
所述钙钛矿吸光层的材料为ABX3结构，ABX3结构由角共享BX6八面体及位于其空隙的A阳离子构成，其中，A为一价阳离子；B为二价阳离子；X为卤素阴离子。A优选为MA、FA、Cs或Rb中的一种或几种，B优选为Pb，X优选为I、Br、Cl卤素或者SCN、BF4、PF6等拟卤素等中的一种或几种；所述钙钛矿子电池的带隙范围在1.5eV至1.85eV之间。
本发明还提供所述钙钛矿/硅异质结叠层太阳能电池的制备方法，包括正式叠层结构的制备方法和反式叠层结构的制备方法，其中，正式叠层结构的制备方法包括如下步骤：
(1)将N型晶硅硅片进行表面制绒处理；
(2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
(3)在第二本征非晶硅层上依次生长p型重掺杂非晶硅层和n型重掺杂非晶硅层；
(4)在第一本征非晶硅层背离N型晶体硅片的一面生长n型掺杂非晶硅层；
(5)在n型重掺杂非晶硅层的表面生长第一电子传输层和第二电子传输层；
(6)在第二电子传输层上制备钙钛矿吸光层；
(7)在钙钛矿吸光层上依次制备第一空穴传输层和第二空穴传输层；
(8)在n型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二空穴传输层上制备第二透明导电层；
(9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层；
所述反式叠层结构的制备方法包括如下步骤：
(1)将N型晶硅硅片进行表面制绒处理；
(2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
(3)在第二本征非晶硅层上依次生长n型重掺杂非晶硅层和p型重掺杂非晶硅层；
(4)在第一本征非晶硅层背离N型晶体硅片的一面生长p型掺杂非晶硅层；
(5)在p型重掺杂非晶硅层的表面生长第一空穴传输层和第二空穴传输层；
(6)在第二空穴传输层上制备钙钛矿吸光层；
(7)在钙钛矿吸光层上依次制备第一电子传输层和第二电子传输层；
(8)在p型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二电子传输层上制备第二透明导电层；
(9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层。
所述第一空穴传输层、第二空穴传输层、第一电子传输层和第二电子传输层的制备方法为物理沉积方法或化学沉积法，其中，物理沉积方法包括真空蒸发法、溅射、离子束沉积和脉冲激光沉积方法；化学沉积法包括化学气相沉积、原子层沉积、旋涂法、狭缝涂布和刮刀法。
所述第一透明导电层和第二透明导电层的制备方法采用真空蒸发法、溅射、离子束沉积和脉冲激光沉积法。
所述钙钛矿吸光层的制备方法为物理沉积方法和/或化学沉积法，其中，物理沉积方法包括真空蒸发法，化学沉积法包括化学气相沉积、旋涂法、狭缝涂布和刮刀法。
本发明的有益效果：本发明的钙钛矿/硅异质结叠层太阳能电池不在使用透明导电层金属氧化物作为顶部的钙钛矿太阳电池和底部的异质结硅太阳电池的 中间层(或者复合层、隧穿层)，而使用p型重掺杂非晶硅层和n型重掺杂非晶硅层作为载流子复合结。一方面大幅度减少制备和设备成本，另一方面可以提高叠层电池的光电流密度和转换效率。
附图说明
为了更清楚地说明本发明或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明钙钛矿/硅异质结叠层太阳能电池的正式叠层结构示意图；
图2为本发明钙钛矿/硅异质结叠层太阳能电池的反式叠层结构示意图。
图中标记为：
1、第一金属电极；2、第一透明导电层；3、n型重掺杂非晶硅层；4、第一本征非晶硅层；5、N型单晶硅层；6、n型重掺杂非晶硅层；7、第一空穴传输层；8、第二空穴传输层；9、钙钛矿吸光层；10、第一电子传输层；11、第二电子传输层；12、第二本征非晶硅层；13、第二透明导电层；14、第二金属电极；31、p型掺杂非晶硅层；32、n型掺杂非晶硅层。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实施例，对本发明进一步详细说明。
需要说明的是，除非另外定义，本发明使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。本发明中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“包括”或者“包含”等类似的词语意指出现该词前面的元 件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
本发明涉及一种钙钛矿/硅异质结叠层太阳能电池，包括硅基子电池和层叠设于硅基子电池上的钙钛矿子电池，所述硅基子电池与钙钛矿子电池之间设有由p型重掺杂非晶硅层和n型重掺杂非晶硅层形成的中间层或复合结。通过采用p型掺杂非晶硅层和n型掺杂非晶硅层作为载流子复合结。一方面大幅度减少制备和设备成本，另一方面可以提高叠层电池的光电流密度和转换效率。
如图1所示，钙钛矿/硅异质结叠层太阳能电池为正式叠层结构，包括由下到上依次层叠设置的第一金属电极、第一透明导电层、n型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层、第二本征非晶硅层、p型重掺杂非晶硅层、n型重掺杂非晶硅层、第一电子传输层、第二电子传输层、钙钛矿吸光层、第一空穴传输层、第二空穴传输层、第二透明导电层和第二金属电极层。
该正式叠层结构的制备方法包括如下步骤：
(1)将N型晶硅硅片进行表面制绒处理；
(2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
(3)在第二本征非晶硅层上依次生长p型重掺杂非晶硅层和n型重掺杂非晶硅层；
(4)在第一本征非晶硅层背离N型晶体硅片的一面生长n型掺杂非晶硅层；
(5)在n型重掺杂非晶硅层的表面生长第一电子传输层和第二电子传输层；
(6)在第二电子传输层上制备钙钛矿吸光层；
(7)在钙钛矿吸光层上依次制备第一空穴传输层和第二空穴传输层；
(8)在n型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二空穴传输层上制备第二透明导电层；
(9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层。
如图2所示，钙钛矿/硅异质结叠层太阳能电池为反式叠层结构，包括由下到上依次层叠设置的第一金属电极、第一透明导电层、p型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层、第二本征非晶硅层、n型重掺杂非晶硅层、p型重掺杂非晶硅层、第一空穴传输层、第二空穴传输层、钙钛矿吸光层、第一电子传输层、第二电子传输层、第二透明导电层和第二金属电极层。
该反式叠层结构的制备方法包括如下步骤：
(1)将N型晶硅硅片进行表面制绒处理；
(2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
(3)在第二本征非晶硅层上依次生长n型重掺杂非晶硅层和p型重掺杂非晶硅层；
(4)在第一本征非晶硅层背离N型晶体硅片的一面生长p型掺杂非晶硅层；
(5)在p型重掺杂非晶硅层的表面生长第一空穴传输层和第二空穴传输层；
(6)在第二空穴传输层上制备钙钛矿吸光层；
(7)在钙钛矿吸光层上依次制备第一电子传输层和第二电子传输层；
(8)在p型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二电子传输层上制备第二透明导电层；
(9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层。
作为一种优选的实施方式，上述的第一金属电极与第二金属电极为相同的 金属电极。第一本征非晶硅层和第二本征非晶硅层为相同的本征非晶硅层。第一透明导电层和第二透明导电层为相同的透明金属氧化物导电层。
其中，p型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3；所述n型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3。
金属电极采用银、铜、金、铝、钯、钛、铬、或镍中的一种或几种材料制成。透明金属氧化物导电层采用氧化铟锡(ITO)、氧化铟钨(IWO)、掺氟氧化锡(FTO)、氧化铟锌(IZO)或掺铝氧化锌(AZO)中的一种或几种材料制成。
第一空穴传输层和/或第二空穴传输层采用p型半导体材料制成；所述第一电子传输层和/或第二电子传输层采用n型半导体材料制成。
可选的，第一空穴传输层和/或第二空穴传输层采用氧化镍、氧化钼、氧化亚铜、碘化铜、酞菁铜、硫氰酸亚铜、氧化还原石墨烯、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9‘-螺二芴(Spiro-OMeTAD)、聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)、聚(3-己基噻吩-2,5-二基)(P3HT)、N2,N2,N2’,N2‘,N7,N7,N7’,N7‘-八(4-甲氧基苯基)螺[芴-9,9’-氧杂蒽]-2,2‘,7,7’-四胺(X60)、N2,N7-二(4-甲氧基苯基)-N2,N7-二(2-螺[芴-9,9‘-氧杂蒽])-螺[芴-9,9’-氧杂蒽]-2,7-二胺(X55)、聚(3,4-乙烯二氧噻吩)-聚(苯乙烯磺酸酯)(PEDOT:PSS)、2,2,7,7-四(N,N-二对甲苯基)氨基-9,9-螺二芴(Spiro-TTB)、聚乙烯基咔唑(PVK)中的一种或几种材料制成。
可选的，所述第一电子传输层和/或第二电子传输层采用氧化钛(TiO2)、氧化锡(SnO2)、氧化锌(ZnO)和氧化锌锡(Zn2SnO4)、富勒烯(C60)、石墨烯或富勒烯衍生物中的一种或几种材料制成。
钙钛矿吸光层的材料为ABX3结构，ABX3结构由角共享BX6八面体及位于其空隙的A阳离子构成，其中，A为一价阳离子；B为二价阳离子；X为卤素 阴离子。A优选为MA、FA、Cs或Rb中的一种或几种，B优选为Pb，X优选为I、Br、Cl卤素或者SCN、BF4、PF6等拟卤素等中的一种或几种；所述钙钛矿子电池的带隙范围在1.5eV至1.85eV之间。
下面通过具体的实例进行说明。
实施例1
制备正式钙钛矿/硅异质结叠层电池
首先利用商业级M6的N型硅片，电阻率在1-10Ω.cm，厚度为150-200um。N型硅片依次经历抛光、制绒以及清洗处理，并利用PECVD在硅片双侧沉积本征非晶硅钝化层(厚度5nm)，在背面制备掺杂(掺杂浓度1019-20cm-3)的n型重掺杂非晶硅(厚度10nm)，在硅片的正面制备掺杂(掺杂浓度1019-20cm-3)的p型重掺杂非晶硅(厚度10nm)和n型重掺杂非晶硅(厚度10nm)构成隧穿结，在硅片的背面n型掺杂非晶硅(厚度10nm)通过PVD方法制备ITO(100nm)，通过以上工艺制得硅基异质结底电池。
采用原子层沉积SnO2(10nm)，然后采用蒸镀法制备C60(5nm)。采用旋涂法制备钙钛矿层(400nm)。如制备MAPbI3薄膜，首先，取PbI2和CH3NH3I按1:1的摩尔比溶解在溶剂中配成钙钛矿前驱体溶液，溶剂为二甲基亚砜(DMSO)与DMF混合溶液，且DMSO与DMF的体积比为1:4；然后，取钙钛矿前驱体溶液旋涂，旋涂参数为：转速为5000rpm、时间为30秒，并在第10s时滴加0.3ml的反溶剂(氯苯或乙醚)；最后，将基底置于100℃的热台上，退火处理10分钟，即制备得到厚度为400纳米的钙铁矿吸光层；采用旋涂法制备空穴传输层PTAA，厚度为50nm。采用ALD制备NiO层，厚度为10nm。采用高真空热蒸发工艺制备银电极，在基底旋转条件下，以2埃/秒的速度均匀蒸镀在空穴传输层上，厚度为200nm。
实施例2
制备反式钙钛矿/硅异质结叠层电池
首先利用商业级M6的N型硅片，电阻率在1-10Ω.cm，厚度为150-200um。N型硅片依次经历抛光、制绒以及清洗处理，并利用PECVD在硅片双侧沉积本征非晶硅钝化层(厚度5nm)，在背面制备掺杂(掺杂浓度1019-20cm-3)的p型重掺杂非晶硅(厚度10nm)，在硅片的正面制备掺杂(掺杂浓度1019-20cm-3)的n型重掺杂非晶硅(厚度10nm)和p型重掺杂非晶硅(厚度10nm)，构成隧穿结，在硅片的背面p型掺杂非晶硅(厚度10nm)通过PVD方法制备ITO(100nm)，通过以上工艺制得硅基异质结底电池。
采用原子层沉积NiO(10nm)，然后采用蒸镀法制备Spiro-TFB(5nm)。采用旋涂法制备钙钛矿层(400nm)。制备钙钛矿Cs0.15FA0.85PbI2.5Br0.5薄膜，溶剂为二甲基亚砜(DMSO)与DMF混合溶液、且DMSO与DMF的体积比为1:5；然后，取钙钛矿前驱体溶液旋涂，旋涂参数为：转速为5000rpm、时间为30秒、并在第10s时滴加0.3ml的反溶剂(氯苯或乙醚)；最后，将基底置于100℃的热台上，退火处理30分钟，即制备得到厚度为500纳米的钙铁矿吸光层；采用蒸镀法制备电子传输层C60，厚度为30nm。采用ALD制备SnO2层，厚度为10nm。采用高真空热蒸发工艺制备银电极，在基底旋转条件下，以2埃/秒的速度均匀蒸镀在空穴传输层上，厚度为200nm。
实施例3
本实施例与实施例1的不同点在于，将实例1中的银电极换为镍电极，ITO替换为IZO，其他不变。
实施例4
本实施例与实施例2的不同点在于，将实例2中的银电极换为铬电极，ITO 替换为IWO，其他不变。
对比例1
制备正式钙钛矿/硅异质结叠层电池
首先利用商业级M6的N型硅片，电阻率在1-10Ω.cm，厚度为150-200um。N型硅片依次经历抛光、制绒以及清洗处理，并利用PECVD在硅片双侧沉积本征非晶硅钝化层(厚度5nm)，在背面制备掺杂的n型掺杂非晶硅(厚度10nm)，在硅片的正面制备掺杂的p型掺杂非晶硅(厚度10nm)，在硅片的正面制备掺杂的p型掺杂非晶硅上PVD镀膜ITO(100nm)，通过以上工艺制得硅基异质结底电池。
采用原子层沉积SnO2(10nm)，然后采用蒸镀法制备C60(5nm)。采用旋涂法制备钙钛矿层(400nm)。如制备MAPbI3薄膜，首先，取PbI2和CH3NH3I按1:1的摩尔比溶解在溶剂中配成钙钛矿前驱体溶液，溶剂为二甲基亚砜(DMSO)与DMF混合溶液，且DMSO与DMF的体积比为1:4；然后，取钙钛矿前驱体溶液旋涂，旋涂参数为：转速为5000rpm、时间为30秒，并在第10s时滴加0.3ml的反溶剂(氯苯或乙醚)；最后，将基底置于100℃的热台上，退火处理10分钟，即制备得到厚度为400纳米的钙铁矿吸光层；采用旋涂法制备空穴传输层PTAA，厚度为50nm。采用ALD制备NiO层，厚度为10nm。采用高真空热蒸发工艺制备银电极，在基底旋转条件下，以2埃/秒的速度均匀蒸镀在空穴传输层上，厚度为200nm。
对比例2
制备反式钙钛矿/硅异质结叠层电池
首先利用商业级M6的N型硅片，电阻率在1-10Ω.cm，厚度为150-200um。N型硅片依次经历抛光、制绒以及清洗处理，并利用PECVD在硅片双侧沉积 本征非晶硅钝化层(厚度5nm)，在背面制备掺杂的p型掺杂非晶硅(厚度10nm)，在硅片的正面制备掺杂的n型掺杂非晶硅(厚度10nm)，在硅片的正面制备的n型掺杂非晶硅上PVD镀膜ITO(100nm)，通过以上工艺制得硅基异质结底电池。
采用原子层沉积NiO(10nm)，然后采用蒸镀法制备Spiro-TFB(5nm)。采用旋涂法制备钙钛矿层(400nm)。制备钙钛矿Cs0.15FA0.85PbI2.5Br0.5薄膜，溶剂为二甲基亚砜(DMSO)与DMF混合溶液、且DMSO与DMF的体积比为1:5；然后，取钙钛矿前驱体溶液旋涂，旋涂参数为：转速为5000rpm、时间为30秒、并在第10s时滴加0.3ml的反溶剂(氯苯或乙醚)；最后，将基底置于100℃的热台上，退火处理30分钟，即制备得到厚度为500纳米的钙铁矿吸光层；采用蒸镀法制备电子传输层C60，厚度为30nm。采用ALD制备SnO2层，厚度为10nm。采用高真空热蒸发工艺制备银电极，在基底旋转条件下，以2埃/秒的速度均匀蒸镀在空穴传输层上，厚度为200nm。
对实施例1-4和对比例1-2进行光电流密度和转换效率的测试，结果如表1所示。
表1光电流密度和转换效率的测试结果
测试结果表明，采用p型重掺杂非晶硅层和n型重掺杂非晶硅层作为载流 子复合结，才可以更好的提高叠层电池的光电流密度和转换效率。
所属领域的普通技术人员应当理解：以上任何实施例的讨论仅为示例性的，并非旨在暗示本发明的范围(包括权利要求)被限于这些例子；在本发明的思路下，以上实施例或者不同实施例中的技术特征之间也可以进行组合，步骤可以以任意顺序实现，并存在如上所述的本发明的不同方面的许多其它变化，为了简明它们没有在细节中提供。
本发明旨在涵盖落入所附权利要求的宽泛范围之内的所有这样的替换、修改和变型。因此，凡在本发明的精神和原则之内，所做的任何省略、修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种钙钛矿/硅异质结叠层太阳能电池，包括硅基子电池和层叠设于硅基子电池上的钙钛矿子电池，其特征在于，所述硅基子电池与钙钛矿子电池之间设有由p型重掺杂非晶硅层和n型重掺杂非晶硅层形成的中间层或复合结。
  2. 根据权利要求1所述钙钛矿/硅异质结叠层太阳能电池，其特征在于，所述p型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3；所述n型重掺杂非晶硅层的厚度为1～30nm，掺杂浓度为1018–1020cm-3。
  3. 根据权利要求1所述钙钛矿/硅异质结叠层太阳能电池，其特征在于，所述叠层太阳能电池为正式叠层结构，所述硅基子电池包括由下到上依次层叠设置的第一金属电极、第一透明导电层、n型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层和第二本征非晶硅层，所述钙钛矿子电池包括由下到上依次层叠设置的第一电子传输层、第二电子传输层、钙钛矿吸光层、第一空穴传输层、第二空穴传输层、第二透明导电层和第二金属电极层，所述中间层或复合结为由下到上依次层叠设置在第二本征非晶硅层与第一电子传输层之间的p型重掺杂非晶硅层和n型重掺杂非晶硅层。
  4. 根据权利要求1所述钙钛矿/硅异质结叠层太阳能电池，其特征在于，所述叠层太阳能电池为反式叠层结构，所述所述硅基子电池包括由下到上依次层叠设置的第一金属电极、第一透明导电层、p型掺杂非晶硅层、第一本征非晶硅层、N型单晶硅层和第二本征非晶硅层，所述钙钛矿子电池包括由下到上依次层叠设置的第一空穴传输层、第二空穴传输层、钙钛矿吸光层、第一电子传输层、第二电子传输层、第二透明导电层和第二金属电极层，所述中间层或复合结为由下到上依次层叠设置在第二本征非晶硅层与第一空穴传输层之间的n型重掺杂非晶硅层和p型重掺杂非晶硅层。
  5. 根据权利要求3或4所述钙钛矿/硅异质结叠层太阳能电池，其特征在于， 所述第一金属电极和第二金属电极采用银、铜、金、铝、钯、钛、铬、或镍中的一种或几种材料制成；所述第一透明导电层和第二透明导电层均为透明金属氧化物导电层，透明金属氧化物导电层采用氧化铟锡、氧化铟钨、掺氟氧化锡、氧化铟锌或掺铝氧化锌中的一种或几种材料制成。
  6. 根据权利要求3或4所述钙钛矿/硅异质结叠层太阳能电池，其特征在于，所述第一空穴传输层和/或第二空穴传输层采用p型半导体材料制成；所述第一电子传输层和/或第二电子传输层采用n型半导体材料制成。
  7. 根据权利要求3或4所述钙钛矿/硅异质结叠层太阳能电池，其特征在于，所述钙钛矿吸光层的材料为ABX3结构，ABX3结构由角共享BX6八面体及位于其空隙的A阳离子构成，其中，A为一价阳离子；B为二价阳离子；X为卤素阴离子。
  8. 根据权利要求1-4任一项所述钙钛矿/硅异质结叠层太阳能电池的制备方法，其特征在于，包括正式叠层结构的制备方法和反式叠层结构的制备方法，其中，正式叠层结构的制备方法包括如下步骤：
    (1)将N型晶硅硅片进行表面制绒处理；
    (2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
    (3)在第二本征非晶硅层上依次生长p型重掺杂非晶硅层和n型重掺杂非晶硅层；
    (4)在第一本征非晶硅层背离N型晶体硅片的一面生长n型掺杂非晶硅层；
    (5)在n型重掺杂非晶硅层的表面生长第一电子传输层和第二电子传输层；
    (6)在第二电子传输层上制备钙钛矿吸光层；
    (7)在钙钛矿吸光层上依次制备第一空穴传输层和第二空穴传输层；
    (8)在n型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二空穴传输层上制备第二透明导电层；
    (9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层；
    所述反式叠层结构的制备方法包括如下步骤：
    (1)将N型晶硅硅片进行表面制绒处理；
    (2)将N型晶体硅片进行双面钝化，利用PECVD在钝化后的N型晶体硅片双面生长第一本征非晶硅层和第二本征非晶硅层；
    (3)在第二本征非晶硅层上依次生长n型重掺杂非晶硅层和p型重掺杂非晶硅层；
    (4)在第一本征非晶硅层背离N型晶体硅片的一面生长p型掺杂非晶硅层；
    (5)在p型重掺杂非晶硅层的表面生长第一空穴传输层和第二空穴传输层；
    (6)在第二空穴传输层上制备钙钛矿吸光层；
    (7)在钙钛矿吸光层上依次制备第一电子传输层和第二电子传输层；
    (8)在p型掺杂非晶硅层背离第一本征非晶硅层的一面制备第一透明导电层，在第二电子传输层上制备第二透明导电层；
    (9)在第一透明导电层和第二透明导电层的表面分别制备金属电极层。
  9. 根据权利要求8所述钙钛矿/硅异质结叠层太阳能电池的制备方法，其特征在于，所述第一空穴传输层、第二空穴传输层、第一电子传输层和第二电子传输层的制备方法为物理沉积方法或化学沉积法，其中，物理沉积方法包括真空蒸发法、溅射、离子束沉积和脉冲激光沉积方法；化学沉积法包括化学气相沉积、原子层沉积、旋涂法、狭缝涂布和刮刀法。
  10. 根据权利要求8所述钙钛矿/硅异质结叠层太阳能电池的制备方法，其特征在于，所述钙钛矿吸光层的制备方法为物理沉积方法和/或化学沉积法，其中，物理沉积方法包括真空蒸发法，化学沉积法包括化学气相沉积、旋涂法、狭缝 涂布和刮刀法。
PCT/CN2023/081524 2022-03-29 2023-03-15 一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 Ceased WO2023185464A1 (zh)

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