CN114335348A - PN heterojunction antimony selenide/perovskite solar cell and preparation method thereof - Google Patents

PN heterojunction antimony selenide/perovskite solar cell and preparation method thereof Download PDF

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CN114335348A
CN114335348A CN202111595116.0A CN202111595116A CN114335348A CN 114335348 A CN114335348 A CN 114335348A CN 202111595116 A CN202111595116 A CN 202111595116A CN 114335348 A CN114335348 A CN 114335348A
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perovskite
antimony selenide
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solar cell
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CN114335348B (en
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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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Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
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Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
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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
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    • 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
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    • 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
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Abstract

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 which are sequentially arranged. Compared with the prior art, the light absorbers with different band gaps form the multi-junction solar cell, so that the utilization range of solar spectrum can be widened, the thermal relaxation loss of photon-generated carriers can be reduced, and the photoelectric conversion efficiency can be improved; and the invention passes through PN heterojunction Sb2Se3The perovskite absorption layer does not need an electron transport layer, a hole transport layer and the like, so that the preparation steps and cost of the process are reduced, and the stability of the battery is improved.

Description

PN heterojunction antimony selenide/perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a PN heterojunction antimony selenide/perovskite solar cell and a preparation method thereof.
Background
Solar cells are receiving attention because they convert solar energy into electric energy through photoelectric conversion and are used directly by people. Solar cells can be classified into three types according to their development and the light absorbing layer materials used. The first type is a silicon-based solar cell, which comprises a monocrystalline silicon, a polycrystalline silicon solar cell, an amorphous silicon thin-film solar cell and a silicon laminated solar cell; the second type is a compound solar cell, including solar cells of Copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe), gallium arsenide (GaAs), perovskite, and the like; the third type is a novel solar cell including a dye-sensitized solar cell, an organic solar cell, a quantum dot solar cell, and the like.
Among them, perovskite solar cells (perovskite solar cells) are solar cells using perovskite organic metal halide semiconductors as light absorbing materials, and belong to the third generation solar cells, which are also called new concept solar cells.
Since 2009 perovskite solar cells have attracted much attention due to simple preparation methods, low production cost and excellent photoelectric properties, the perovskite solar cells rapidly increase the photoelectric conversion efficiency from 3.8% to 25%, become the most rapidly developing photovoltaic technology, and are the emerging photovoltaic technology which is the most spotlighted worldwide.
The single-junction solar cell has a Shockley-Queti (Shockley-Q) structure because it can only absorb photons in a specific rangeueisser) efficiency limit. The light absorbers with different band gaps form the multi-junction solar cell, so that the utilization range of solar spectrum can be widened, and the thermal relaxation loss of photon-generated carriers can be reduced. At present, perovskite is mainly overlapped with crystalline silicon, copper indium gallium selenide, perovskite and the like to form a double-junction or multi-junction battery device. However, the double-junction perovskite laminated cell is prepared by working procedures of an electron transmission layer, a wide band gap absorption layer, a hole transmission layer, a middle tunneling layer, a hole transmission layer, a narrow band gap absorption layer, an electron transmission layer and the like, and has a complex structure, for example, Chinese patent with the publication number of CN111244220A discloses an all-inorganic P/N heterojunction antimony selenide/perovskite solar cell and a preparation method thereof, wherein the structure of the solar cell sequentially comprises an FTO conductive glass substrate and titanium dioxide (TiO) (TiO 111244220A)2) Layer, inorganic CsPbBrI2Perovskite layer, selenized Sb2Se3A layer and a metal counter electrode layer, in which the inorganic perovskite layer is not N-type treated and still requires an electron transport layer TiO2And (4) preparing.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a PN heterojunction antimony selenide/perovskite solar cell with a wider 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 which are sequentially arranged.
Preferably, the substrate is a flexible metal substrate; the thickness of the substrate is 0.1-0.3 mm.
Preferably, the metal back electrode is made of metal molybdenum; the thickness of the metal back electrode is 800-1000 mm.
Preferably, the thickness of the P-type antimony selenide layer is 50-300 nm.
Preferably, the thickness of the N-type perovskite absorption layer is 100-200 mm.
Preferably, the material of the N-type perovskite absorption layer is ABX doped with N-type material3(ii) a Wherein A is MA, FA, Cs andone or more of PEA; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; the N-type material comprises Bi3+、Sb3+、Fe3+With Al3+One or more of (a).
Preferably, the molar ratio of the N-type material to B in the N-type perovskite absorption layer is (0.01-0.05): (0.95-0.99).
The invention also provides a preparation method of the PN heterojunction antimony selenide/perovskite solar cell, which comprises the following steps:
s1) depositing a metal back electrode on the substrate to obtain a substrate of a composite metal back electrode;
s2) evaporating a P-type antimony selenide layer on the substrate of the composite metal back electrode to obtain a substrate of the composite P-type antimony selenide layer;
s3) coating the N-type perovskite precursor solution on the surface of the substrate of the composite P-type antimony selenide layer, and annealing to obtain the substrate of the composite N-type perovskite absorption layer;
s4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorption layer to obtain the PN heterojunction antimony selenide/perovskite solar cell.
Preferably, the vapor deposition in step S2) is vacuum vapor deposition; the vacuum degree of the vapor deposition is less than 4 multiplied by 10-4Pa; the temperature of the evaporation is 300-600 ℃; the evaporation rate is 0.3-1.5 angstroms/second; the evaporation plating raw materials are Se and Sb2Se3。
Preferably, the N-type perovskite precursor solution comprises AX and BX2And an N-type doped material; a is one or more of MA, FA, Cs and PEA; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; the N-type doped material comprises Bi3+、Sb3+、Fe3+With Al3+One or more of; the annealing temperature is 70-150 ℃; the annealing time is 10-60 min.
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 which are sequentially arranged. Compared with the prior art, the light absorbers with different band gaps form the multi-junction solar cell, so that the utilization range of solar spectrum can be widened, the thermal relaxation loss of photon-generated carriers can be reduced, and the photoelectric conversion efficiency can be improved; and the invention passes through PN heterojunction Sb2Se3The perovskite absorption layer does not need an electron transport layer, a hole transport layer and the like, so that the preparation steps and cost of the process are reduced, and the stability of the battery is improved.
Compared with a double-junction perovskite laminated cell, the preparation of an electron and/or hole transport layer and an intermediate composite layer is not needed, the metal ion-doped wide-band-gap N-type perovskite cell with the thickness of 1.4-2.0 eV is prepared by blade coating on the P-type antimony selenide layer with the narrow band gap of 1.1-1.3 eV, a PN heterojunction structure with different band gaps can be formed, and meanwhile, the preparation of an electron transport layer and/or an electron transport layer is not needed by doping of the perovskite layer strong N-type ions, so that the preparation method has the advantages of simple process, low cost, wide light absorption range and the like, and the technical difficulty in cell design and preparation is reduced.
Experiments show that the photoelectric conversion efficiency of the PN heterojunction antimony selenide/perovskite solar cell prepared by the method can reach 17.5%.
Drawings
Fig. 1 is a schematic structural diagram of a PN heterojunction antimony selenide/perovskite solar cell provided by the present invention;
fig. 2 is a schematic structural diagram of an antimony selenide evaporation device used in the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope 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 which are sequentially arranged.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a 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 is an N-type perovskite absorption layer, and 5 is a conductive electrode.
Wherein, the substrate is a substrate known to those skilled in the art, and is not particularly limited, and in the present invention, a metal foil is preferred, and a stainless steel foil is more preferred; the thickness of the substrate is preferably 0.1-0.3 mm.
A metal back electrode is arranged on the substrate; the metal back electrode is a metal back electrode well known to the skilled person, and is not particularly limited, and in the present invention, molybdenum is preferred; the thickness of the back electrode is preferably 800-1000 nm.
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.
An N-type perovskite absorption layer is arranged on the P-type antimony selenide layer; the thickness of the N-type perovskite absorption layer is preferably 100-200 mm, more preferably 120-150 nm, further preferably 130-150 nm, and most preferably 150 mm; the material of the N-type perovskite absorption layer is preferably ABX doped with N-type material3(ii) a Wherein A is one or more of MA, FA, Cs and PEA; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; in the embodiment provided by the invention, A is specifically MA and/or Cs and FA; the molar ratio of MA and/or Cs to FA is preferably (0.1-0.2): (0.8 to 0.9), more preferably 0.15: 0.85; the N-type material comprises Bi3+、Sb3+、Fe3+With Al3+One or more of; the molar ratio of the N-type material to B in the N-type perovskite absorption layer is preferably (0.01-0.05): (0.95 to 0.99), more preferablySelecting (0.03-0.05): (0.95-0.97).
A conductive electrode is arranged on the N-type perovskite absorption layer; the conductive electrode is preferably a transparent electrode, and more preferably one or more of ITO, zinc oxide and aluminum-doped zinc oxide; the thickness of the conductive electrode is preferably 100-1000 nm.
The light absorbers with different band gaps form the multi-junction solar cell, so that the utilization range of solar spectrum can be widened, the thermal relaxation loss of photon-generated carriers can be reduced, and the photoelectric conversion efficiency is improved; and the invention passes through PN heterojunction Sb2Se3The perovskite absorption layer does not need an electron transport layer, a hole transport layer and the like, so that the preparation steps and cost of the process are reduced, and the stability of the battery is improved.
The invention also provides a preparation method of the PN heterojunction antimony selenide/perovskite solar cell, which comprises the following steps: s1) depositing a metal back electrode on the substrate to obtain a substrate of a composite metal back electrode; s2) evaporating a P-type antimony selenide layer on the substrate of the composite metal back electrode to obtain a substrate of the composite P-type antimony selenide layer; s3) coating the N-type perovskite precursor solution on the surface of the substrate of the composite P-type antimony selenide layer, and annealing to obtain the substrate of the composite N-type perovskite absorption layer; s4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorption layer to obtain the PN heterojunction antimony selenide/perovskite solar cell.
Wherein, the sources of all raw materials are not specially limited and can be sold in the market; the substrate, the metal back electrode, the P-type antimony selenide layer, the N-type perovskite absorption layer and the conductive electrode are the same as those described above, and are not described herein again.
In the present invention, it is preferable that the substrate is pretreated first; because the substrate is preferably a metal foil, the pretreatment preferably comprises grinding and polishing, and then ultrasonic cleaning and drying are sequentially carried out by using deionized water, absolute ethyl alcohol and acetone.
Depositing a metal back electrode on the pretreated substrate to obtain a substrate of a composite metal back electrode; the method for depositing the metal back electrode is known to those skilled in the art, and is not particularly limited, and magnetron sputtering is preferably used in the present invention.
Evaporating a P-type antimony selenide layer on the substrate of the composite back electrode to obtain a substrate of the P-type antimony selenide layer; the method of evaporation is preferably a method well known to those skilled in the art, and is not particularly limited, and vacuum evaporation is preferred in the present invention; the vapor deposition is preferably performed in a vacuum degree of less than 4X 10-4Under the conditions of (a); the evaporation temperature is preferably 300-600 ℃; the evaporation rate is preferably 0.1-1.5 angstroms/second; the raw materials for vapor deposition are preferably Se and Sb2Se3(ii) a The Se and Sb2Se3The ratio of the evaporation rates of (1): (10-15), more preferably 1: (10-12).
Coating the N-type perovskite precursor solution on the substrate surface of the composite P-type antimony selenide layer, and annealing to obtain the substrate of the composite N-type perovskite absorption layer; the N-type perovskite precursor solution preferably comprises AX and BX2And N-type material; a is one or more of MA, FA, Cs and PEA, and more preferably one or two of Cs and MA and FA; the molar ratio of one or two of the Cs and MA to FA is preferably (0.05-0.5): (0.7-0.95), more preferably (0.1-0.5): (0.7-0.9), preferably (0.15-0.5): 0.85; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; the N-type material preferably comprises Bi3+、Sb3+、Fe3+With Al3+One or more of; the solvent of the N-type perovskite precursor solution is preferably one or more of DMF, NMP, 2ME, DMSO, DMPU, acetonitrile and methanol, and more preferably one or more of NMP, 2ME, DMSO, DMPU, acetonitrile and methanol and DMF; the volume ratio of one or more of NMP, 2ME, DMSO, DMPU, acetonitrile and methanol to DMF is preferably (2-4): (6-8); in the embodiment provided by the invention, the solvent of the N-type perovskite precursor solution is specifically a solvent with a volume ratio of 6: 4, a mixed solution of DMF and DMSO with a volume ratio of 6: 2: 2, a mixed solution of DMF, DMSO and 2ME, wherein the volume ratio is 7: 3:0.25 of a mixed solution of DMF and 2ME and NMP or a volume ratio of 8: 2: 0.25 of a mixed solution of DMF and 2ME and NMP; ABX in the N-type perovskite precursor solution3The concentration of (b) is preferably 0.1-1.5 mol/mL; wet filming the N-type perovskite precursor solution by coating, wherein the coating method can be coating, spraying, spin coating or the like, and is not particularly limited; the annealing temperature is preferably 70-150 ℃; the annealing time is preferably 10-60 min.
Depositing a conductive electrode on the substrate of the composite N-type perovskite absorption layer to obtain a PN heterojunction antimony selenide/perovskite solar cell; the method for depositing the conductive electrode is not particularly limited as long as it is a method known to those skilled in the art, and vacuum evaporation or magnetron sputtering is preferable in the present invention.
In order to further illustrate the present invention, the PN heterojunction antimony selenide/perovskite solar cell and the preparation method thereof provided by the present invention are described in detail below with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
1) Selecting a stainless steel foil (1) with the thickness of 0.2mm, grinding and polishing, then respectively adopting deionized water, absolute ethyl alcohol and acetone to carry out ultrasonic cleaning for 30min, and then drying;
2) preparation of the metal back electrode (2): mo is deposited on the stainless steel foil (1) by adopting magnetron sputtering to be used as a back electrode of the battery, and the deposition thickness is 800 nm;
3)Sb2Se3preparation of the absorbing layer (3): under vacuum degree less than 4 x 10-4Evaporating a layer of Sb with the thickness of 300nm by adopting a vacuum evaporation method at the temperature of 350 ℃ under Pa2Se3And (3) a layer. Wherein the evaporation raw materials are Se and Sb2Se3Powder, Se powder, evaporation rate of 0.1 Angstrom/s, Sb2Se3The evaporation rate of the powder was 1.2 angstroms/second. The schematic structure of the evaporation equipment is shown in FIG. 2; wherein 2-1 is a heat insulation layer, 2-2 is a Se evaporation source, 2-3 is a bottom heater, 2-4 is Sb2Se3The evaporation source, 2-5 are top heaters, and 2-6 are distributors.
4) Preparation of the N-type perovskite absorption layer (4): preparing N-type perovskite material solution, wherein the solute is PbI2MAI, FAI, wherein the molar ratio of MAI to FAI is 0.15: 0.85. PbI2Molar ratio to (MAI + FAI) 1: 1. bi is selected in the present embodiment3+As N-type doping material, wherein BiI3And PbI2Is 0.05: 0.95, the solvent is DMF and DMSO, wherein the volume ratio of DMF to DMSO is 6: 4, forming 1mol/mL perovskite precursor solution doped with N-type materials; then coating an N-type perovskite material solution by a wet method to form a film, wherein the coating speed is 12mm/s, the coating liquid injection amount is 170uL, and then annealing treatment is carried out at 120 ℃ for 20min to form an N-type perovskite material layer, and the thickness is about 120 nm;
5) preparation of the counter electrode (5): and carrying out magnetron sputtering on a layer of indium-doped tin oxide with the thickness of 200nm on the N-type perovskite absorption layer (4).
Example 2
1) Selecting a stainless steel foil (1) with the thickness of 0.2mm, grinding and polishing, then respectively adopting deionized water, absolute ethyl alcohol and acetone to carry out ultrasonic cleaning for 30min, and then drying;
2) preparation of the metal back electrode (2): mo is deposited on the stainless steel foil (1) by adopting magnetron sputtering to be used as a back electrode of the battery, and the deposition thickness is 1000 nm;
3)Sb2Se3preparation of the absorbing layer (3): under vacuum degree less than 4 x 10-4Evaporating a layer of Sb with the thickness of 300nm by adopting a vacuum evaporation method at the temperature of 350 ℃ under Pa2Se3And (3) a layer. Wherein the evaporation raw materials are Se and Sb2Se3Powder, Se powder, evaporation rate of 0.1 Angstrom/s, Sb2Se3The evaporation rate of the powder was 1 angstrom/sec. The schematic structure of the evaporation equipment is shown in figure 2.
4) Preparation of the N-type perovskite absorption layer (4): preparing N-type perovskite material solution, wherein the solute is PbI2CsBr and FAI, wherein the molar ratio of CsBr to FAI is 0.15: 0.85. PbI2Molar ratio to (CsBr + FAI) 1: 1. sb is selected in the present embodiment3+As N-type doping material, wherein SbI3And PbI2Is 0.03: 0.97, the solvent is DMF, DMSO, 2ME, and the volume ratio is 6: 2: 2, forming 1mol/ml perovskite precursor solution doped with N-type materials; then coating an N-type perovskite material solution by a wet method to form a film, wherein the coating speed is 11mm/s, the coating liquid injection amount is 170uL, and then annealing treatment is carried out at 120 ℃ for 20min to form an N-type perovskite material layer, and the thickness is about 110 nm;
5) preparation of the counter electrode (5): and carrying out magnetron sputtering on a layer of indium-doped tin oxide with the thickness of 300nm on the N-type perovskite absorption layer (4).
Example 3
1) Selecting a stainless steel foil (1) with the thickness of 0.2mm, grinding and polishing, then respectively adopting deionized water, absolute ethyl alcohol and acetone to carry out ultrasonic cleaning for 30min, and then drying;
2) preparation of the metal back electrode (2): mo is deposited on the stainless steel foil (1) by adopting magnetron sputtering to be used as a back electrode of the battery, and the deposition thickness is 800 nm;
3)Sb2Se3preparation of the absorbing layer (3): under vacuum degree less than 4 x 10-4Evaporating a layer of Sb with the thickness of 300nm by adopting a vacuum evaporation method at the temperature of 350 ℃ under Pa2Se3And (3) a layer. Wherein the evaporation raw materials are Se and Sb2Se3Powder, Se powder, evaporation rate of 0.1 Angstrom/s, Sb2Se3The evaporation rate of the powder was 1.2 angstroms/second. The schematic structure of the evaporation equipment is shown in figure 2.
4) Preparation of the N-type perovskite absorption layer (4): preparing N-type perovskite material solution, wherein the solute is PbI2CsBr, FAI, MACl, wherein the molar ratio of CsBr to FAI is 0.15: 0.85. PbI2Molar ratio to (CsBr + FAI) 1: 1, molar ratio of MACl to (CsBr + FAI) 0.35: 1. bi is selected in the present embodiment3+As N-type doping material, wherein BiI3And PbI2Is 0.03: 0.97, the solvent is DMF, 2ME and NMP, and the volume ratio is 7: 3: 0.25, forming 1mol/ml perovskite precursor solution doped with N-type materials; then the N-type perovskite material solution is coated by a wet method to form a film, wherein the coating speed is 15mm/s, the coating liquid injection amount is 170uL, and then the film is annealed at 130 ℃ for 20minForming a layer of N-type perovskite material with a thickness of about 150 nm.
5) Preparation of the counter electrode (5): and carrying out magnetron sputtering on a layer of indium-doped tin oxide with the thickness of 300nm on the N-type perovskite absorption layer (4).
Example 4
1) Selecting a stainless steel foil (1) with the thickness of 0.2mm, grinding and polishing, then respectively adopting deionized water, absolute ethyl alcohol and acetone to carry out ultrasonic cleaning for 30min, and then drying;
2) preparation of the metal back electrode (2): mo is deposited on the stainless steel foil (1) by adopting magnetron sputtering to be used as a back electrode of the battery, and the deposition thickness is 1000 nm;
3)Sb2Se3preparation of the absorbing layer (3): under vacuum degree less than 4 x 10-4Evaporating a layer of Sb with the thickness of 300nm by adopting a vacuum evaporation method at the temperature of 350 ℃ under Pa2Se3And (3) a layer. Wherein the evaporation raw materials are Se and Sb2Se3Powder, Se powder, evaporation rate of 0.1 Angstrom/s, Sb2Se3The evaporation rate of the powder was 1.2 angstroms/second. The schematic structure of the evaporation equipment is shown in figure 2.
4) Preparation of the N-type perovskite absorption layer (4): preparing N-type perovskite material solution, wherein the solute is PbI2MAI, FAI and CsBr, wherein the molar ratio of the MAI to the FAI to the CsBr is 0.10: 0.85: 0.05. PbI2Molar ratio to (MAI + FAI + CsBr) 1: 1. bi is selected in the present embodiment3+As N-type doping material, wherein BiI3And PbI2Is 0.03: 0.97, the solvent is DMF, NMP and 2ME, wherein the volume ratio of the DMF, the 2ME and the NMP is 8: 2: 0.25, forming 1.03mol/ml perovskite precursor solution doped with N-type materials; then coating an N-type perovskite material solution by a wet method to form a film, wherein the coating speed is 13mm/s, the coating liquid injection amount is 170uL, and then annealing treatment is carried out for 20min at 130 ℃ to form an N-type perovskite material layer, and the thickness is about 130 nm;
5) preparation of the counter electrode (5): and carrying out magnetron sputtering on a layer of indium-doped tin oxide with the thickness of 300nm on the N-type perovskite absorption layer (4).
The performance of the PN heterojunction antimony selenide/perovskite solar cell obtained in examples 1 to 4 was examined, and the obtained results are shown in table 1. The detection method is as follows.
I-V efficiency test: the test I-V curves and steady state Jsc are data recorded by a solar simulator (7SS1503A, beijing simulated am1.5g sunlight, light intensity 100mW/cm2, using digimatic table 2400Keithley Instruments Inc). The incident light intensity was calibrated with a silicon solar cell calibrated with NREL (Newport Stratford Inc 91150V). The scan rate was 50mV/s, with a delay time of 0.1 s. The reverse scan is from 1.2V to 0.05V, while the forward scan is from 0.05V to 1.2V.
TABLE 1 Effect of different N-type doping and solvent ratios on cell Performance
Figure BDA0003430289020000091

Claims (10)

1. A PN heterojunction antimony selenide/perovskite solar cell is characterized by comprising 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.
2. The PN heterojunction antimony selenide/perovskite solar cell of claim 1, wherein the substrate is a flexible metal substrate; the thickness of the substrate is 0.1-0.3 mm.
3. The PN heterojunction antimony selenide/perovskite solar cell of claim 1, wherein the material of the metal back electrode is metal molybdenum; the thickness of the metal back electrode is 800-1000 mm.
4. 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. The PN heterojunction antimony selenide/perovskite solar cell according to claim 1, wherein the thickness of the N-type perovskite absorption layer is 100-200 mm.
6. The PN heterojunction antimony selenide/perovskite solar cell of claim 1, wherein the material of the N-type perovskite absorption layer is ABX doped with N-type material3(ii) a Wherein A is one or more of MA, FA, Cs and PEA; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; the N-type material comprises Bi3+、Sb3+、Fe3+With Al3+One or more of (a).
7. The PN heterojunction antimony selenide/perovskite solar cell of claim 6, wherein the molar ratio of the N-type material to B in the N-type perovskite absorption layer is (0.01-0.05): (0.95-0.99).
8. A preparation method of a PN heterojunction antimony selenide/perovskite solar cell is characterized by comprising the following steps:
s1) depositing a metal back electrode on the substrate to obtain a substrate of a composite metal back electrode;
s2) evaporating a P-type antimony selenide layer on the substrate of the composite metal back electrode to obtain a substrate of the composite P-type antimony selenide layer;
s3) coating the N-type perovskite precursor solution on the surface of the substrate of the composite P-type antimony selenide layer, and annealing to obtain the substrate of the composite N-type perovskite absorption layer;
s4) depositing a conductive electrode on the substrate of the composite N-type perovskite absorption layer to obtain the PN heterojunction antimony selenide/perovskite solar cell.
9. The production method according to claim 8, wherein the evaporation in step S2) is vacuum evaporation; the vacuum degree of the vapor deposition is less than 4 multiplied by 10-4Pa; the temperature of the evaporation is 300-600 ℃; the evaporation rate is 0.3-1.5 angstroms/second; the evaporation coating raw material is Se and Sb2Se3。
10. The production method according to claim 8, wherein the N-type perovskite precursor solution includes AX, BX2And an N-type doped material; a is one or more of MA, FA, Cs and PEA; MA is CH3NH3(ii) a FA is NH2CHNH2(ii) a PEA is C8H9NH3(ii) a B is Pb and/or Sn; x is one or more of Cl, Br and I; the N-type doped material comprises Bi3+、Sb3+、Fe3+With Al3+One or more of; the annealing temperature is 70-150 ℃; the annealing time is 10-60 min.
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