CN113871539B - Preparation method of perovskite solar cell - Google Patents

Preparation method of perovskite solar cell Download PDF

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CN113871539B
CN113871539B CN202111458904.5A CN202111458904A CN113871539B CN 113871539 B CN113871539 B CN 113871539B CN 202111458904 A CN202111458904 A CN 202111458904A CN 113871539 B CN113871539 B CN 113871539B
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perovskite
layer
fto
solar cell
preparation
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CN113871539A (en
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肖平
刘家梁
文军
赵志国
丁坤
赵东明
李梦洁
熊继光
秦校军
李芳富
冯笑丹
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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
    • 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
    • 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
    • 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
    • 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
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    • 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

Abstract

The invention provides a preparation method of a perovskite solar cell, which comprises the following steps: a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell; the residual temperature of the in-situ prepared FTO is 450-650 ℃. Compared with the prior art, the preparation method provided by the invention does not need to additionally provide an external heat source in the preparation process, so that the energy consumption is saved, lead iodide is used as a seed layer to directionally generate the perovskite, the perovskite can be induced to preferentially grow along crystal faces (110) and (220), and the prepared perovskite solar cell has high photoelectric conversion efficiency. Experimental results show that the perovskite solar cell obtained by the preparation method provided by the invention has the photoelectric conversion efficiency of more than 16%.

Description

Preparation method of perovskite solar cell
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a preparation method of a perovskite solar cell.
Background
Perovskite solar cells (perovskite solar cells) are solar cells using perovskite type organic metal halide semiconductors as light absorbing materials, and belong to the third generation solar cells, which are also called new concept solar cells. When receiving the sunlight irradiation, the perovskite layer firstly absorbs photons to generate electron-hole pairs; due to the difference of exciton binding energy of perovskite materials, the carriers become free carriers or form excitons, and because the perovskite materials often have lower carrier recombination probability and higher carrier mobility, the diffusion distance and the service life of the carriers are longer; then, these non-recombined electrons and holes are collected by the electron transport layer and the hole transport layer, respectively, i.e. the electrons are transported from the perovskite layer to the electron transport layer and are finally collected by ITO, and the holes are transported from the perovskite layer to the hole transport layer and are finally collected by the metal electrode, of course, these processes are not always accompanied by some carrier losses, such as reversible recombination of electrons of the electron transport layer and holes of the perovskite layer, recombination of electrons of the electron transport layer and holes of the hole transport layer (in the case that the perovskite layer is not dense), and recombination of electrons of the perovskite layer and holes of the hole transport layer, so to improve the overall performance of the battery, these carrier losses should be minimized; finally, the photocurrent is generated through the electrical circuit connecting the FTO and the metal electrode.
At present, the perovskite solar cell has a good development status, but in the perovskite solar cell preparation process in the prior art, the preparation process of tin oxide or nickel oxide and perovskite material layer needs to be heated at high temperature alone, so that the energy consumption is high, the energy waste is further caused, and the energy recovery period of the whole assembly is longer.
Disclosure of Invention
In view of this, the present invention provides a method for manufacturing a perovskite solar cell, and the method provided by the present invention does not need to additionally provide an external heat source in the manufacturing process, so as to save energy consumption, and the perovskite solar cell manufactured by the method has high photoelectric conversion efficiency.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps:
a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell;
the residual temperature of the in-situ prepared FTO is 450-650 ℃.
Preferably, the preparation method of the FTO prepared in situ in step a) specifically comprises:
inserting a multi-channel coating device into a narrow section of a tin bath of a float glass production line, and coating by using monobutyl tin trichloride with the purity of 95wt% as a precursor, using trifluoroacetic acid with the purity of 99wt% as a doping agent, and using air and water as an oxidant and a catalyst for reaction; the method comprises the steps of adopting 1-2% of MBTC, 0.5-1% of TFA, 4-6% of water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film.
Preferably, the step a) of forming the semiconductor material layer specifically includes:
and spraying a precursor solution of the semiconductor material when the residual temperature of the in-situ prepared FTO is reduced to 300-500 ℃, and forming a semiconductor material layer with the thickness of 5-100 nm by taking the residual temperature as a heat source.
Preferably, the precursor solution of the semiconductor material is selected from a precursor solution comprising a tin source or a precursor solution comprising a nickel source; the tin source is selected from SnCl2、SnCl4、C4H9SnCl3And SnCl4·5H2One or more of O; the nickel source is selected from NiNO3·6H2O, nickel acetate, NiCl2And NiCl; the solvent of the precursor solution of the semiconductor material is selected from one or more of water, ethanol, methanol, n-butanol and isopropanol; the concentration of the semiconductor material in the precursor solution of the semiconductor material is 0.01-5 mol/L.
Preferably, the precursor solution comprising the tin source further comprises:
doping metal ions; the doping metal ion is selected from Li+、Mg2+、Al3+、Y3+、Sb3+And Nb5+One or more of; the concentration of doped metal ions in the precursor solution containing the tin source is 0.001-0.1 mol/L.
Preferably, the precursor solution comprising a nickel source further comprises:
one or more of doping with basic metal cations, doping with transition metal cations, and doping with non-metal molecules; the doped basic metal cation is selected from K+、Mg+、Li+And Na+One or more of; the doped transition metal cation is selected from Zn2+、Cu+、Co2+、Al3+And Ag+One or more of; the doped non-metal molecule is guanidine nitrate.
Preferably, the lead iodide seed layer is formed in the step a) by spraying a DMF and/or DMSO solution of lead iodide; the concentration of lead iodide in the DMF and/or DMSO solution of lead iodide is 0.01-1 mol/L; the thickness of the lead iodide seed layer is 1 nm-10 nm.
Preferably, the process of forming the perovskite material layer in step a) is specifically:
spraying perovskite solution when the residual temperature of the FTO prepared in situ is reduced to 200-300 ℃, and directionally generating a 200-500 nm perovskite material layer by taking the residual temperature as a heat source.
Preferably, the perovskite solution is prepared from a perovskite precursor material and an organic solvent; the perovskite precursor material is selected from PbI2、PbBr2One or more of CsI, CsBr, FAI, MAI, MACl and MABr; the organic solvent is selected from one or more of DMF, DMSO, 2-ME, ACN and GBL; the concentration of the perovskite precursor material in the perovskite solution is 0.05-1.5 mol/L.
Preferably, the carrier transport layer in step a) is an electron transport layer or a hole transport layer; the material of the electron transport layer is selected from C60 and SnO2And TiO2One or more of; the material of the hole transport layer is selected from PTAA and/or Spiro; the thickness of the carrier transmission layer is 20 nm-100 nm.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps: a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell; the residual temperature of the in-situ prepared FTO is 450-650 ℃. Compared with the prior art, the preparation method provided by the invention does not need to additionally provide an external heat source in the preparation process, so that the energy consumption is saved, lead iodide is used as a seed layer to directionally generate the perovskite, the perovskite can be induced to preferentially grow along crystal faces (110) and (220), and the prepared perovskite solar cell has high photoelectric conversion efficiency. Experimental results show that the perovskite solar cell obtained by the preparation method provided by the invention has the photoelectric conversion efficiency of more than 16%.
In addition, the preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
Drawings
Fig. 1 is a structural diagram of a perovskite solar cell obtained by the preparation method provided in embodiment 2 of the invention;
fig. 2 is an XRD crystal orientation diagram of oriented formation of perovskite by using lead iodide as a seed layer in the preparation method provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 preparation method of a perovskite solar cell, which comprises the following steps:
a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell;
the residual temperature of the in-situ prepared FTO is 450-650 ℃.
In the present invention, the preparation method of the in-situ prepared FTO is preferably specifically:
inserting a multi-channel coating device into the narrow section of a tin bath of a float glass production line, and adding monobutyl tin trichloride (C) with the purity of 95wt%4H9SnCl3MBTC) as a precursor, 99wt% trifluoroacetic acid (CF)3COOH and TFA) as doping agent, and taking air and water as the oxidizing agent and catalyst of the reaction to carry out film coating; the method comprises the steps of adopting 1-2% of MBTC, 0.5-1% of TFA, 4-6% of water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film.
More preferably:
inserting a multi-channel coating device into the narrow section of a tin bath of a float glass production line, wherein the purity of the multi-channel coating device is95% by weight of monobutyl tin trichloride (C)4H9SnCl3MBTC) as a precursor, 99wt% trifluoroacetic acid (CF)3COOH and TFA) as doping agent, and taking air and water as the oxidizing agent and catalyst of the reaction to carry out film coating; using a mole fraction of 1.6% MBTC, 0.88% TFA, 4.8% water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film.
According to the invention, after the FTO is prepared by adopting the method for preparing the FTO in situ, the semiconductor material layer is firstly formed on the surface of the FTO prepared in situ. In the present invention, the process of forming the semiconductor material layer is preferably as follows:
spraying a precursor solution of the semiconductor material when the residual temperature of the in-situ prepared FTO is reduced to 300-500 ℃, and forming a semiconductor material layer with the thickness of 5-100 nm by taking the residual temperature as a heat source;
more preferably:
and spraying a precursor solution of the semiconductor material when the residual temperature of the in-situ prepared FTO is reduced to 350 ℃, and forming the semiconductor material layer with the thickness of 10 nm-50 nm by taking the residual temperature as a heat source.
In the invention, the residual temperature of the in-situ prepared FTO is 450-650 ℃; in the subsequent process of forming the semiconductor material layer, the residual temperature is firstly reduced to 300-500 ℃.
In the present invention, the precursor solution of the semiconductor material is preferably selected from a precursor solution comprising a tin source or a precursor solution comprising a nickel source; wherein the tin source is preferably selected from SnCl2、SnCl4、C4H9SnCl3And SnCl4·5H2One or more of O, more preferably SnCl2、SnCl4、C4H9SnCl3Or SnCl4·5H2O; the nickel source is preferably selected from the group consisting of NiNO3·6H2O, nickel acetate (C)4H6NiO4)、NiCl2And in NiClOne or more, more preferably NiNO3·6H2O, nickel acetate (C)4H6NiO4)、NiCl2Or NiCl; the sources of the tin source and the nickel source are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the solvent of the precursor solution of the semiconductor material is preferably selected from one or more of water, ethanol, methanol, n-butanol, and isopropanol, and more preferably water, ethanol, methanol, n-butanol, or isopropanol; the source of the solvent is not particularly limited in the present invention, and deionized water well known to those skilled in the art and commercially available products of the above-mentioned ethanol, methanol, n-butanol and isopropanol may be used.
In the invention, the concentration of the semiconductor material in the precursor solution of the semiconductor material is preferably 0.01-5 mol/L, and more preferably 0.5-4 mol/L.
In the present invention, the precursor solution including the tin source preferably further includes:
doping metal ions; so that the tin source can be modified by doping.
In the present invention, the doping metal ions are preferably selected from Li+、Mg2+、Al3+、Y3+、Sb3+And Nb5+More preferably Li+、Mg2+、Al3+、Y3+、Sb3+Or Nb5+. In the invention, the doped metal ions are sprayed together with a tin source by dissolving a doped raw material containing the doped metal ions in a solvent of a precursor solution containing the tin source; the concentration of the doped metal ions in the precursor solution containing the tin source is preferably 0.001-0.1 mol/L, and more preferably 0.005-0.05 mol/L.
In the present invention, the precursor solution including a nickel source preferably further includes:
one or more of doping with basic metal cations, doping with transition metal cations, and doping with non-metal molecules;
more preferably:
doping with basic metal cations, transition metal cations, or non-metal molecules; so that the nickel source can be doped and modified.
In the present invention, the doping of the basic metal cation is preferably selected from K+、Mg+、Li+And Na+More preferably K+、Mg+、Li+Or Na+(ii) a The doped transition metal cation is preferably selected from Zn2+、Cu+、Co2+、Al3+And Ag+More preferably Zn2+、Cu+、Co2+、Al3+Or Ag+(ii) a The doped non-metallic molecule is preferably guanidine nitrate. In the invention, one or more of the doped alkaline metal cations, the doped transition metal cations and the doped non-metal molecules are sprayed together with a nickel source by dissolving a doping raw material comprising one or more of the doped alkaline metal cations, the doped transition metal cations and the doped non-metal molecules in a solvent of a precursor solution comprising the nickel source; the concentration of the doping raw material in the precursor solution containing the nickel source is preferably 0.001-0.1 mol/L, and more preferably 0.005-0.05 mol/L.
After the semiconductor material layer is formed, a lead iodide seed layer is further formed on the semiconductor material layer. In the present invention, the lead iodide seed layer is preferably formed by spraying a DMF and/or DMSO solution of lead iodide, and more preferably by spraying a DMF solution of lead iodide.
In the invention, the concentration of the lead iodide in the DMF and/or DMSO solution of the lead iodide is preferably 0.01-1 mol/L, and more preferably 0.1-0.5 mol/L.
In the invention, the thickness of the lead iodide seed layer is preferably 1 nm-10 nm, and more preferably 8 nm-8 nm.
After the lead iodide seed layer is formed, the invention further forms a perovskite material layer on the lead iodide seed layer. In the present invention, the process of forming the perovskite material layer is preferably embodied as follows:
spraying a perovskite solution when the residual temperature of the FTO prepared in situ is reduced to 200-300 ℃, and directionally generating a 200-500 nm perovskite material layer by taking the residual temperature as a heat source;
more preferably:
and spraying a perovskite solution when the residual temperature of the in-situ FTO preparation is reduced to 250 ℃, and directionally generating a 300-350 nm perovskite material layer by taking the residual temperature as a heat source.
In the invention, the residual temperature of the in-situ prepared FTO is 450-650 ℃; in the subsequent process of forming the semiconductor material layer, the residual temperature is firstly reduced to 300-500 ℃; in the process of further forming the lead iodide seed layer, the residual temperature is not particularly limited; and finally, in the process of forming the perovskite material layer, the residual temperature needs to be reduced to 200-300 ℃. The process takes the generated lead iodide as a seed layer to directionally generate a perovskite material layer, and simultaneously utilizes the residual heat (200-300 ℃ in the stage) in the in-situ preparation process of the FTO as the energy for forming the perovskite material layer, so that a heating link is not separately arranged.
In the present invention, the perovskite material solution is preferably prepared from a perovskite precursor material and an organic solvent. In the present invention, the perovskite precursor material is preferably selected from PbI2、PbBr2One or more of CsI, CsBr, FAI, MAI, MACl and MABr, more preferably PbI2、PbBr2CsI, CsBr, FAI, MAI, MACl or MABr; the organic solvent is preferably selected from one or more of DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), 2-ME (ethylene glycol methyl ether), ACN (acetonitrile) and GBL (γ -butyrolactone). The invention is about the PbI2、PbBr2The sources of CsI, CsBr, FAI, MAI, MACl and MABr and the above organic solvents are not particularly limited, and commercially available products or self-products known to those skilled in the art may be used.
In the invention, the concentration of the perovskite precursor material in the perovskite solution is preferably 0.05-1.5 mol/L, and more preferably 0.5-1 mol/L.
After the perovskite material layer is formed, the invention further forms a current carrier transmission layer and a metal electrode on the perovskite material layer in sequence to obtain the perovskite solar cell.
In the present invention, the carrier transport layer is preferably an electron transport layer or a hole transport layer; depending on the type of semiconductor material layer: the semiconductor material layer is P-type (NiO)x) A semiconductor material layer, on the formed perovskite material layer, an electron transport layer is further prepared; the semiconductor material layer is N-type (SnO)2) And a semiconductor material layer, wherein a hole transport layer is further prepared on the formed perovskite material layer.
In the present invention, the material of the electron transport layer is preferably selected from C60, SnO2And TiO2More preferably C60, SnO2Or TiO2(ii) a The material of the hole transport layer is preferably selected from PTAA and/or Spiro, more preferably PTAA or Spiro; the present invention is not particularly limited in terms of the source of the material for the electron transport layer and the material for the hole transport layer, and commercially available products known to those skilled in the art may be used.
In the invention, the thickness of the carrier transport layer is preferably 20nm to 100nm, and more preferably 40nm to 80 nm.
In the present invention, the metal of the metal electrode is preferably selected from one or more of Cu, Al, Au, and Ag, more preferably Cu, Al, Au, or Ag; the present invention is not particularly limited in this regard.
The invention provides a preparation method of a perovskite solar cell, which comprises the steps of firstly preparing FTO by adopting an in-situ preparation method, spraying a precursor solution of a tin source or a nickel source, and converting the FTO into tin oxide/nickel oxide by using residual heat in the in-situ preparation process, namely, a heating link is not independently arranged in the process of forming the tin oxide or the nickel oxide; then, continuously utilizing the residual heat in the in-situ FTO preparation process to prepare a layer of lead iodide, taking the generated lead iodide as a seed layer to directionally generate a perovskite material layer, and simultaneously forming the generated perovskite material layer, namely utilizing the residual heat in the in-situ FTO preparation process without independently arranging a heating link; lead iodide is used as a seed layer to directionally generate perovskite, the perovskite can be induced to preferentially grow along crystal faces (110) and (220), and the prepared perovskite solar cell is high in photoelectric conversion efficiency. In addition, the preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps: a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell; the residual temperature of the in-situ prepared FTO is 450-650 ℃. Compared with the prior art, the preparation method provided by the invention does not need to additionally provide an external heat source in the preparation process, so that the energy consumption is saved, lead iodide is used as a seed layer to directionally generate the perovskite, the perovskite can be induced to preferentially grow along crystal faces (110) and (220), and the prepared perovskite solar cell has high photoelectric conversion efficiency. Experimental results show that the perovskite solar cell obtained by the preparation method provided by the invention has the photoelectric conversion efficiency of more than 16%.
In addition, the preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
(1) The method for preparing FTO in situ was used as follows: inserting a multi-channel coating device into the narrow section of a tin bath of a float glass production line, and adding monobutyl tin trichloride (C) with the purity of 95wt%4H9SnCl3MBTC) as a precursor, 99wt% trifluoroacetic acid (CF)3COOH and TFA) as doping agent, and taking air and water as the oxidizing agent and catalyst of the reaction to carry out film coating; using a mole fraction of 1.6% MBTC, 0.88% TFA, 4.8% water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film; the residual temperature for the in situ preparation of FTO was 550 ℃.
(2) Spraying SnCl when the residual temperature of the in-situ preparation of FTO is reduced to 350 DEG C2Forming SnO with the thickness of 20 nm-30 nm by using an aqueous solution (the concentration is 2.5 mol/L)2。
(3) In the formed SnO2Spraying DMF solution (with the concentration of 0.5 mol/L) of lead iodide on the layer to form a lead iodide seed layer with the thickness of 2 nm-8 nm.
(4) Spraying perovskite solution (the perovskite material is PbI) on the formed lead iodide seed layer when the residual temperature is reduced to 250 DEG C2And MAI, molar ratio 1: 1, the solvent is methanol and acetonitrile, the concentration is 1 mol/L), and the perovskite material layer with the thickness of 320 nm-330 nm is directionally generated.
(5) And sequentially forming a PTAA hole transport layer with the thickness of 60nm and a metal Cu electrode on the formed perovskite material layer to obtain the perovskite solar cell.
The photovoltaic conversion efficiency of the perovskite solar cell provided in example 1 was detected to be 16%.
Example 2
(1) The method for preparing FTO in situ was used as follows: inserting a multi-channel coating device into the narrow section of a tin bath of a float glass production line, and adding monobutyl tin trichloride (C) with the purity of 95wt%4H9SnCl3MBTC) as a precursor, 99wt% trifluoroacetic acid (CF)3COOH and TFA) as doping agent, and taking air and water as the oxidizing agent and catalyst of the reaction to carry out film coating; using a mole fraction of 1.6% MBTC, 0.88% TFA, 4.8% water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film; the residual temperature for the in situ preparation of FTO was 550 ℃.
(2) Spraying NiNO when the residual temperature of the in-situ FTO preparation is reduced to 350 DEG C3·6H2An aqueous solution of O (the concentration is 2.5 mol/L) to form NiO with the thickness of 20nm to 30nmx。
(3) In the formation of NiOxDMF solution sprayed with lead iodide on layerAnd (4) forming a lead iodide seed layer with the thickness of 2 nm-8 nm by using the solution (the concentration is 0.5 mol/L).
(4) Spraying perovskite solution (the perovskite material is PbI) on the formed lead iodide seed layer when the residual temperature is reduced to 250 DEG C2And MAI, molar ratio 1: 1, the solvent is methanol and acetonitrile, the concentration is 1 mol/L), and the perovskite material layer with the thickness of 320 nm-330 nm is directionally generated.
(5) And sequentially forming a C60 electron transport layer with the thickness of 60nm and a metal Ag electrode on the formed perovskite material layer to obtain the perovskite solar cell, wherein the structure of the perovskite solar cell is shown in figure 1.
The photovoltaic conversion efficiency of the perovskite solar cell provided in example 2 was detected to be 18%.
Example 3
The preparation process provided in example 1 was used with the difference that: in the step (2), the spraying comprises doping the raw material (ZnCl)2/CuCl2) SnCl of2Aqueous solution (SnCl)2The concentration of (2.5 mol/L) and the concentration of the doping raw material of 0.05 mol/L) to form Nb with the thickness of 20nm to 30nm5+Doped SnO2(ii) a And obtaining the perovskite solar cell.
The photovoltaic conversion efficiency of the perovskite solar cell provided in example 3 was detected to be 18%.
Example 4
The preparation process provided in example 2 was used with the difference that: in the step (2), the spraying comprises doping the raw material (Cu (NO)3)2·2.5H2O/Zn(NO3)2·6H2O) NiNO3·6H2Aqueous solution of O (NiNO)3·6H2The concentration of O is 2.5mol/L, the concentration of doping raw material is 0.05 mol/L) to form Co with the thickness of 20 nm-30 nm2+Doped NiOx(ii) a And obtaining the perovskite solar cell.
The photovoltaic conversion efficiency of the perovskite solar cell provided in example 4 was detected to be 16.5%.
According to the preparation method provided by the embodiments 1-4, the dense perovskite thin film is prepared by using the waste heat in the in-situ FTO preparation process under the condition of no anti-solvent in the perovskite spraying process, an external heat source does not need to be additionally provided in the preparation process, and the energy consumption is saved; moreover, lead iodide is used as a seed layer to directionally generate perovskite, and the perovskite can be induced to grow preferentially along the (110) and (220) crystal planes (see fig. 2).
Comparative example
(1) Inserting a multi-channel coating device into the narrow section of a tin bath of a float glass production line, and adding monobutyl tin trichloride (C) with the purity of 95wt%4H9SnCl3MBTC) as a precursor, 99wt% trifluoroacetic acid (CF)3COOH and TFA) as doping agent, and taking air and water as the oxidizing agent and catalyst of the reaction to carry out film coating; using a mole fraction of 1.6% MBTC, 0.88% TFA, 4.8% water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film; the residual temperature for the in situ preparation of FTO was 550 ℃.
(2) Spraying perovskite solution (the perovskite material is PbI) when the residual temperature of the in-situ FTO preparation is reduced to 250 DEG C2And MAI, molar ratio 1: 1, the solvent is methanol and acetonitrile, and the concentration is 1 mol/L), and a perovskite material layer with the thickness of 320 nm-330 nm is generated.
(3) And sequentially forming a PTAA hole transport layer with the thickness of 60nm and a metal Cu electrode on the formed perovskite material layer to obtain the perovskite solar cell.
Through detection, the perovskite layer is only directly prepared on the FTO in the comparative example, the energy levels are not matched, and the photoelectric conversion efficiency of the obtained perovskite solar cell is only 3%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A preparation method of a perovskite solar cell comprises the following steps:
a) sequentially forming a semiconductor material layer, a lead iodide seed layer, a perovskite material layer, a current carrier transmission layer and a metal electrode on the surface of the FTO prepared in situ to obtain a perovskite solar cell;
the preparation method of the in-situ prepared FTO in the step a) comprises the following specific steps:
inserting a multi-channel coating device into a narrow section of a tin bath of a float glass production line, and coating by using monobutyl tin trichloride with the purity of 95wt% as a precursor, using trifluoroacetic acid with the purity of 99wt% as a doping agent, and using air and water as an oxidant and a catalyst for reaction; the method comprises the steps of adopting 1-2% of MBTC, 0.5-1% of TFA, 4-6% of water and N2Is used as carrier gas, and is gasified at 175 ℃ after entering an evaporator; after being gasified, the mixture enters a gas mixing chamber to be mixed and sprayed on the surface of glass with the temperature of 675 ℃ through a coating device, and the mixed gas reacts on a gas-solid phase interface to deposit and form a compact FTO solid film;
the residual temperature of the in-situ prepared FTO is 450-650 ℃;
the process for forming the semiconductor material layer in the step a) specifically comprises the following steps:
spraying a precursor solution of the semiconductor material when the residual temperature of the in-situ prepared FTO is reduced to 300-500 ℃, and forming a semiconductor material layer with the thickness of 5-100 nm by taking the residual temperature of 300-500 ℃ as a heat source;
the process for forming the perovskite material layer in the step a) is specifically as follows:
spraying perovskite solution when the residual temperature of the in-situ FTO preparation is reduced to 200-300 ℃, and directionally generating a 200-500 nm perovskite material layer by taking the residual temperature of 200-300 ℃ as a heat source.
2. The method according to claim 1, wherein the semiconductor material is a semiconductor materialThe precursor solution of the material is selected from a precursor solution comprising a tin source or a precursor solution comprising a nickel source; the tin source is selected from SnCl2、SnCl4、C4H9SnCl3And SnCl4·5H2One or more of O; the nickel source is selected from NiNO3·6H2O, nickel acetate, NiCl2And NiCl; the solvent of the precursor solution of the semiconductor material is selected from one or more of water, ethanol, methanol, n-butanol and isopropanol; the concentration of the semiconductor material in the precursor solution of the semiconductor material is 0.01-5 mol/L.
3. The method of claim 2, wherein the precursor solution including the tin source further includes:
doping metal ions; the doping metal ion is selected from Li+、Mg2+、Al3+、Y3+、Sb3+And Nb5+One or more of; the concentration of the doped metal ions in the precursor solution containing the tin source is 0.001-0.1 mol/L.
4. The method of claim 2, wherein the precursor solution comprising the nickel source further comprises:
one or more of doping with basic metal cations, doping with transition metal cations, and doping with non-metal molecules; the doped basic metal cation is selected from K+、Mg+、Li+And Na+One or more of; the doped transition metal cation is selected from Zn2+、Cu+、Co2+、Al3+And Ag+One or more of; the doped non-metal molecule is guanidine nitrate.
5. The method according to claim 1, wherein the lead iodide seed layer is formed in step a) by spraying a DMF and/or DMSO solution of lead iodide; the concentration of lead iodide in the DMF and/or DMSO solution of lead iodide is 0.01-1 mol/L; the thickness of the lead iodide seed layer is 1 nm-10 nm.
6. The production method according to claim 1, wherein the perovskite solution is prepared from a perovskite precursor material and an organic solvent; the perovskite precursor material is selected from PbI2、PbBr2One or more of CsI, CsBr, FAI, MAI, MACl and MABr; the organic solvent is selected from one or more of DMF, DMSO, 2-ME, ACN and GBL; the concentration of the perovskite precursor material in the perovskite solution is 0.05 mol/L-1.5 mol/L.
7. The production method according to claim 1, wherein the carrier transport layer in step a) is an electron transport layer or a hole transport layer; the material of the electron transport layer is selected from C60 and SnO2And TiO2One or more of; the material of the hole transport layer is selected from PTAA and/or Spiro; the thickness of the carrier transmission layer is 20 nm-100 nm.
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