CN112234146A - Preparation method of perovskite light absorption layer, perovskite solar cell and preparation method - Google Patents

Preparation method of perovskite light absorption layer, perovskite solar cell and preparation method Download PDF

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CN112234146A
CN112234146A CN202011222581.5A CN202011222581A CN112234146A CN 112234146 A CN112234146 A CN 112234146A CN 202011222581 A CN202011222581 A CN 202011222581A CN 112234146 A CN112234146 A CN 112234146A
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perovskite
layer
substrate
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state material
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李雄
李敏
刘凤翔
杨佳庆
刘然然
尤帅
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Huazhong University of Science and Technology
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Abstract

The invention provides a preparation method of a perovskite light absorption layer, a perovskite solar cell and a preparation method of the perovskite light absorption layer, wherein the preparation method of the perovskite light absorption layer comprises the following steps: preparing a first perovskite transition state material on one side of a first substrate; preparing a second perovskite transition state material on one side of the second substrate; and (3) attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thus obtaining the perovskite light absorption layer. According to the preparation method of the perovskite light absorption layer, the prepared perovskite light absorption layer is small in holes and defects, the obtained perovskite light absorption layer is high in flatness, the quality of the perovskite light absorption layer is greatly improved, and the photoelectric conversion efficiency and the stability of the perovskite solar cell are improved.

Description

Preparation method of perovskite light absorption layer, perovskite solar cell and preparation method
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite light absorption layer preparation method, a perovskite solar cell and a preparation method.
Background
With the continuous development and progress of society, the demand of human beings for energy is also increasing. Solar energy is renewable, clean and environmentally friendly, compared to the non-renewable and environmentally polluting nature of traditional fossil energy sources. The traditional solar cell is represented by an amorphous silicon solar cell, but the amorphous silicon solar cell has high manufacturing cost, complicated manufacturing procedure and great pollution to the environment. As a third-generation solar cell, the perovskite solar cell has the advantages of solution-soluble processing, low cost and the like, the photoelectric conversion efficiency of the perovskite solar cell is improved from 3.8% in 2009 to 25.2% of authentication efficiency, and the perovskite solar cell is concerned and researched by researchers.
At present, a spin-coating method is generally adopted for preparing the perovskite solar cell, a perovskite light absorption layer formed by the spin-coating method is thin, a microstructure has many holes, and electric leakage is serious; a large number of defects are generated, and perovskite decomposition is promoted; the uniformity is poor, the surface is uneven, and the interface charge transmission is influenced, so that the electrical performance and the stability of the perovskite solar cell are obviously reduced. Therefore, the high-quality perovskite light absorption layer is obtained, is a key factor for improving the performance of the perovskite solar cell, and is beneficial to commercialization of the perovskite solar cell.
Based on the defects of the perovskite light absorption layers prepared at present, improvement on the defects is needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a perovskite light absorption layer, a perovskite solar cell and a preparation method thereof, so as to solve the technical defects in the prior art.
In a first aspect, the present invention provides a method for preparing a perovskite light-absorbing layer, comprising the following steps:
preparing a first perovskite transition state material on one side of a first substrate;
preparing a second perovskite transition state material on one side of the second substrate;
and (3) attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thus obtaining the perovskite light absorption layer.
Optionally, in the preparation method of the perovskite light absorption layer, after the second perovskite transition state material is transferred to the first substrate, heating is performed at 30-150 ℃ for 5-40 min to obtain the perovskite light absorption layer.
Optionally, in the preparation method of the perovskite light absorption layer, the structural formula of the perovskite light absorption layer material is ABX3(ii) a Wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
Optionally, the preparation method of the perovskite light absorption layer, wherein the preparation of the first perovskite transition state material or the preparation of the second perovskite transition state material specifically includes: depositing the perovskite precursor on the first substrate or the second substrate, and then annealing for 1 s-5 min at 30-150 ℃ to obtain the first perovskite transition state material or the second perovskite transition state material.
Optionally, in the preparation method of the perovskite light absorption layer, the first substrate and the second substrate are made of one of ITO glass, FTO glass, polydimethylsiloxane and its derivatives, polythiophene and its derivatives, polytriphenylamine and its derivatives, polypyrrole and its derivatives, polymethyl methacrylate, polyetherimide, ethylene-vinyl acetate copolymer, polyvinyl butyral resin, ethylene methacrylic acid copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
In a second aspect, the invention further provides a perovskite solar cell, which comprises a conductive substrate layer, a first charge transport layer and an interface layer which are sequentially stacked, and a perovskite light absorption layer, a second charge transport layer, a hole blocking layer and a counter electrode which are prepared by the preparation method.
Optionally, in the perovskite solar cell, the first charge transport layer and the second charge transport layer are electron transport layers or hole transport layers, where the hole transport layer is made of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly-bis (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly-3-hexylthiophene (P3HT), poly-3, 4-ethylenedioxythiophene, polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, or vanadium pentoxide; the electron transport layer is made of one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
Optionally, in the perovskite solar cell, the counter electrode is made of one of Al, Ag, Au, Mo, Cr and C.
In a third aspect, the invention further provides a preparation method of the perovskite solar cell, which comprises the following steps:
providing a conductive substrate layer;
preparing a first charge transport layer on the surface of the conductive substrate layer;
preparing an interface layer on the surface of the first charge transport layer;
preparing a perovskite light absorption layer on the surface of the interface layer;
preparing a second charge transport layer on the surface of the perovskite light absorption layer;
preparing a hole blocking layer on the surface of the second charge transport layer;
and preparing a counter electrode on the surface of the hole blocking layer.
Compared with the prior art, the preparation method of the perovskite light absorption layer has the following beneficial effects:
(1) according to the preparation method of the perovskite light absorption layer, the side face of the second substrate with the second perovskite transition state material is attached to the side face of the first substrate with the first perovskite transition state material, the second perovskite transition state material is transferred to the first substrate by heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃, and the prepared perovskite light absorption layer is small in holes and defects, high in flatness and greatly improved in quality and photoelectric conversion efficiency and stability of the perovskite solar cell.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a flow chart of a manufacturing process of a method of manufacturing a perovskite light-absorbing layer according to the present invention;
FIG. 2 is a schematic illustration of a method of making a perovskite light absorbing layer of the present invention;
FIG. 3 is a schematic structural view of a perovskite solar cell of the present invention;
FIG. 4 is a cross-sectional Scanning Electron Microscope (SEM) image of a perovskite light-absorbing layer prepared in inventive example 1 and a perovskite light-absorbing layer prepared in comparative example 1;
fig. 5 is a current density-voltage graph of the perovskite solar cell prepared in example 2 of the present invention and comparative example 1.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment of the application provides a preparation method of a perovskite light absorption layer, as shown in fig. 1, comprising the following steps:
s1, preparing a first perovskite transition state material on one side of the first substrate;
s2, preparing a second perovskite transition state material on one side of the second substrate;
and S3, attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thereby obtaining the perovskite light absorption layer.
It should be noted that the first substrate and the second substrate in the embodiments of the present application are flexible substrates or rigid materials, and specifically, the materials of the first substrate and the second substrate in the embodiments of the present application are ITO glass, FTO glass, polydimethylsiloxane PDMS and its derivatives, polythiophenes such as pdot: pss and P3HT and their derivatives, polytriphenylamine such as PTAA and its derivatives, polypyrrole and its derivatives, polymethyl methacrylate (PMMA), Polyetherimide (PEI), ethylene-vinyl acetate copolymer, polyvinyl butyral resin, ethylene methyl acrylate copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
In the embodiment of the application, after the second perovskite transition state material is transferred to the first substrate, the perovskite light absorption layer is obtained by heating at the temperature of 30-150 ℃ for 5-40 min.
In the embodiment of the application, the perovskite active layer material comprises two or more perovskite light absorption layer materials with the same or different elements, and the structural formula of the perovskite light absorption layer material is ABX3Structure; wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
In the embodiment of the present application, the preparing the first perovskite transition state material or the preparing the second perovskite transition state material specifically includes: depositing a perovskite precursor on a first substrate or a second substrate, and annealing at 30-150 ℃ for 1 s-5 min to obtain a first perovskite transition state material or a second perovskite transition state material; deposition methods for perovskite precursor materials include, but are not limited to, vacuum evaporation, electron beam evaporation, magnetron sputtering, atomic layer deposition, photolithography, chemical vapor deposition, screen printing, hydrothermal, electrochemical deposition, spin coating, blade coating, rod coating, slot-and-squeeze coating, spray coating, and ink-jet printing.
Specifically, the perovskite precursor used for preparing the first perovskite transition state material in the embodiment of the present application is (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55，(MA0.15FA0.8Cs0.05)PbBr0.45I2.55The perovskite precursor is prepared by the following specific method:
according to the molar ratio of the components of 1.5M of Pb to 1, the bromomethylamine MABr to the lead bromide PbBr2Amitraz iodide FAI lead iodide PbI2Cesium iodide CsI (0.15: 0.15:0.8:0.85: 0.05), DMF (DMF) and DMSO (4: 1) are mixed in a solvent, and the mixture is dissolved in the solvent to form (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55And (3) precursor solution.
The perovskite precursor used for preparing the second perovskite transition state material is (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55The preparation method is the same as above.
Specifically, fig. 2 shows a schematic diagram of a preparation method of a perovskite light absorption layer in an embodiment of the present application, wherein a first perovskite transition state material 12 is prepared on a first substrate 11, a second perovskite transition state material 14, the second perovskite transition state material 14 and the first perovskite transition state material 12 are prepared on a second substrate 13, and the second perovskite transition state material 14 is heated at a temperature of 30 to 150 ℃ under a pressure of 0.1 to 100Mpa for 3 to 20min to transfer the second perovskite transition state material 14 to the first substrate, so as to obtain the perovskite light absorption layer 4.
Based on the same inventive concept, the embodiment of the present application further provides a perovskite solar cell, as shown in fig. 3, which includes a conductive substrate layer 1, a first charge transport layer 2, an interface layer 3, a perovskite light absorption layer 4 prepared by the preparation method, a second charge transport layer 5, a hole blocking layer 6, and a counter electrode 7, which are sequentially stacked.
Specifically, in the embodiment of the present application, the first charge transport layer 2 and the second charge transport layer 5 are electron transport layers or hole transport layers, when the first charge transport layer 2 is an electron transport layer, the second charge transport layer 5 is a hole transport layer, and when the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer.
Specifically, in the embodiment of the present application, the material of the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly-bis (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly-3-hexylthiophene (P3HT), poly-3, 4-ethylenedioxythiophene, which is one of polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, and vanadium pentoxide; the material of the electron transport layer is one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
Specifically, in the embodiment of the present application, the material of the counter electrode 7 is one of Al, Ag, Au, Mo, Cr, and C.
Based on the same inventive concept, the preparation method of the perovskite solar cell comprises the following steps:
using ITO conductive glass as a conductive substrate, and depositing a hole transport layer on the conductive substrate, wherein the hole transport layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; then depositing an interface layer on the hole transport layer, wherein the interface layer is made of PMMA (polymethyl methacrylate) and the deposition method is a spin-coating method;
preparing perovskite precursor solution (MA) according to Pb concentration of 1.5M0.15FA0.8Cs0.05)PbBr0.45I2.55Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using an anti-solvent in the spin coating process, and annealing at 50 ℃ for 2min to prepare a first perovskite transition state material;
depositing an interface layer on the surface of the other ITO conductive glass, wherein the interface layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; preparing perovskite precursor (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using an anti-solvent in the spin coating process, and annealing at 50 ℃ for 2min to prepare a second perovskite transition state material;
specifically, the anti-solvent is one or two mixtures of chlorobenzene, ethyl acetate or isopropanol, and the like, the mixture of chlorobenzene and ethyl acetate is adopted in the application, and the redundant solvents are solvents DMF and DMSO for dissolving perovskite.
Attaching one side of a conductive substrate deposited with a first perovskite transition state material to one side of another ITO conductive glass deposited with a second perovskite transition state material, applying 1Mpa pressure, heating at 50 ℃ for 5min to transfer the second perovskite transition state material onto the conductive substrate, and then heating the conductive substrate at 40 ℃ for 10min to obtain a perovskite light absorption layer;
depositing an electron transport layer on the perovskite light absorption layer, wherein the electron transport layer is made of PCBM and the deposition method is a spin-coating method;
depositing a hole blocking layer on the electron transport layer, wherein the hole blocking layer is made of BCP (bulk blend positive) and the deposition mode is a spin coating method;
and evaporating metal Ag with the thickness of 100nm on the prepared hole blocking layer by adopting an evaporation method to be used as a metal counter electrode, so that the perovskite solar cell is prepared.
Example 2
The embodiment of the application provides a preparation method of a perovskite light absorption layer, as shown in fig. 1, comprising the following steps:
s1, preparing a first perovskite transition state material on one side of the first substrate;
s2, preparing a second perovskite transition state material on one side of the second substrate;
and S3, attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thereby obtaining the perovskite light absorption layer.
It should be noted that the first substrate and the second substrate in the embodiments of the present application are flexible substrates or rigid materials, and specifically, the materials of the first substrate and the second substrate in the embodiments of the present application are ITO glass, FTO glass, polydimethylsiloxane PDMS and its derivatives, polythiophenes such as pdot: pss and P3HT and their derivatives, polytriphenylamine such as PTAA and its derivatives, polypyrrole and its derivatives, polymethyl methacrylate (PMMA), Polyetherimide (PEI), ethylene-vinyl acetate copolymer, polyvinyl butyral resin, ethylene methyl acrylate copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
In the embodiment of the application, after the second perovskite transition state material is transferred to the first substrate, the perovskite light absorption layer is obtained by heating at the temperature of 30-150 ℃ for 5-40 min.
In the embodiment of the application, the perovskite active layer material comprises two or more perovskite light absorption layer materials with the same or different elements, and the structural formula of the perovskite light absorption layer material is ABX3Structure; wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
In the embodiment of the present application, the preparing the first perovskite transition state material or the preparing the second perovskite transition state material specifically includes: depositing a perovskite precursor on a first substrate or a second substrate, and annealing at 30-150 ℃ for 1 s-5 min to obtain a first perovskite transition state material or a second perovskite transition state material; deposition methods for perovskite precursor materials include, but are not limited to, vacuum evaporation, electron beam evaporation, magnetron sputtering, atomic layer deposition, photolithography, chemical vapor deposition, screen printing, hydrothermal, electrochemical deposition, spin coating, blade coating, rod coating, slot-and-squeeze coating, spray coating, and ink-jet printing.
Specifically, the perovskite precursor used for preparing the first perovskite transition state material in the embodiment of the present application is (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55The perovskite precursor used for preparing the second perovskite transition state material is (MA)0.16FA0.84)PbBr0.48I2.52And the like.
(MA0.16FA0.84)PbBr0.48I2.52The perovskite precursor is prepared by the following specific method:
according to the molar ratio of the components of 1.5M of Pb to 1, the bromomethylamine MABr to the lead bromide PbBr2Amitraz iodide FAI lead iodide PbI2The components were dissolved in a solvent (DMF: DMSO: 4:1 (volume ratio)) to form (MA), which was weighed out at a ratio of 0.16:0.16:0.84:0.890.16FA0.84)PbBr0.48I2.52And (3) precursor solution.
Based on the same inventive concept, the embodiment of the present application further provides a perovskite solar cell, as shown in fig. 3, which includes a conductive substrate layer 1, a first charge transport layer 2, an interface layer 3, a perovskite light absorption layer 4 prepared by the preparation method, a second charge transport layer 5, a hole blocking layer 6, and a counter electrode 7, which are sequentially stacked.
Specifically, in the embodiment of the present application, the first charge transport layer 2 and the second charge transport layer 5 are electron transport layers or hole transport layers, when the first charge transport layer 2 is an electron transport layer, the second charge transport layer 5 is a hole transport layer, and when the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer.
Specifically, in the embodiment of the present application, the material of the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly-bis (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly-3-hexylthiophene (P3HT), poly-3, 4-ethylenedioxythiophene, which is one of polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, and vanadium pentoxide; the material of the electron transport layer is one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
Specifically, in the embodiment of the present application, the material of the counter electrode 7 is one of Al, Ag, Au, Mo, Cr, and C.
Based on the same inventive concept, the preparation method of the perovskite solar cell comprises the following steps:
using ITO conductive glass as a conductive substrate, and depositing a hole transport layer on the conductive substrate, wherein the hole transport layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; then depositing an interface layer on the hole transport layer, wherein the interface layer is made of PMMA (polymethyl methacrylate) and the deposition method is a spin-coating method;
preparing perovskite precursor (MA) according to Pb concentration of 1.5M0.15FA0.8Cs0.05)PbBr0.45I2.55The preparation method is the same as that of the embodiment 1, 30 mu L of perovskite precursor is dripped on the interface layer, the anti-solvent is used for extracting the redundant solvent in the spin coating process, and the annealing is carried out for 2min at 50 ℃ to prepare the first perovskite transition state material;
depositing an interface layer on the surface of the other ITO conductive glass, wherein the interface layer is made of PTAA, the deposition method is a spin-coating method, and the deposition mode is a spin-coating method; preparing perovskite precursor (MA) according to Pb concentration of 1.5M0.16FA0.84)PbBr0.48I2.52Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using anti-solvent in the spin coating process, annealing at 50 ℃ for 2min, and preparing to obtain a second perovskite transition state material；
Specifically, the anti-solvent is one or two mixtures of chlorobenzene, ethyl acetate or isopropanol, and the like, the mixture of chlorobenzene and ethyl acetate is adopted in the application, and the redundant solvents are solvents DMF and DMSO for dissolving perovskite.
Attaching one side of a conductive substrate deposited with a first perovskite transition state material to one side of another ITO conductive glass deposited with a second perovskite transition state material, applying 1Mpa pressure, heating at 50 ℃ for 5min to transfer the second perovskite transition state material onto the conductive substrate, and then heating the conductive substrate at 40 ℃ for 10min to obtain a perovskite light absorption layer;
depositing an electron transport layer on the perovskite light absorption layer, wherein the electron transport layer is made of PCBM and the deposition method is a spin-coating method;
depositing a hole blocking layer on the electron transport layer, wherein the hole blocking layer is made of BCP (bulk blend positive) and the deposition mode is a spin coating method;
and evaporating metal Ag with the thickness of 100nm on the prepared hole blocking layer by adopting an evaporation method to be used as a metal counter electrode, so that the perovskite solar cell is prepared.
Example 3
The embodiment of the application provides a preparation method of a perovskite light absorption layer, as shown in fig. 1, comprising the following steps:
s1, preparing a first perovskite transition state material on one side of the first substrate;
s2, preparing a second perovskite transition state material on one side of the second substrate;
and S3, attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thereby obtaining the perovskite light absorption layer.
It should be noted that the first substrate and the second substrate in the embodiments of the present application are flexible substrates or rigid materials, and specifically, the materials of the first substrate and the second substrate in the embodiments of the present application are ITO glass, FTO glass, polydimethylsiloxane PDMS and its derivatives, polythiophenes such as pdot: pss and P3HT and their derivatives, polytriphenylamine such as PTAA and its derivatives, polypyrrole and its derivatives, polymethyl methacrylate (PMMA), Polyetherimide (PEI), ethylene-vinyl acetate copolymer, polyvinyl butyral resin, ethylene methyl acrylate copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
In the embodiment of the application, after the second perovskite transition state material is transferred to the first substrate, the perovskite light absorption layer is obtained by heating at the temperature of 30-150 ℃ for 5-40 min.
In the embodiment of the application, the perovskite active layer material comprises two or more perovskite light absorption layer materials with the same or different elements, and the structural formula of the perovskite light absorption layer material is ABX3Structure; wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
In the embodiment of the present application, the preparing the first perovskite transition state material or the preparing the second perovskite transition state material specifically includes: depositing a perovskite precursor on a first substrate or a second substrate, and annealing at 30-150 ℃ for 1 s-5 min to obtain a first perovskite transition state material or a second perovskite transition state material; deposition methods for perovskite precursor materials include, but are not limited to, vacuum evaporation, electron beam evaporation, magnetron sputtering, atomic layer deposition, photolithography, chemical vapor deposition, screen printing, hydrothermal, electrochemical deposition, spin coating, blade coating, rod coating, slot-and-squeeze coating, spray coating, and ink-jet printing.
Specifically, the perovskite precursor used for preparing the first perovskite transition state material in the embodiment of the present application is (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55Preparing the second perovskite transition materialThe perovskite precursor is CsPbBr3And the like.
CsPbBr3The perovskite precursor is prepared by the following specific method:
weighing 1.5M Pb and 1:1 mol ratio of cesium bromide CsBr and lead bromide PbBr, and dissolving in DMSO to obtain 0.15M Pb CsPbBr3A perovskite precursor solution.
Based on the same inventive concept, the embodiment of the present application further provides a perovskite solar cell, as shown in fig. 3, which includes a conductive substrate layer 1, a first charge transport layer 2, an interface layer 3, a perovskite light absorption layer 4 prepared by the preparation method, a second charge transport layer 5, a hole blocking layer 6, and a counter electrode 7, which are sequentially stacked.
Specifically, in the embodiment of the present application, the first charge transport layer 2 and the second charge transport layer 5 are electron transport layers or hole transport layers, when the first charge transport layer 2 is an electron transport layer, the second charge transport layer 5 is a hole transport layer, and when the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer.
Specifically, in the embodiment of the present application, the material of the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly-bis (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly-3-hexylthiophene (P3HT), poly-3, 4-ethylenedioxythiophene, which is one of polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, and vanadium pentoxide; the material of the electron transport layer is one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
Specifically, in the embodiment of the present application, the material of the counter electrode 7 is one of Al, Ag, Au, Mo, Cr, and C.
Based on the same inventive concept, the embodiment of the application also discloses a preparation method of the perovskite solar cell, which comprises the following steps:
using ITO conductive glass as a conductive substrate, and depositing a hole transport layer on the conductive substrate, wherein the hole transport layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; then depositing an interface layer on the hole transport layer, wherein the interface layer is made of PMMA (polymethyl methacrylate) and the deposition method is a spin-coating method;
preparing perovskite precursor (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55The preparation method is the same as that of the embodiment 1, 30 mu L of perovskite precursor is dripped on the interface layer, the anti-solvent is used for extracting the redundant solvent in the spin coating process, and the annealing is carried out for 2min at 50 ℃ to prepare the first perovskite transition state material;
depositing an interface layer on the surface of the other ITO conductive glass, wherein the interface layer is made of PTAA, the deposition method is a spin-coating method, and the deposition mode is a spin-coating method; the perovskite precursor CsPbBr is prepared according to the concentration of 1.5M Pb3Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using an anti-solvent in the spin coating process, and annealing at 50 ℃ for 2min to prepare a second perovskite transition state material;
specifically, the anti-solvent is one or two mixtures of chlorobenzene, ethyl acetate or isopropanol, and the like, and the mixture of chlorobenzene and ethyl acetate is adopted in the application, and the redundant solvent is a solvent DMSO for dissolving the perovskite.
Attaching one side of a conductive substrate deposited with a first perovskite transition state material to one side of another ITO conductive glass deposited with a second perovskite transition state material, applying 1Mpa pressure, heating at 50 ℃ for 5min to transfer the second perovskite transition state material onto the conductive substrate, and then heating the conductive substrate at 40 ℃ for 10min to obtain a perovskite light absorption layer;
depositing an electron transport layer on the perovskite light absorption layer, wherein the electron transport layer is made of PCBM and the deposition method is a spin-coating method;
depositing a hole blocking layer on the electron transport layer, wherein the hole blocking layer is made of BCP (bulk blend positive) and the deposition mode is a spin coating method;
and evaporating metal Ag with the thickness of 100nm on the prepared hole blocking layer by adopting an evaporation method to be used as a metal counter electrode, so that the perovskite solar cell is prepared.
Example 4
The embodiment of the application provides a preparation method of a perovskite light absorption layer, as shown in fig. 1, comprising the following steps:
s1, preparing a first perovskite transition state material on one side of the first substrate;
s2, preparing a second perovskite transition state material on one side of the second substrate;
and S3, attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thereby obtaining the perovskite light absorption layer.
It should be noted that the first substrate and the second substrate in the embodiments of the present application are flexible substrates or rigid materials, and specifically, the materials of the first substrate and the second substrate in the embodiments of the present application are ITO glass, FTO glass, polydimethylsiloxane PDMS and its derivatives, polythiophenes such as pdot: pss and P3HT and their derivatives, polytriphenylamine such as PTAA and its derivatives, polypyrrole and its derivatives, polymethyl methacrylate (PMMA), Polyetherimide (PEI), ethylene-vinyl acetate copolymer, polyvinyl butyral resin, ethylene methyl acrylate copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
In the embodiment of the application, after the second perovskite transition state material is transferred to the first substrate, the perovskite light absorption layer is obtained by heating at the temperature of 30-150 ℃ for 5-40 min.
In the embodiment of the application, the perovskite active layer material comprises two or more perovskite light absorption layer materials with the same or different elements, and the structural formula of the perovskite light absorption layer material is ABX3Structure; wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
In the embodiment of the present application, the preparing the first perovskite transition state material or the preparing the second perovskite transition state material specifically includes: depositing a perovskite precursor on a first substrate or a second substrate, and annealing at 30-150 ℃ for 1 s-5 min to obtain a first perovskite transition state material or a second perovskite transition state material; deposition methods for perovskite precursor materials include, but are not limited to, vacuum evaporation, electron beam evaporation, magnetron sputtering, atomic layer deposition, photolithography, chemical vapor deposition, screen printing, hydrothermal, electrochemical deposition, spin coating, blade coating, rod coating, slot-and-squeeze coating, spray coating, and ink-jet printing.
Specifically, the perovskite precursor used for preparing the first perovskite transition state material in the embodiment of the present application is (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55The perovskite precursor used for preparing the second perovskite transition state material is PEA2MA4Pb5I16And the like.
In particular, PEA2MA4Pb5I16The preparation method comprises the following steps: according to the Pb concentration of 1.5M, the mole ratio of each component is phenylethylamine hydroiodide (PEAI), iodomethylamine (MAI) and lead iodide (PbI)2) The components are dissolved in a solvent to form PEA, wherein the solvent is DMF and DMSO is 4:1 (volume ratio)2MA4Pb5I16And (3) precursor solution.
Based on the same inventive concept, the embodiment of the present application further provides a perovskite solar cell, as shown in fig. 3, which includes a conductive substrate layer 1, a first charge transport layer 2, an interface layer 3, a perovskite light absorption layer 4 prepared by the preparation method, a second charge transport layer 5, a hole blocking layer 6, and a counter electrode 7, which are sequentially stacked.
Specifically, in the embodiment of the present application, the first charge transport layer 2 and the second charge transport layer 5 are electron transport layers or hole transport layers, when the first charge transport layer 2 is an electron transport layer, the second charge transport layer 5 is a hole transport layer, and when the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer.
Specifically, in the embodiment of the present application, the material of the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly-bis (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly-3-hexylthiophene (P3HT), poly-3, 4-ethylenedioxythiophene, which is one of polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, and vanadium pentoxide; the material of the electron transport layer is one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
Specifically, in the embodiment of the present application, the material of the counter electrode 7 is one of Al, Ag, Au, Mo, Cr, and C.
Based on the same inventive concept, the embodiment of the application also discloses a preparation method of the perovskite solar cell, which comprises the following steps:
using ITO conductive glass as a conductive substrate, and depositing a hole transport layer on the conductive substrate, wherein the hole transport layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; then depositing an interface layer on the hole transport layer, wherein the interface layer is made of PMMA (polymethyl methacrylate) and the deposition method is a spin-coating method;
preparing perovskite precursor (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55The preparation method is the same as that of the embodiment 1, 30 mu L of perovskite precursor is dripped on the interface layer, the anti-solvent is used for extracting the redundant solvent in the spin coating process, and the annealing is carried out for 2min at 50 ℃ to prepare the first perovskite transition state material;
depositing an interface layer on the surface of the other ITO conductive glass, wherein the interface layer is made of PTAA, the deposition method is a spin-coating method, and the deposition mode is a spin-coating method; preparation of perovskite precursor PEA2MA4Pb5I16Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using an anti-solvent in the spin coating process, and annealing at 50 ℃ for 2min to prepare a second perovskite transition state material;
specifically, the anti-solvent is one or two mixtures of chlorobenzene, ethyl acetate or isopropanol, and the like, the mixture of chlorobenzene and ethyl acetate is adopted in the application, and the redundant solvents are solvents DMF and DMSO for dissolving perovskite.
Attaching one side of a conductive substrate deposited with a first perovskite transition state material to one side of another ITO conductive glass deposited with a second perovskite transition state material, applying 1Mpa pressure, heating at 50 ℃ for 5min to transfer the second perovskite transition state material onto the conductive substrate, and then heating the conductive substrate at 40 ℃ for 10min to obtain a perovskite light absorption layer;
depositing an electron transport layer on the perovskite light absorption layer, wherein the electron transport layer is made of PCBM and the deposition method is a spin-coating method;
depositing a hole blocking layer on the electron transport layer, wherein the hole blocking layer is made of BCP (bulk blend positive) and the deposition mode is a spin coating method;
and (3) evaporating and plating 100nm thick metal Ag on the prepared hole transport layer by adopting an evaporation method to serve as a metal counter electrode, so as to prepare the perovskite solar cell.
Comparative example 1
A preparation method of a perovskite solar cell comprises the following steps:
using ITO conductive glass as a conductive substrate, and depositing a hole transport layer on the conductive substrate, wherein the hole transport layer is made of PTAA (Polybutylece terephthalate), and the deposition method is a spin-coating method; then depositing an interface layer on the hole transport layer, wherein the interface layer is made of PMMA (polymethyl methacrylate) and the deposition method is a spin-coating method;
preparing perovskite precursor (MA)0.15FA0.8Cs0.05)PbBr0.45I2.55Dripping 30 mu L of perovskite precursor on the interface layer, extracting redundant solvent by using an anti-solvent in the spin coating process, and annealing at 50 ℃ for 2min to prepare a perovskite light absorption layer;
depositing an electron transport layer on the perovskite light absorption layer, wherein the electron transport layer is made of PCBM and the deposition method is a spin-coating method;
depositing a hole blocking layer on the electron transport layer, wherein the hole blocking layer is made of BCP (bulk blend positive) and the deposition mode is a spin coating method;
and evaporating metal Ag with the thickness of 100nm on the prepared hole blocking layer by adopting an evaporation method to be used as a metal counter electrode, so that the perovskite solar cell is prepared.
Cross-sectional Scanning Electron Micrographs (SEM) of the perovskite light-absorbing layer prepared in the perovskite solar cell preparation process of example 1 and the perovskite light-absorbing layer prepared in comparative example 1 are shown in fig. 4, where (a) in fig. 4 is a cross-sectional scanning electron micrograph of the perovskite light-absorbing layer prepared in example 1 and (b) in fig. 4 is a cross-sectional scanning electron micrograph of the perovskite light-absorbing layer prepared in comparative example 1, and it can be seen from fig. 4 that (a) in the figure shows a perovskite light-absorbing layer consisting of two transition perovskite layers, while (b) in the figure shows only one perovskite light-absorbing layer.
The current density-voltage (J-V) profiles of the perovskite solar cells prepared in example 2 of the present invention and comparative example 1 were tested, and as shown in fig. 5, a curve a is a current density-voltage profile of the perovskite solar cell prepared in comparative example 1, a curve b is a current density-voltage profile of the perovskite solar cell prepared in example 2, a curve b is 1085mv in voltage Voc, and a current Jsc is 20.48mA/cm2The fill factor FF is 0.6 percent and the efficiency eta is 13.34 percent; in the curve a, the Voc is 971mv, and the Jsc is 16.75mA/cm2FF was 0.52% and η was 8.51%, and as can be seen from fig. 5, the Photoelectric Conversion Efficiency (PCE) of the perovskite solar cell prepared in example 2 was higher than that of comparative example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a perovskite light absorption layer is characterized by comprising the following steps:
preparing a first perovskite transition state material on one side of a first substrate;
preparing a second perovskite transition state material on one side of the second substrate;
and (3) attaching the side surface of the second substrate with the second perovskite transition state material to the side surface of the first substrate with the first perovskite transition state material, and heating for 3-20 min at the pressure of 0.1-100 Mpa and the temperature of 30-150 ℃ to transfer the second perovskite transition state material to the first substrate, thus obtaining the perovskite light absorption layer.
2. The method for preparing a perovskite light-absorbing layer as claimed in claim 1, wherein after the second perovskite transition material is transferred onto the first substrate, the method further comprises heating at 30-150 ℃ for 5-40 min to obtain the perovskite light-absorbing layer.
3. The method of making a perovskite light absorbing layer as defined in claim 1 wherein the perovskite light absorbing layer material has the formula ABX3(ii) a Wherein A is one of amido, amidino and alkali, B is one of Pb, Sn, Ca, Ba, Sr, Co, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Hg, Tl, Bi, polonium and Eu, and X is one of I, Br, Cl, astatine and thiocyanate.
4. The method of making a perovskite light absorbing layer as defined in claim 1 wherein the making of the first perovskite transition state material or the making of the second perovskite transition state material specifically comprises: depositing the perovskite precursor on the first substrate or the second substrate, and then annealing for 1 s-5 min at 30-150 ℃ to obtain the first perovskite transition state material or the second perovskite transition state material.
5. The method of making a perovskite light absorbing layer as defined in claim 1 wherein the first and second substrates are made of one of ITO glass, FTO glass, polydimethylsiloxane and its derivatives, polythiophene and its derivatives, polytriphenylamine and its derivatives, polypyrrole and its derivatives, polymethylmethacrylate, polyetherimide, ethylene-vinyl acetate copolymer, polyvinylbutyral resin, ethylene methacrylic acid copolymer, tetrafluoroethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polylactic acid, polyamide and its derivatives.
6. A perovskite solar cell is characterized by comprising a conductive substrate layer, a first charge transport layer, an interface layer, a perovskite light absorption layer prepared by the preparation method of any one of claims 1 to 5, a second charge transport layer, a hole blocking layer and a counter electrode which are sequentially stacked.
7. The perovskite solar cell according to claim 6, wherein the first charge transport layer and the second charge transport layer are electron transport layers or hole transport layers, wherein the material of the hole transport layer is one of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly (4-phenyl) (2,4, 6-trimethylphenyl) amine, poly 3-hexylthiophene (P3HT), poly 3, 4-ethylenedioxythiophene, polystyrene sulfonate, nickel oxide, cuprous thiocyanate, cuprous iodide, molybdenum oxide, tungsten oxide, vanadium pentoxide; the electron transport layer is made of one of [6,6] -phenyl-C61-isopropyl butyrate, titanium oxide, zirconium oxide, zinc oxide, tin oxide, graphene and derivatives thereof.
8. The perovskite solar cell of claim 6, wherein the material of the counter electrode is one of Al, Ag, Au, Mo, Cr, C.
9. A method of manufacturing a perovskite solar cell as defined in any one of claims 6 to 8, comprising the steps of:
providing a conductive substrate layer;
preparing a first charge transport layer on the surface of the conductive substrate layer;
preparing an interface layer on the surface of the first charge transport layer;
preparing a perovskite light absorption layer on the surface of the interface layer;
preparing a second charge transport layer on the surface of the perovskite light absorption layer;
preparing a hole blocking layer on the surface of the second charge transport layer;
and preparing a counter electrode on the surface of the hole blocking layer.
CN202011222581.5A 2020-11-05 2020-11-05 Preparation method of perovskite light absorption layer, perovskite solar cell and preparation method Pending CN112234146A (en)

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CN105470400A (en) * 2015-11-19 2016-04-06 华北电力大学 Perovskite film preparation method and application
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