CN110854274B - Preparation method of perovskite thin film and application of perovskite thin film in solar cell - Google Patents

Preparation method of perovskite thin film and application of perovskite thin film in solar cell Download PDF

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CN110854274B
CN110854274B CN201911156823.2A CN201911156823A CN110854274B CN 110854274 B CN110854274 B CN 110854274B CN 201911156823 A CN201911156823 A CN 201911156823A CN 110854274 B CN110854274 B CN 110854274B
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袁永波
罗师强
蔺云
王继飞
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Central South University
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Abstract

The invention discloses a perovskiteThe invention provides a method for controlling solvation BX by adjusting the solubility of each component based on understanding the nucleation process of halogen perovskite crystal containing multi-component solute2Compounds (e.g. PbI)2‑DMF，PbI2-DMSO) and complexes thereof (e.g. MAI-PbI)2‑DMF，MAI‑PbI2-DMSO), thereby realizing the regulation and control of nucleation rate, density and spatial distribution of the seed crystal in the solution and obtaining the perovskite thin film with high crystallization quality and optimized crystal orientation; the invention provides two specific implementation processes for regulating the perovskite segregation crystallization process: 1. regulating the nucleation speed and density of the solvated lead halide compound and the compound thereof by using the AX additive; 2. controlling the temperature and volatilization rate of local area of the solution and controlling the solvated BX by solution coating process2And the compound thereof are subjected to segregation crystallization in different areas to obtain the perovskite thin film with good crystallinity and uniform appearance.

Description

Preparation method of perovskite thin film and application of perovskite thin film in solar cell
Technical Field
The invention belongs to the field of perovskite solar cells, relates to a preparation method of a perovskite thin film and application of the perovskite thin film in a solar cell, and particularly relates to a method for regulating and controlling the film forming morphology and the crystallization quality of perovskite based on regulation and control of perovskite segregation crystals.
Background
As a third-generation novel solar cell technology, the perovskite solar cell has the advantages of solution preparation, low cost, excellent photoelectric property and the like. The perovskite solar cell is improved from 3.8% originally reported in 2009 to 25.2% which is currently approved, is close to the efficiency of a crystalline silicon solar cell, and shows good application potential and commercialization prospect. The morphology and microstructure of the perovskite thin film directly affect the performance of the perovskite solar cell. For example, reducing the pores of the perovskite thin film can inhibit the short circuit of the perovskite battery, improving the uniformity of the perovskite thin film can increase the repeatability of the efficiency of the battery and the efficiency of a large-area die, and increasing the grain size and optimizing the crystal orientation of the grains can respectively reduce the crystal boundary defects and improve the transmission efficiency of charges.
Due to the colloidal property of the perovskite solution, the solvent is combined with the solute of the perovskite solution to generate a solvated lead halide in a crystalline state, the solvated lead halide is generated earlier than the perovskite crystal, the later perovskite forming process is directly influenced, and the surface morphology of the perovskite thin film and the crystal orientation of the perovskite crystal are influenced. When the solute is a multicomponent component, such as a complex ionic perovskite, a two-dimensional layered perovskite, the perovskite nucleation process is more complicated. The perovskite nucleation process not only determines the phase distribution of different solutes of the perovskite, but also affects the crystallographic orientation of the perovskite crystal, which are directly related to the carrier transport efficiency in the perovskite crystal and the efficiency and stability of the final solar cell.
There are many methods for controlling the perovskite crystallization and thus the morphology and microstructure of the thin film, such as adding additives to the perovskite precursor solution, adjusting the hydrophilicity of the substrate surface, rapidly crystallizing the perovskite by an anti-solvent, and regrowing the crystal grains by high temperature annealing or solvent annealing post-treatment. However, how to add the additive into the perovskite solution is to control the morphology of the perovskite thin film by controlling the nucleation process of the perovskite, and a complete and mature process is not formed yet.
Disclosure of Invention
Aiming at the problems of unclear regulation and control mechanism and lack of pertinence of the process on the nucleation rate, the nucleation area and the crystallization process of the perovskite in the prior art, the invention aims to provide a regulation and control principle and a method for effectively regulating the nucleation rate and the density of solvated lead halide compound segregation crystals and the nucleation area, and the regulation and control principle and method are used for improving the morphology of the perovskite thin film and the performance of a related solar cell.
In order to achieve the purpose, the invention provides the following technical scheme: a method for regulating a perovskite nucleation process, comprising:
the perovskite comprises but is not limited to lead-based perovskite and multi-component perovskite with lead element as the leading B site, and solvated BX is regulated and controlled by adding additive AX into the prepared perovskite precursor solution2Compounds (e.g. PbI)2-DMF，PbI2-DMSO) and complexation thereofSubstance (e.g. MAI-PbI)2-DMF，MAI-PbI2-DMSO) control of solvated BX2Segregated crystallization of compounds and their complexes;
coating the perovskite precursor solution on a substrate by adopting a solution coating method, controlling the temperature and the volatilization rate of the local area of the solution, and controlling the solvated BX2Carrying out segregation crystallization on the compound and the compound thereof in different areas to obtain a perovskite thin film with good crystallinity and uniform appearance;
in the structural formula of the additive AX, A is NH4 +，CH3NH3 +，NH2CHNH2 +，CH3NH2CH3 +Any one of the above; x represents Cl-，Br-，I-，SCN-，CH3COO−Any one of the above;
the BX2In the compound, X is any one of I, Br and Cl, and B is Pb or a polymetallic element composition taking Pb as a main component.
In a preferred embodiment, the present invention provides a method for regulating a perovskite nucleation process, comprising the following steps:
(1) separately weighing PbI2And Methyl Ammonium Iodide (MAI) in DMF solvent to obtain PbI2DMF solution, MAI/DMF solution;
(2) adding Butylamine (BA) into the MAI/DMF solution obtained in the step (1) to obtain a mixed solution of methylammonium iodide (MAI) and butylammonium iodide (BAI);
(3) weighing an additive AX, dissolving the additive AX in PbI obtained in the step (1)2Heating DMF solution until additive AX is completely dissolved, and controlling the molar ratio AX/PbI20.05-5 to obtain an additive solution;
(4) uniformly mixing the solutions prepared in the step (2) and the step (3), standing and aging to obtain a two-dimensional layered perovskite precursor solution (BA)2MAn-1PbnI3n+1，n=4）；
(5) Two-dimensional coating by solution coating methodCoating a perovskite precursor solution on a substrate, annealing, and controlling the temperature and volatilization rate of a local area of the solution to control the solvated PbI2And (3) performing segregation crystallization on the compound in different areas to induce segregation precipitation of the quasi-three-dimensional perovskite on the surface of the coating film, so as to obtain the two-dimensional perovskite film with good crystallinity and uniform appearance.
Preferably, in step (1), the PbI is2The concentration of the/DMF solution is 400-600 mg/ml; the concentration of the MAI/DMF solution is 400-600 mg/ml.
Preferably, in the step (2), the molar ratio of the butylammonium iodide to the methylammonium iodide is 2: (1-9).
Preferably, in step (3), the additive AX is NH4Cl。
Preferably, in step (5), the solution coating method includes, but is not limited to, any one of spin coating, knife coating, spray coating, slit coating, and czochralski method.
Further, in the step (5), preparing the perovskite thin film by adopting a spin coating method: and spin-coating the two-dimensional perovskite precursor solution on a substrate at the rotating speed of 4000-6000 rpm.
Further, in the step (5), a blade coating method is adopted to prepare the perovskite thin film: and (3) blade-coating the two-dimensional perovskite precursor solution on a substrate at the speed of 1-100 mm/s, wherein the film is blown by hot air in the blade-coating process, and segregation of the quasi-three-dimensional perovskite on the surface of the coated film is induced to be separated out.
Preferably, in the step (5), the annealing treatment is: annealing at 50-80 ℃ for 0-10 min, and then annealing at 90-150 ℃ for 5-60 min.
As a general inventive concept, the present invention also provides a method of fabricating a perovskite thin film-based solar cell, comprising the steps of:
s1, use of Sn-doped In2O3(ITO) conductive glass as a device substrate;
s2. preparing a hole transport layer: using PEDOT: the PSS material is used as a hole transport layer and is coated on the ITO substrate after ultraviolet treatment in a spinning mode;
s3, preparing the two-dimensional perovskite thin film on the hole transport layer by adopting a solution coating method;
s4, preparing an electron transport layer: preparing a fullerene derivative PCBM/chlorobenzene solution, spin-coating the fullerene derivative PCBM/chlorobenzene solution on a two-dimensional perovskite film, and drying the fullerene derivative PCBM/chlorobenzene solution;
s5. preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method;
s6, preparing a back electrode: and depositing copper on the hole blocking layer by a vacuum thermal evaporation method to obtain the perovskite thin film based solar cell.
Further, in step S1, the ITO conductive glass has a specification of transmittance >85%, sheet resistance <10 Ω, and a size of 15mm × 15 mm.
Further, in step S4, the fullerene derivative PCBM/chlorobenzene solution with the mass concentration of 5-50 mg/ml is spin-coated on a two-dimensional perovskite thin film and dried at 60-120 ℃.
The mechanism analysis of the invention is as follows:
the solubility of different components of the perovskite is different, and the different solubility of different components leads the component with low solubility to be more easily separated out, namely, segregated crystallization; the existence of segregation crystallization phenomenon has influence on the morphology and the component uniformity of the finally formed film, and a clear experimental conclusion is lacked in the past. For ternary or higher order components (e.g., complex ionic perovskites and two-dimensional layered perovskites), segregated crystals not only determine the perovskite nucleation mode, but also affect the phase separation of the different solute phases of the perovskite. The control of the morphology and component distribution of the final thin film perovskite is realized by focusing on and utilizing the segregation process (such as the formation of solvated lead halide compounds) of the perovskite component and utilizing the control of the segregation crystallization process (such as the control of the relative solubility of each component). Based on the mechanism analysis of segregation crystallization, the invention provides two regulation and control methods:
firstly, regulating and controlling the forming speed and density of solvated lead halide: by controlling BX2Component (e.g. PbI)2-DMF，PbI2-DMSO) and complexes thereof (e.g. MAI-PbI)2-DMF，MAI-PbI2-DMSO), i.e. segregation of solvated lead halide compoundsCrystallization, including the use of AX (A = NH)4 +，CH3NH3 +，NH2CHNH2 +，CH3NH2CH3 +；X=Cl-，Br-，I-，SCN-，CH3COO−) And (3) an additive is added to regulate and control the morphology and crystallization of the perovskite thin film.
By adding the additive AX, the BX can be increased2Solubility of solute to inhibit BX2And the precipitation of the intermediate phase thereof, thereby controlling the morphology and crystallization of the perovskite. It is demonstrated that additives can increase PbI2The solubility of the solute, and further the appearance of the perovskite thin film is improved. Because of the different difficulty of the additive in the annealing process, we choose NH that volatilizes most easily by heating4And the Cl additive further verifies the effects of regulating segregation crystallization and improving film morphology crystallization by the additive on a device, so that the efficiency of the perovskite battery is improved.
Secondly, regulating and controlling the formation area of the solvated lead halide compound: the segregated crystallization on different areas of the solvated lead-halogen compound is controlled by controlling the temperature, volatilization rate and the like of local areas of the solution, including controlling the substrate temperature, the surface temperature of the perovskite precursor solution and the volatilization rate of the solvent during the film coating process.
In the preparation method of the large-area film by the blade coating method, the overall battery efficiency is directly influenced by regulating the morphology uniformity and the crystallization condition of the film, and the volatilization of a surface solvent is promoted in a hot air blowing mode in the complex system perovskite (ternary and above components), so that the segregation crystallization of a surface solute is induced, the nucleation position of the film is regulated, the uniform and smooth perovskite film is further obtained, the photoelectric conversion efficiency of the perovskite battery is further improved, and a key process and mechanism guidance is provided for preparing the complex system perovskite in a large area.
In the spin-coating method, because the surface air flow is large, hot air is not needed, the segregation of the quasi-three-dimensional perovskite on the surface of the coating film is induced through annealing treatment, the morphology and crystallization of the perovskite film are regulated, and the two-dimensional perovskite film with good crystallinity and uniform morphology is obtained.
Compared with the prior art, the invention has the beneficial technical effects that:
1) the invention emphasizes that the segregation concentrations of different components of the perovskite are different, for the composite ion perovskite and the two-dimensional layered perovskite, the sequential separation of the multi-component perovskite directly influences the appearance and the phase distribution of the perovskite, and NH is added4Cl and other additives to regulate and control the segregation and crystallization of solvated lead halide.
2) In the blade coating process, the method of blowing hot air is used for accelerating the segregation and crystallization of solvated lead halide and solvated tin halide on the surface of the solution (taking two-dimensional layered perovskite as an example, due to the solubility PbI2<MAI<BAI, the formation of solvated lead halide compounds on the surface of the perovskite precursor solution, such as: PbI2-DMF，MAI-PbI2DMF) to regulate and control the crystallization and morphology of the film.
3) Reflecting on the performance of the device, the photoelectric conversion efficiency of the solar cell based on the perovskite thin film prepared by the spin-coating method is improved by 13.2 percent from 0.3 percent of the control group; the photoelectric conversion efficiency of the solar cell based on the perovskite thin film prepared by the blade coating method is improved to 12.2 percent from 0.4 percent of the control group.
Drawings
Fig. 1 is a segregated crystal diagram of solvated lead halide compounds observed under a microscope.
FIG. 2 is PbI2Solubility of MAI and BAI in DMF solvent.
FIG. 3 (a) shows the non-segregation control technique (without NH addition)4Cl); (b) using segregation regulation (addition of NH)4Cl), two-dimensional layered perovskite BA2MAn-1PbnI3n+1(n = 4) film surface morphology.
FIG. 4 shows PbI with and without addition of AX additives2Nucleation concentration in DMF.
Fig. 5 is a schematic device structure diagram of a perovskite thin film based solar cell in an embodiment of the present invention.
Fig. 6 is a photocurrent-voltage curve of the device prepared in example 2 of the present invention and comparative example 2.
FIG. 7 is a graph showing photocurrent-voltage curves of devices fabricated in example 3, comparative example 3-1, and comparative example 3-2 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
The embodiment of the invention provides a method for regulating and controlling a perovskite nucleation process, which comprises the following steps:
(1) separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain PbI2The concentration of the/DMF solution and the concentration of the MAI/DMF solution are both 500 mg/mL;
(2) adding 24.8 μ L of Butylamine (BA) into 198.2 μ L of MAI/DMF solution with the mass fraction of 500mg/mL prepared by 3.1 to prepare a mixed solution of Methyl Ammonium Iodide (MAI) and butylammonium iodide (BAI);
(3) for the controlled segregation crystallization experimental group: weigh 12.4mg NH4PbI of 500mg/mL mass fraction prepared by dissolving Cl in 461. mu.L2DMF solution, heated at 65 ℃ for about half an hour until NH4Cl additive is completely dissolved, molar ratio NH4Cl/PbI2=1:2；
(4) Uniformly mixing the solutions prepared in the step (2) and the step (3), standing and aging for 30min to obtain a two-dimensional layered perovskite precursor solution (BA)2MAn-1PbnI3n+1，n=4）；
(5) Spin coating the two-dimensional perovskite precursor solution on PEDOT at 5000 rpm: PSS substrates were annealed at 65 ℃ for 5 minutes and then at 100 ℃ for 30min to a thickness of about 300nm, as shown in FIG. 1.
Comparative example 1
(1) Separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain PbI2The concentration of the/DMF solution and the concentration of the MAI/DMF solution are both 500 mg/mL;
(2) adding 24.8 μ L of Butylamine (BA) into 198.2 μ L of MAI/DMF solution with the mass fraction of 500mg/mL prepared by 3.1 to prepare a mixed solution of Methyl Ammonium Iodide (MAI) and butylammonium iodide (BAI);
(3) for the controlled segregation crystallization control: 461 μ L of the formulated PbI at 500mg/mL mass fraction were extracted directly2DMF solution;
(4) uniformly mixing the solutions prepared in the step (2) and the step (3), standing and aging for 30min to obtain a two-dimensional layered perovskite precursor solution (BA)2MAn-1PbnI3n+1，n=4）；
(5) Spin coating the two-dimensional perovskite precursor solution on PEDOT at 5000 rpm: the PSS substrate was annealed at 65 ℃ for 5 minutes and then at 100 ℃ for 30min to a thickness of about 300 nm.
As shown in FIG. 2, for two-dimensional layered perovskite BA2MAn-1PbnI3n+1Solubility of the component PbI2<MAI<BAI, hence solute PbI2More easily separated out and forms a dendritic intermediate phase with a solvent DMF, and when the solvent DMF is volatilized, a film which is composed of dendritic perovskite crystals and has rough surface and a plurality of holes is obtained (as shown in figure 3). An additive (such as AX (a = CH) is added to the perovskite precursor solution3NH3 +，NH4 +；X=Cl-，Br-，I-）），PbI2Increased nucleation concentration of, thus PbI2Nucleation of (a) is suppressed, and thus a perovskite thin film having a flat surface and completely covered is formed, as shown in fig. 4.
Example 2
The embodiment of the invention provides a preparation method of a perovskite thin film based solar cell, which comprises the following steps:
1) the specification of use is light transmittance>85% square resistance<10 omega, 15mm Sn doped In2O3(ITO) conductive glass as a device substrate;
2) preparing a hole transport layer: using a PEDOT (PSS) material as a hole transport layer, spin-coating PEDOT (4083) on the ITO substrate after ultraviolet treatment at the rotating speed of 3000rpm for 60s, and then heating at 120 ℃ for 20 minutes;
3) light absorptionLayer (b): preparation of BA2MAn-1PbnI3n+1Two-dimensional layered perovskite precursor solution:
3.1: separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain a solution with the same concentration of 500 mg/mL;
3.2: adding 24.8 μ L of Butylamine (BA) into 198.2 μ L of MAI/DMF solution with the mass fraction of 500mg/mL prepared by 3.1 to prepare a mixed solution of Methyl Ammonium Iodide (MAI) and butylammonium iodide (BAI);
3.3: regulating and controlling segregation crystallization: weigh 12.4mg NH4PbI of 500mg/mL mass fraction prepared by dissolving Cl in 461. mu.L of 3.12DMF solution, heated at 65 ℃ for about half an hour until NH4The Cl additive is completely dissolved;
3.4: mixing the 3.2 and 3.3 solutions, standing and aging for 30min to obtain BA2MAn-1PbnI3n+1(n = 4) a two-dimensional layered perovskite precursor solution;
3.5: spin coating the two-dimensional perovskite precursor solution on PEDOT at 5000 rpm: on the PSS substrate, annealing at 65 ℃ for 5 minutes, and then annealing at 100 ℃ for 30min to obtain the PSS substrate with the thickness of about 300 nm;
4) preparing an electron transport layer: weighing fullerene derivative PCBM with the mass of 15mg, dissolving in 1mL chlorobenzene, fully dissolving, spin-coating on a two-dimensional perovskite film, and drying at 80 ℃;
5) preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method, wherein the evaporation rate is about 7nm and is 0.2A/s;
6) preparing a back electrode: copper was deposited on the hole blocking layer by a simple vacuum thermal evaporation method at about 70nm with an evaporation rate of 1 a/s, fig. 5 is a schematic device structure diagram of the perovskite thin film based solar cell in this example.
Through detection, the perovskite solar cell prepared by the spin-coating method has better photoelectric conversion performance under the irradiation of standard simulated sunlight, the open-circuit voltage is 1.1V, and the current density is 16.5mAcm-2Fill factor of 72.7%, photoelectric conversion efficiency13.2%。
Comparative example 2
1) The specification of use is light transmittance>85% square resistance<10 omega, 15mm Sn doped In2O3(ITO) conductive glass as a device substrate;
2) preparing a hole transport layer: using a PEDOT (PSS) material as a hole transport layer, spin-coating PEDOT (4083) on the ITO substrate after ultraviolet treatment at the rotating speed of 3000rpm for 60s, and then heating at 120 ℃ for 20 minutes;
3) light absorbing layer: preparation of BA2MAn-1PbnI3n+1Two-dimensional layered perovskite precursor solution:
3.1: separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain a solution with the same concentration of 500 mg/mL;
3.2: adding 24.8 μ L of Butylamine (BA) into 198.2 μ L of MAI/DMF solution with the mass fraction of 500mg/mL prepared by 3.1 to prepare a mixed solution of Methyl Ammonium Iodide (MAI) and butylammonium iodide (BAI);
3.3: 461 μ L of PbI prepared at 3.1 and 500mg/mL mass fraction2DMF solution;
3.4: mixing the 3.2 and 3.3 solutions, standing and aging for 30min to obtain BA2MAn-1PbnI3n+1(n = 4) a two-dimensional layered perovskite precursor solution;
3.5: spin coating the two-dimensional perovskite precursor solution on PEDOT at 5000 rpm: on the PSS substrate, annealing at 65 ℃ for 5 minutes, and then annealing at 100 ℃ for 30min to obtain the PSS substrate with the thickness of about 300 nm;
4) preparing an electron transport layer: weighing fullerene derivative PCBM with the mass of 15mg, dissolving in 1mL chlorobenzene, fully dissolving, spin-coating on a two-dimensional perovskite film, and drying at 80 ℃;
5) preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method, wherein the evaporation rate is about 7nm and is 0.2A/s;
6) preparing a back electrode: copper was deposited on the hole blocking layer by simple vacuum thermal evaporation, about 70 nm. The evaporation rate is 1A/s.
Through detection, the perovskite solar cell prepared by the spin-coating method has poor photoelectric conversion performance under the irradiation of standard simulated sunlight, the open-circuit voltage of the perovskite solar cell is 0.3V, and the current density of the perovskite solar cell is 2.8mAcm-2The filling factor is 30.2%, and the photoelectric conversion efficiency is 0.3%.
Example 2 addition of NH to perovskite precursor solution4Cl additive and no hot air blowing during spin coating, comparative example 2 is perovskite precursor solution without NH4The photoelectric conversion efficiency of the perovskite solar cell prepared by the embodiment of the invention is obviously superior to that of the perovskite solar cell prepared by the comparative example as shown in FIG. 6, wherein the Cl additive is not blown with hot air during spin coating.
Example 3
The embodiment of the invention provides a preparation method of a perovskite thin film based solar cell, which comprises the following steps:
1) the specification of use is light transmittance>85% square resistance<10 omega, 15mm Sn doped In2O3(ITO) conductive glass as a device substrate;
2) preparing a hole transport layer: using a PEDOT (PSS) material as a hole transport layer, spin-coating PEDOT (4083) on the ITO substrate after ultraviolet treatment at the rotating speed of 3000rpm for 60s, and then heating at 120 ℃ for 20 minutes;
3) light absorbing layer: preparation of BA2MAn-1PbnI3n+1A two-dimensional layered perovskite precursor solution;
3.1: separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain a solution with the same concentration of 500 mg/mL;
3.2: adding 24.8 μ L of Butylamine (BA) into 198.2 μ L of MAI/DMF solution with the mass fraction of 500mg/mL prepared by 3.1 to prepare a mixed solution of Methyl Ammonium Iodide (MAI) and butylammonium iodide (BAI);
3.3: regulating and controlling segregation crystallization: weigh 12.4mg NH4PbI of 500mg/mL mass fraction prepared by dissolving Cl in 461. mu.L of 3.12DMF solution, heated at 65 ℃ for about half an hour until NH4Cl additive completeDissolving;
3.4: mixing the 3.2 and 3.3 solutions, standing and aging for 30min to obtain BA2MAn-1PbnI3n+1(n = 4) a two-dimensional layered perovskite precursor solution;
3.5: and (3) blade-coating the two-dimensional perovskite precursor solution on PEDOT at the speed of 1 mm/s: annealing the PSS substrate at 65 ℃ for 5 minutes, then annealing the PSS substrate at 100 ℃ for 30 minutes, wherein the thickness of the PSS substrate is about 300nm, and in the blade coating process, hot air is blown to the film to improve the segregation of quasi-three-dimensional perovskite on the surface of the blade coated film so as to regulate and control the morphology and the crystallization of the perovskite film;
4) preparing an electron transport layer: weighing fullerene derivative PCBM with the mass of 15mg, dissolving in 1mL chlorobenzene, fully dissolving, spin-coating on a two-dimensional perovskite film, and drying at 80 ℃;
5) preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method, wherein the evaporation rate is about 7nm and is 0.2A/s;
6) preparing a back electrode: copper was deposited on the hole blocking layer by a simple vacuum thermal evaporation method, about 70nm, with an evaporation rate of 1 a/s.
Through detection, the perovskite solar cell prepared by the blade coating method has the best photoelectric conversion performance under the irradiation of standard simulated sunlight, the open-circuit voltage is 1.06V, and the current density is 16.8mAcm-2The fill factor is 68.1%, and the photoelectric conversion efficiency is 12.2%.
Comparative example 3-1
1) The specification of use is light transmittance>85% square resistance<10 omega, 15mm Sn doped In2O3(ITO) conductive glass as a device substrate;
2) preparing a hole transport layer: using a PEDOT (PSS) material as a hole transport layer, spin-coating PEDOT (4083) on the ITO substrate after ultraviolet treatment at the rotating speed of 3000rpm for 60s, and then heating at 120 ℃ for 20 minutes;
3) light absorbing layer: preparation of BA2MAn-1PbnI3n+1A two-dimensional layered perovskite precursor solution;
3.1: separately weighing lead iodide (PbI)2) Anddissolving Methyl Ammonium Iodide (MAI) in Dimethylformamide (DMF) solvent at 65 ℃ to obtain solution with the same concentration of 500 mg/mL;
3.2: mu.L of Butylamine (BA) 24.8. mu.L was added to 3.1 of MAI/DMF at a mass fraction of 500mg/mL to prepare a mixed solution of methylammonium iodide (MAI) and butylammonium iodide (BAI).
3.3: regulating and controlling segregation crystallization: weigh 12.4mg NH4PbI of 500mg/mL mass fraction prepared by dissolving Cl in 461. mu.L of 3.12DMF solution, heated at 65 ℃ for about half an hour until NH4The Cl additive is completely dissolved;
3.4: mixing the 3.2 and 3.3 solutions, standing and aging for 30min to obtain BA2MAn-1PbnI3n+1(n = 4) a two-dimensional layered perovskite precursor solution;
3.5: and (3) blade-coating the two-dimensional perovskite precursor solution on PEDOT at the speed of 1 mm/s: annealing the PSS substrate at 65 ℃ for 5 minutes, then annealing the PSS substrate at 100 ℃ for 30 minutes, wherein the thickness of the PSS substrate is about 300nm, and the segregation crystallization of the quasi-three-dimensional perovskite on the surface of the blade-coated film is improved by blowing the film without hot air in the blade coating process;
4) preparing an electron transport layer: weighing fullerene derivative PCBM with the mass of 15mg, dissolving in 1mL chlorobenzene, fully dissolving, spin-coating on a two-dimensional perovskite film, and drying at 80 ℃;
5) preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method, wherein the evaporation rate is about 7nm and is 0.2A/s;
6) preparing a back electrode: copper was deposited on the hole blocking layer by a simple vacuum thermal evaporation method, about 70nm, with an evaporation rate of 1 a/s.
Through detection, the perovskite solar cell prepared by the blade coating method has poor photoelectric conversion performance under the irradiation of standard simulated sunlight, the open-circuit voltage of the perovskite solar cell is 0.4V, and the current density of the perovskite solar cell is 2.5mAcm-2The fill factor is 40.3%, and the photoelectric conversion efficiency is 0.43%.
Comparative examples 3 to 2
1) The specification of use is light transmittance>85% square resistance<10 omega, 15mm Sn doped In2O3(ITO) conductive glass as a device substrate;
2) preparing a hole transport layer: using a PEDOT (PSS) material as a hole transport layer, spin-coating PEDOT (4083) on the ITO substrate after ultraviolet treatment at the rotating speed of 3000rpm for 60s, and then heating at 120 ℃ for 20 minutes;
3) light absorbing layer: preparation of BA2MAn-1PbnI3n+1A two-dimensional layered perovskite precursor solution;
3.1: separately weighing lead iodide (PbI)2) And Methyl Ammonium Iodide (MAI) dissolved in Dimethylformamide (DMF) solvent at 65 ℃ to obtain a solution with the same concentration of 500 mg/mL;
3.2: mu.L of Butylamine (BA) 24.8. mu.L was added to 3.1 of MAI/DMF at a mass fraction of 500mg/mL to prepare a mixed solution of methylammonium iodide (MAI) and butylammonium iodide (BAI).
3.3: 461 μ L of 3.1 formulations of 500mg/mL mass fraction of PbI were withdrawn2DMF solution;
3.4: mixing the 3.2 and 3.3 solutions, standing and aging for 30min to obtain BA2MAn-1PbnI3n+1(n = 4) a two-dimensional layered perovskite precursor solution;
3.5: and (3) blade-coating the two-dimensional perovskite precursor solution on PEDOT at the speed of 1 mm/s: annealing the PSS substrate at 65 ℃ for 5 minutes, then annealing the PSS substrate at 100 ℃ for 30 minutes, wherein the thickness of the PSS substrate is about 300nm, and in the blade coating process, hot air is blown to the film to improve the segregation of quasi-three-dimensional perovskite on the surface of the blade coated film so as to regulate and control the morphology and the crystallization of the perovskite film;
4) preparing an electron transport layer: weighing fullerene derivative PCBM with the mass of 15mg, dissolving in 1mL chlorobenzene, fully dissolving, spin-coating on a two-dimensional perovskite film, and drying at 80 ℃;
5) preparing a hole blocking layer: evaporating Bathocuproine (BCP) on the electron transport layer by a vacuum thermal evaporation method, wherein the evaporation rate is about 7nm and is 0.2A/s;
6) preparing a back electrode: copper was deposited on the hole blocking layer by a simple vacuum thermal evaporation method, about 70nm, with an evaporation rate of 1 a/s.
Through detection, the perovskite solar cell prepared by the blade coating method has improved photoelectric conversion performance under the irradiation of standard simulated sunlight, the open-circuit voltage of the perovskite solar cell is 1.03V, and the current density of the perovskite solar cell is 7.21mAcm-2The fill factor is 51.3%, and the photoelectric conversion efficiency is 3.81%.
Example 3 addition of NH to perovskite precursor solution4Cl additive and hot air blowing during blade coating, comparative example 3-1 is adding NH to perovskite precursor solution4Cl additive and no hot air blowing during blade coating, comparative example 3-2 is perovskite precursor solution without NH4The photoelectric conversion efficiency of the perovskite solar cell prepared by the embodiment of the invention is obviously superior to that of the perovskite solar cell prepared by the comparative example as shown in FIG. 7, wherein the Cl additive is used for blade coating and hot air is used for blade coating.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (9)

1. A method for regulating and controlling a perovskite nucleation process is characterized by comprising the following steps: the perovskite comprises but is not limited to lead-based perovskite and multi-component perovskite with lead element as the leading B site, and solvated BX is regulated and controlled by adding additive AX into the prepared perovskite precursor solution2Formation rate and density of compounds and complexes thereof, control of solvated BX2Segregated crystallization of compounds and their complexes;
coating the perovskite precursor solution on a substrate by adopting a solution coating method, controlling the temperature and the volatilization rate of the local area of the solution, and controlling the solvated BX2Carrying out segregation crystallization on the compound and the compound thereof in different areas to obtain a perovskite thin film with good crystallinity and uniform appearance;
in the structural formula of the additive AX, A is NH4 +，CH3NH3 +，NH2CHNH2 +，CH3NH2CH3 +Any one of the above; x represents Cl-，Br-，I-，SCN-，CH3COO−Any one of the above;
the BX2In the compound, X is any one of I, Br and Cl, B is Pb or a multi-metal element composition taking Pb as a main component;
the regulation and control method for the perovskite nucleation process comprises the following steps:
(1) separately weighing PbI2And methyl ammonium iodide, dissolved in DMF solvent to obtain PbI2DMF solution, MAI/DMF solution;
(2) adding butylamine into the MAI/DMF solution obtained in the step (1) to obtain a mixed solution of methylammonium iodide and butylammonium iodide;
(3) weighing an additive AX, dissolving the additive AX in PbI obtained in the step (1)2Heating DMF solution until additive AX is completely dissolved, and controlling the molar ratio AX/PbI20.05 to 5;
(4) uniformly mixing the solutions prepared in the step (2) and the step (3), standing and aging to obtain a two-dimensional layered perovskite precursor solution with the structural formula of BA2MAn-1PbnI3n+1，n=4；
(5) Coating a two-dimensional perovskite precursor solution on a substrate by adopting a solution coating method, annealing, and controlling the temperature and volatilization rate of a local area of the solution to control the solvated PbI2And (3) performing segregation crystallization on the compound in different areas to induce segregation precipitation of the quasi-three-dimensional perovskite on the surface of the coating film, so as to obtain the two-dimensional perovskite film with good crystallinity and uniform appearance.
2. The method for regulating the perovskite nucleation process according to claim 1, wherein in step (1), the PbI is2The concentration of the/DMF solution is 400-600 mg/ml; the concentration of the MAI/DMF solution is 400-600 mg/ml.
3. The method for regulating and controlling the perovskite nucleation process according to claim 1, wherein in the step (2), the molar ratio of the butylammonium iodide to the methylammonium iodide is 2: (1-9).
4. The method for controlling a perovskite nucleation process according to claim 1, wherein in the step (3), the additive AX is NH4Cl。
5. A regulating method for the perovskite nucleation process according to claim 1, wherein in the step (5), the solution coating method comprises any one of a spin coating method, a blade coating method, a spray coating method, a slit coating method and a Czochralski method.
6. A regulating method for the perovskite nucleation process according to claim 5, wherein in the step (5), the perovskite thin film is prepared by a spin coating method: spin-coating the two-dimensional perovskite precursor solution on a substrate at the rotating speed of 4000-6000 rpm;
preparing a perovskite film by adopting a blade coating method: and (3) blade-coating the two-dimensional perovskite precursor solution on a substrate at the speed of 1-100 mm/s, wherein the film is blown by hot air in the blade-coating process, and segregation of the quasi-three-dimensional perovskite on the surface of the coated film is induced to be separated out.
7. The method for regulating the perovskite nucleation process according to any one of claims 1, 5 and 6, wherein in the step (5), the annealing treatment is: annealing at 50-80 ℃ for 0-10 min, and then annealing at 90-150 ℃ for 5-60 min.
8. A method for preparing a solar cell by a perovskite thin film is characterized by comprising the following steps:
s1, use of Sn-doped In2O3The conductive glass ITO is used as a device substrate;
s2. preparing a hole transport layer: using PEDOT: the PSS material is used as a hole transport layer and is coated on the ITO substrate after ultraviolet treatment in a spinning mode;
s3, preparing a two-dimensional perovskite thin film on the hole transport layer by adopting a solution coating method according to the regulation and control method of any one of claims 1-6;
s4, preparing an electron transport layer: preparing a fullerene derivative PCBM/chlorobenzene solution, spin-coating the fullerene derivative PCBM/chlorobenzene solution on a two-dimensional perovskite film, and drying the fullerene derivative PCBM/chlorobenzene solution;
s5. preparing a hole blocking layer: evaporating Bathocuproine on the electron transport layer by a vacuum thermal evaporation method;
s6, preparing a back electrode: and depositing copper on the hole blocking layer by a vacuum thermal evaporation method to obtain the perovskite thin film based solar cell.
9. The method for preparing a solar cell from the perovskite thin film as claimed in claim 8, wherein the conductive glass ITO has a specification of light transmittance in step S1>85% square resistance<10
Figure DEST_PATH_IMAGE001
And the size is 15mm by 15 mm.
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