CN114276353B - Synthetic method and application of hole transport material with polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as core - Google Patents
Synthetic method and application of hole transport material with polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as core Download PDFInfo
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Abstract
The invention belongs to the technical field of organic functional materials, and particularly discloses a synthesis method and application of a hole transport material taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core, and particularly application of the hole transport material to a perovskite solar cell. The hole transport material takes pyrrole- [3,2-b ] pyrrole as a core structure, fluorine substituted benzene is introduced into N position, and two ends are connected with N, N-dimethoxy aniline. The hole transport material has the characteristics of high thermal stability, low synthesis cost, high hole mobility, high conductivity and the like. The invention creates a novel core and has wide application prospect, and the hole transport material taking the polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as the core provides a novel choice for preparing the perovskite solar cell with high efficiency and stability in the aspect of the hole transport material.
Description
Technical Field
The invention belongs to the technical field of organic functional materials, and relates to a hole transport material taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core, a preparation method thereof and application thereof in perovskite solar cells.
Background
As an emerging solar cell technology, perovskite solar cells (Perovskite Solar Cell) have been developed particularly rapidly, and their photoelectric conversion efficiency has reached 25.5% only after no more than 10 years, and have been evaluated by Science journal as one of the ten Science findings in 2013. The perovskite solar cell has excellent photovoltaic performance, has low requirement on the purity of materials, and can be prepared by a simple solution method at room temperature, so that the production and preparation process is greatly simplified, and the manufacturing cost is reduced, thereby providing possibility for large-scale production and industrialization of the perovskite solar cell and having huge commercial application potential.
The traditional perovskite solar cell device consists of a conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode. And the hole transport layer plays a role in extracting and transporting holes injected in the perovskite layer in the perovskite solar cell. In a high-performance perovskite solar cell, the hole transport material needs to have the following conditions: matching with the energy band of perovskite, high hole mobility and conductivity, excellent film forming property, good light and heat stability and the like. Currently, the most efficient hole transport materials used in perovskite solar cells are poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) of the polymer type and small organic molecules to give 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (spira-ome tad), (F.Li, X.Deng, F.Qi, Z.Li, D.Liu, D.Shen, M.Qin, S.Wu, F.Lin, S.H.Jang, J.Zhang, X.Lu, D.Lei, C.S.Lee, Z.Zhu, A.K.Jen, J.Am.Chem.Soc.2020,142,20134-20142;J.Jeong,M.Kim,J.Seo,H.Lu,P.Ahlawat,A.Mishra,Y.Yang,M.A.Hope,F.T.Eickemeyer,M.Kim,Y.J.Yoon,I.W.Choi,B.P.Darwich,S.J.Choi,Y.Jo,J.H.Lee,B.Walker,S.M.Zakeeruddin,L.Emsley,U.Rothlisberger,A.Hagfeldt,D.S.Kim,M.Gratzel,J.Y.Kim,Nature 2021 ]), however, there are still many drawbacks with these two hole transport materials: complex synthesis and purification results in high price, high resistivity inherent to the material itself and low charge mobility. Therefore, to avoid these problems, dopants are often added to improve charge transport properties. However, commonly used dopants, such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), cobalt complexes, and Tertiary Butyl Pyridine (TBP), are inherently hygroscopic and volatile, which can accelerate device aging. Therefore, the development of the undoped hole transport material integrating the advantages of simple synthesis and purification, low cost, high stability, high film forming property, high hole mobility and the like is very important for commercialization of perovskite solar cells in the future.
In 2019, the Tang Weihua group reported that a semiconductor molecule with dithiophene [3,2-b:2',3' -d ] pyrrole as a core was applied as an undoped hole transport material to perovskite solar cells of a formal planar structure, and a high efficiency of 20.38% was obtained. In (J.Zhou, X.Yin, Z.Dong, A.Ali, Z.Song, N.Shrestha, S.S.Bista, Q.Bao, R.J.Ellingson, Y.Yan, W.Tang, angew.Chem.Int.Ed.Engl.2019,58, 13717-13721.) 2020, the She Xuan subject group introduced a tetraphenyl ethylene-based undoped hole transport material prepared by sulfur atoms, which was applied to perovskite solar cells of inverted planar structure, and obtained a high efficiency of 21.0%. (K.Jiang, J.Wang, F.Wu, Q.Xue, Q.Yao, J.Zhang, Y.Chen, G.Zhang, Z.Zhu, H.Yan, L.Zhu, H.L.Yip, adv.Mater.2020,32, e 1908011.) 2021, xu Baomin group reported that an undoped hole transporting material having a fluorine unit based on a conjugated group (2, 5-bis (4, 4-bis (methoxyphenyl) aminophenol-4-yl) -benzene, which was applied to a perovskite solar cell of an inverted planar structure, gave a high efficiency of 20.51% (J.Wu, M.Hu, L.Zhang, G.Song, Y.Li, W.Tan, Y.Tian, B.Xu, chem.Eng.J.2021,422.)
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to develop a hole transport material which is used for a perovskite solar cell and takes polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core, the material takes pyrrole- [3,2-b ] pyrrole as a core structure, fluorobenzene is introduced into N position, and meanwhile, two ends are connected with 4,4' -dimethoxy triphenylamine. The synthesized material has the characteristics of energy level matching, high thermal stability, low synthesis cost and high hole mobility. The invention not only can improve the photoelectric performance of the perovskite solar cell and enhance the stability of the cell, but also can reduce the manufacturing cost of the cell
The present invention achieves the above technical object by the following means.
A hole transport material with polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core is characterized in that: the organic micromolecular functional material is formed by taking pyrrole- [3,2-b ] pyrrole as a core structure, introducing an R group into an N position, and connecting 4,4' -dimethoxy triphenylamine at two ends. The hole transport material has the following chemical structural formula:
said polyfluoro-substituted pyrrole- [3,2-b]The synthesis method of the hole transport material taking pyrrole as a core comprises the following steps: NH (NH) 2 R and butanedione react with domino to obtain a compound 1; the compound 1 and 4,4' -dimethoxy diphenylamine undergo carbon-nitrogen coupling reaction to obtain the final product pyrrole- [3,2-b]Pyrrole compoundsThe fluorine-substituted hole transport materials 2FPPY,4FPPY and 6FPPY serving as cores comprise the following specific steps:
(i) Adding fluoroaniline NH into a dry reaction bottle 2 R, p-bromobenzaldehyde, p-toluenesulfonic acid and glacial acetic acid solvent, heating the reaction solution to 90-100 ℃, reacting for 30-60 min, then adding butanedione, continuing to react for 2-3h, cooling to room temperature after the reaction is finished, performing suction filtration to obtain a solid product, separating and purifying the obtained solid, and performing vacuum drying to obtain the compound 1.
(ii) Adding the compound 1, 4' -dimethoxy diphenylamine, palladium acetate, potassium tert-butoxide and toluene which are obtained in the step (i) into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, adding tri-tert-butyl phosphine, heating to 120-130 ℃, reacting for 12-15h, cooling to room temperature after the reaction is finished, extracting with dichloromethane for several times, collecting an organic layer, distilling under reduced pressure to remove the solvent, separating and purifying the obtained solid, and drying in vacuum to obtain the hole transport material taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core.
The synthesis flow is as follows:
in step (i), NH 2 R: p-bromobenzaldehyde: butanedione: the molar ratio of the p-toluenesulfonic acid is 1:1:0.5:0.1; the reaction concentration of the fluoroaniline is 0.15-0.2 mol/L.
In step (ii), compound 1:4,4' -dimethoxydiphenylamine: potassium tert-butoxide: tri-tert-butylphosphine: the molar ratio of palladium acetate is 1:2:3:0.1:0.05; the reaction concentration of the compound 1 is 0.25 to 0.3mol/L.
The hole transport material prepared by the invention and taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core is used as a hole transport layer for application in perovskite solar cells. The perovskite solar cell consists of a transparent conductive substrate, a hole transmission layer, a perovskite absorption layer, an electron transmission layer, a hole blocking layer and a metal electrode, and comprises the following specific steps:
(1) Cutting a transparent conductive substrate into fixed sizes, performing etching treatment, respectively ultrasonically cleaning the etched conductive substrate in different solvents, and then performing ultraviolet ozone sterilization treatment;
(2) Transferring the transparent conductive substrate treated in the step (1) into a glove box, and spin-coating a hole transport material solution taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core onto a perovskite absorption layer by a spin-coating method to form a hole transport layer;
(3) Spin-coating the perovskite precursor liquid on the hole transport layer by a spin-coating method to form a perovskite absorption layer;
(4) PC was applied by spin coating 61 Spin-coating BM solution on the perovskite absorption layer to form an electron transport layer;
(5) Spin-coating a Bath Copper (BCP) solution onto the electron transport layer to form a hole blocking layer;
(6) The metal electrode is deposited onto the hole transport layer by vacuum evaporation.
The transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a flexible substrate;
the hole transport material solution is prepared by dissolving 3-5 mg of hole transport material taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core in 1mL of chlorobenzene;
the perovskite precursor liquid is prepared by the following steps: NH is added to 3 CH 3 I and PbI 2 、PbCl 2 Or PbBr 2 Mixing and dissolving N, N-dimethylformamide with the volume ratio of 4:1 in a molar ratio of 3:1-1:1: in the mixed solution of dimethyl sulfoxide, stirring at room temperature to obtain CH 3 NH 3 PbI 3 、CH 3 NH 3 PbI 3-x Br x Or CH (CH) 3 NH 3 PbI 3-x Cl x Is a precursor liquid of (a);
the perovskite absorption layer is CH 3 NH 3 PbI 3 、CH 3 NH 3 PbI 3-x Br x Or CH (CH) 3 NH 3 PbI 3-x Cl x (0.ltoreq.x.ltoreq.3);
the electricity isSub-transport layer, PC 61 BM solution is prepared by mixing 15-30 mg of PC 61 BM is dissolved in 1mL of chlorobenzene;
the cavity blocking layer, the bathocuproine BCP solution is prepared by dissolving 0.5-1 mg of BCP in 1mL of isopropanol;
the metal electrode is one of gold, silver or copper.
The invention has the advantages that:
the hole transport material synthesized by the invention, which takes the polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as the core, has novel core structure, and has the advantages of simple synthesis, low cost, high thermal stability, high hole mobility, high conductivity and the like, compared with the traditional hole transport materials Spiro-OMeTAD and PTAA, which only need two steps of synthesis.
The perovskite solar cell based on the hole transport material taking the polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as the core has lower preparation cost, higher photoelectric conversion efficiency and better stability.
Drawings
Fig. 1 is a molecular structural formula of hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 of the present invention.
Fig. 2 a) is a graph showing conductivity test of the hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 according to the present invention; fig. 2 b) is a graph showing hole mobility test of the hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 according to the present invention.
Fig. 3 a) is a scanning electron microscope image of a cross section of a perovskite solar cell using compounds 2FPPY and 6FPPY synthesized as examples of the present invention as hole transport materials; b) J-V curves of perovskite solar cells using the compounds 2FPPY and 6FPPY synthesized in examples 1 and 2 of the present invention as hole transport materials; c) IPCE diagram of perovskite solar cell with 2FPPY and 6FPPY as hole transport materials; d) Efficiency stability test chart of perovskite solar cell using compound 2FPPY and compound 6FPPY synthesized in examples 1 and 2 of the present invention as hole transport material.
Detailed Description
The invention will be further described with reference to specific examples for a better understanding of the invention by those skilled in the art, but the scope of the invention is not limited thereto and the scope of the invention shall be determined by the claims.
Example 1:
synthesis of hole transport material 2FPPY and application thereof in perovskite solar cells:
(i) 4-fluoroaniline (1.11 g,10 mmol), p-bromobenzaldehyde (1.85 g,10 mmol), p-toluenesulfonic acid (0.172 g,1 mmol) and 75mL glacial acetic acid as solvent were added into a dry reaction bottle, the reaction solution was heated to 90 ℃ for 30min, butanedione (440 μl,5 mmol) was then added into a constant pressure dropping funnel, the reaction was continued for 2-3h, after the reaction was completed, cooled to room temperature, and filtered with 200mL glacial acetic acid under suction to obtain a solid product, the obtained solid was separated and purified by a silica gel chromatographic column, petroleum ether/dichloromethane (1:1 vol/vol) was used as eluent, and dried in vacuo to obtain pale yellow solid compound 1 (0.612 g, yield: 20.3%), which was dried in vacuo to obtain compound 1. 1 H NMR(400MHz,CDCl 3 )δ7.40–7.36(m,4H),7.25(ddd,J＝10.3,5.2,2.8Hz,4H),7.14–7.06(m,8H),6.36(s,2H).HR-MS:(ESI)m/z:C 30 H 18 Br 2 F 2 N 2 Calculated 601.9805, measured 601.9783.
(ii) In a dry reaction vessel, adding 1 (1.203 g,2 mmol), 4' -dimethoxy diphenylamine (0.917 g,4 mmol), palladium acetate (0.024 g,0.1 mmol), potassium tert-butoxide (0.673 g,6 mmol) and toluene (85 mL) as solvents, stirring under nitrogen protection and at room temperature for 5min, adding tri-tert-butyl phosphine (10% solution, 0.501g,0.2 mmol), heating to 120 ℃, reacting for 12-15h, cooling to room temperature after the reaction is finished, adding 20mL of water to quench the reaction, extracting three times with dichloromethane (150 mL×3), collecting an organic layer, adding anhydrous sodium sulfate to stir for 30min to remove water, distilling the solution under reduced pressure after suction filtration, separating and purifying the obtained solid by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (1.5:1 vol/vol) as eluent, and drying in vacuum to obtain yellow solid0.958g, yield: 53.2%) and vacuum drying to give pyrrole- [3,2-b ]]Pyrrole-core fluorine-substituted hole transport material 2FPPY. 1 H NMR(400MHz,DMSO)δ7.32–7.27(m,8H),6.99(dd,J＝12.4,8.9Hz,16H),6.90(d,J＝9.0Hz,8H),6.28(s,2H),3.74(d,J＝3.3Hz,12H).HR-MS:(ESI)m/z:C 58 H 46 F 2 N 4 O 4 Calculated 900.3487, measured 900.3484.
The synthesized hole transport material 2FPPY is applied to perovskite solar cells, and the preparation process is as follows:
the purchased ITO (indium tin oxide) conductive glass substrate (1.5 cm. Times.1.5 cm) was ultrasonically cleaned in deionized water, acetone and ethanol, respectively, for 20min, then placed in an ultraviolet ozone machine for 30min, and then the glass substrate was transferred to a glove box filled with nitrogen, and the subsequent operation steps were all completed in the glove box filled with nitrogen. A hole transport material 2FPPY solution (3 mg of 2FPPY dissolved in 1mL of chlorobenzene) was spin-coated on the ITO surface by spin-coating, the spin-coating time was 30s, and then annealed at 100℃for 10min, with a rotation speed of 2000 rpm. Lead iodide (PbI) 2 ) Lead formamidinate iodide (FAI), lead bromide (PbBr) 2 ) Methyl ammonia bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) under stirring at room temperature. The prepared 30. Mu.L of perovskite solution was spin-coated on a 2FPPY film using a spin coater, the spin-coating time was 10s at 1000rpm, the spin-coating time was 30s at 5000rpm, and 200. Mu.L of chlorobenzene was rapidly dropped onto the film during the spin-coating, and the perovskite film was annealed at 100℃for 30 minutes. Subsequently, the electron transporting material PC was applied by spin coating 61 BM solution (20 mg PC) 61 BM dissolved in 1mL chlorobenzene) was spin-coated onto the perovskite film surface at 2000rpm for 40s. Thereafter, hole blocking solution BCP (0.5 mg BCP was dissolved in 1mL isopropyl alcohol) was spin-coated on the surface of the electron transport layer by spin coating at 4000rpm for 30s. Finally 120nm Ag is deposited on the device film by a vacuum evaporation method.
Example 2:
synthesis of hole transport material 6FPPY and its application in perovskite solar cells:
(i) 3,4, 5-trifluoroaniline (1.471 g,10 mmol), p-bromobenzaldehyde (1.85 g,10 mmol), p-toluenesulfonic acid (0.172 g,1 mmol) and 75mL glacial acetic acid as solvent were added into a dry reaction bottle, the reaction solution was heated to 90 ℃ for 30min, butanedione (440 μl,5 mmol) was then added into a constant pressure dropping funnel, the reaction was slowly dropped, the reaction was continued for 2-3h, after the reaction was completed, cooled to room temperature, and filtered with 200mL glacial acetic acid under suction to obtain a solid product, the obtained solid was separated and purified by a silica gel chromatographic column, petroleum ether/dichloromethane (1:1 vol/vol) was used as eluent, and dried under vacuum to obtain pale yellow solid compound 1 (0.743 g, yield: 22.0%) which was dried under vacuum to obtain compound 1. 1 H NMR(400MHz,CDCl 3 )δ7.46(d,J＝8.4Hz,4H),7.09(d,J＝8.3Hz,4H),6.95–6.86(m,4H),6.40(s,2H).HR-MS:(ESI)m/z:C 30 H 14 Br 2 F 6 N 2 Calculated values: 673.9428, found: 673.9425.
(ii) In a dry reaction vessel, adding 1 (1.353 g,2 mmol), 4' -dimethoxydiphenylamine (0.917 g,4 mmol), palladium acetate (0.024 g,0.1 mmol), potassium tert-butoxide (0.673 g,6 mmol) and toluene (85 mL) as solvents, stirring under nitrogen protection and at room temperature for 5min, adding tri-tert-butylphosphine (10% solution, 0.501g,0.2 mmol), heating to 120deg.C, reacting for 12-15h, cooling to room temperature after the reaction is finished, adding 20mL of water to quench the reaction, extracting three times with dichloromethane (150 mL×3), collecting the organic layer, adding anhydrous sodium sulfate to stir for 30min, vacuum filtering, distilling the solution under reduced pressure, separating and purifying the obtained solid with silica gel chromatographic column, using petroleum ether/dichloromethane (1.5:1 vol/vol) as eluent, vacuum drying to obtain yellow solid (1.26 g, yield: 64.8%), and vacuum drying to obtain pyrrole- [3,2-b ]]Pyrrole-cored fluorine replaces hole transport material 6FPPY. 1 H NMR(400MHz,CDCl 3 )δ7.09(d,J＝8.5Hz,8H),7.05–6.90(m,8H),6.90–6.82(m,12H),6.32(s,2H),3.82(s,12H).HR-MS:(ESI)m/z:C 58 H 42 F 6 N 4 O 4 Calculated 972.3110, measured 972.3108.
The synthesized hole transport material 6FPPY is applied to a perovskite solar cell, and the preparation process comprises the following steps:
the purchased ITO (indium tin oxide) conductive glass substrate (1.5 cm. Times.1.5 cm) was ultrasonically cleaned in deionized water, acetone and ethanol, respectively, for 20min, then placed in an ultraviolet ozone machine for 30min, and then the glass substrate was transferred to a glove box filled with nitrogen, and the subsequent operation steps were all completed in the glove box filled with nitrogen. A hole transport material 6FPPY solution (3 mg of 6FPPY dissolved in 1mL of chlorobenzene) was spin-coated on the ITO surface by spin-coating, the spin-coating time was 30s, and then annealed at 100℃for 10min, with a rotation speed of 2000 rpm. Lead iodide (PbI) 2 ) Lead formamidinate iodide (FAI), lead bromide (PbBr) 2 ) Methyl ammonia bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) under stirring at room temperature. The prepared 30. Mu.L of perovskite solution was spin-coated on a 6FPPY film using a spin coater, the spin-coating time was 10s at 1000rpm, the spin-coating time was 30s at 5000rpm, 200. Mu.L of chlorobenzene was rapidly dropped onto the film during the spin-coating, and the perovskite film was annealed at 100℃for 30 minutes. Subsequently, the electron transporting material PC was applied by spin coating 61 BM solution (20 mg PC) 61 BM dissolved in 1mL chlorobenzene) was spin-coated onto the perovskite film surface at 2000rpm for 40s. Thereafter, hole blocking solution BCP (0.5 mg BCP was dissolved in 1mL isopropyl alcohol) was spin-coated on the surface of the electron transport layer by spin coating at 4000rpm for 30s. Finally 120nm Ag is deposited on the device film by a vacuum evaporation method.
Fig. 1 is a molecular structural formula of hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 of the present invention.
Fig. 2 a) is a graph showing conductivity test of the hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 according to the present invention; fig. 2 b) is a graph showing hole mobility test of the hole transport materials 2FPPY and 6FPPY synthesized in examples 1 and 2 according to the present invention. As can be seen from the figure, the hole transport material 6FPPY has higher hole mobility and conductivity.
Fig. 3 a) is a scanning electron microscope image of a cross section of a perovskite solar cell using the compounds 2FPPY and 6FPPY synthesized in examples 1 and 2 of the present invention as hole transport materials; b) In order to obtain J-V graphs of perovskite solar cells using the compound 2FPPY and 6FPPY synthesized in examples 1 and 2 of the present invention as hole transport materials, it can be seen that 13.8% (J) of the hole transport materials 2FPPY and 6FPPY, respectively, were obtained SC ＝19.9mA/cm -2 ，V OC =1.04 v, ff=66.7%) and 20.1% (J SC ＝23.7mA/cm -2 ，V OC =1.11v, ff=76.8%), it is apparent that the perovskite solar cell based on 6FPPY has higher photoelectric conversion efficiency; c) As can be seen from the IPCE graph of the perovskite solar cell using 2FPPY and 6FPPY as hole transport materials, the cell device using 2FPPY and 6FPPY as hole transport materials has higher photo-response in the whole spectrum of 300 to 800nm, and the integral J is calculated SC A value of 2FPPY of 21.75mA/cm -2 6FPPY of 23.51mA/cm -2 The data obtained by the actual experimental test are well matched; d) Efficiency stability test chart of perovskite solar cell using compound 2FPPY and compound 6FPPY synthesized in examples 1 and 2 of the present invention as hole transport material. As can be seen from the figure, the hole transport material 6FPPY has better stability than the hole transport material 2FPPY, and the original 78% photoelectric conversion efficiency is maintained after aging for 720 hours.
Claims (10)
1. The hole transport material is an organic small molecule functional material which is formed by taking pyrrole- [3,2-b ] pyrrole as a core structure, introducing an R group at the N position and connecting 4,4' -dimethoxy triphenylamine at two ends, and has the chemical structural formula as follows:
r: is that
2. A method for synthesizing a hole transport material based on a polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as defined in claim 1, comprising the steps of:
(i) Adding fluoroaniline NH into a dry reaction bottle 2 R, p-bromobenzaldehyde, p-toluenesulfonic acid and glacial acetic acid solvent, heating the reaction solution to 90-100 ℃, reacting for 30-60 min, then adding butanedione, continuing to react for 2-3h, cooling to room temperature after the reaction is finished, performing suction filtration to obtain a solid product, separating and purifying the obtained solid, and performing vacuum drying to obtain a compound 1;
(ii) Adding the compound 1, 4' -dimethoxy diphenylamine, palladium acetate, potassium tert-butoxide and toluene which are obtained in the step (i) into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, adding tri-tert-butyl phosphine, heating to 120-130 ℃, reacting for 12-15h, cooling to room temperature after the reaction is finished, extracting with dichloromethane for several times, collecting an organic layer, distilling under reduced pressure to remove the solvent, separating and purifying the obtained solid, and drying in vacuum to obtain the hole transport material taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core.
3. The method of claim 2, wherein in step (i), fluoroaniline NH is used 2 R: p-bromobenzaldehyde: butanedione: the molar ratio of the p-toluenesulfonic acid is 1:1:0.5:0.1; fluoroaniline NH 2 The reaction concentration of R is 0.15-0.2 mol/L.
4. The synthetic method of claim 2 wherein in step (ii), compound 1:4,4' -dimethoxydiphenylamine: potassium tert-butoxide: tri-tert-butylphosphine: the molar ratio of palladium acetate is 1:2:3:0.1:0.05; the reaction concentration of the compound 1 is 0.25 to 0.3mol/L.
5. Use of a hole transport material with polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as core according to claim 1 as hole transport layer in perovskite solar cells.
6. The use according to claim 5, wherein the perovskite solar cell is composed of a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, a hole blocking layer and a metal electrode, and the specific steps are as follows:
(1) Cutting a transparent conductive substrate into fixed sizes, performing etching treatment, respectively ultrasonically cleaning the etched conductive substrate in different solvents, and then performing ultraviolet ozone sterilization treatment;
(2) Transferring the transparent conductive substrate treated in the step (1) into a glove box, and spin-coating a hole transport material solution taking polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core onto a perovskite absorption layer by a spin-coating method to form a hole transport layer;
(3) Spin-coating the perovskite precursor liquid on the hole transport layer by a spin-coating method to form a perovskite absorption layer;
(4) PC was applied by spin coating 61 Spin-coating BM solution on the perovskite absorption layer to form an electron transport layer;
(5) Spin-coating a BCP solution of bathocuproine onto the electron transport layer to form a hole blocking layer;
(6) The metal electrode is deposited onto the hole transport layer by vacuum evaporation.
7. The use of claim 6, wherein in step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass, or a flexible substrate.
8. The use according to claim 6, wherein in step (2), the hole transporting material solution is prepared by dissolving 3 to 5mg of a hole transporting material having a polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as a core in 1mL of chlorobenzene.
9. The use according to claim 6, wherein in step (3), the perovskite precursor liquid is disposed by: NH is added to 3 CH 3 I and PbI 2 、PbCl 2 Or PbBr 2 Mixing and dissolving N, N-dimethylformamide with the volume ratio of 4:1 in a molar ratio of 3:1-1:1: in the mixed solution of dimethyl sulfoxide, stirring at room temperature to obtain CH 3 NH 3 PbI 3 、CH 3 NH 3 PbI 3- x Br x Or CH (CH) 3 NH 3 PbI 3-x Cl x Is a precursor liquid of (a);
the perovskite absorption layer is CH 3 NH 3 PbI 3 、CH 3 NH 3 PbI 3-x Br x Or CH (CH) 3 NH 3 PbI 3-x Cl x Wherein x is more than 0 and less than or equal to 3.
10. The use according to claim 6, wherein,
in the step (4), the electron transport layer, PC 61 BM solution is prepared by mixing 15-30 mg of PC 61 BM is dissolved in 1mL of chlorobenzene;
in the step (5), the hole blocking layer, the bathocuproine BCP solution is prepared by dissolving 0.5-1 mg of BCP in 1mL of isopropanol;
in the step (6), the metal electrode is one of gold, silver or copper.
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