CN110408009B - Hole transport layer for improving stability of perovskite solar cell and preparation method thereof - Google Patents

Hole transport layer for improving stability of perovskite solar cell and preparation method thereof Download PDF

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CN110408009B
CN110408009B CN201910640111.1A CN201910640111A CN110408009B CN 110408009 B CN110408009 B CN 110408009B CN 201910640111 A CN201910640111 A CN 201910640111A CN 110408009 B CN110408009 B CN 110408009B
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李坚
贾正
任强
汪称意
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Changzhou University
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Abstract

The invention belongs to the technical field of solar cells, and particularly relates to a hole transport layer for improving the stability of a perovskite solar cell and a preparation method thereof. The invention adopts Suzuki coupling reaction to synthesize the fluorine-containing triphenylamine copolymer. And dissolving the prepared fluorine-containing triphenylamine copolymer in chlorobenzene to obtain a fluorine-containing triphenylamine copolymer solution, and spin-coating the fluorine-containing triphenylamine copolymer solution serving as a hole transport material on an active layer perovskite layer of a solar cell device to obtain a hole transport layer with the thickness of 1-500 nm. Compared with the common hole transport layer material, the hole transport layer material provided by the invention can obviously improve the stability of the titanium ore solar cell.

Description

Hole transport layer for improving stability of perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a hole transport layer for improving the stability of a perovskite solar cell and a preparation method thereof.
Background
Since 2009 organic-inorganic hybrid perovskite materials were first used in the field of photovoltaics, perovskite solar cells based on such materials have attracted great attention, because perovskite solar cells have low cost and high energy conversion efficiency, completing a leap that other types of solar cells could have been completed for decades. At present, although the photoelectric conversion efficiency of the perovskite solar cell has been greatly improved after the development of the perovskite solar cell in the last decade, the poor stability of the perovskite solar cell, especially the poor moisture stability of the perovskite material, seriously hinders the commercialization of the perovskite solar cell. Therefore, the research on the material capable of improving the stability of the perovskite solar cell is of great significance.
To improve the stability of perovskite solar cells, Michael
Figure BDA0002131566540000011
Et al have studied mixed cation perovskite systems, using MA+、FA+And Cs+Three cations are prepared into the Cs with the mesoporous structure by a one-step spin coating methodx(MA0.17FA0.83)(100-x)Pb(I0.83Br0.17)3Perovskite solar cells, achieving a high efficiency of 21.1% and in stability tests it was found that the cells still maintain a photoelectric conversion efficiency of around 18% after 250 hours (Michael S, taisuuke M, Ji-young S&Environmental Science,6(2016) (1989) -1997). The stability of the battery is improved by changing cations in the perovskite active layer. Kijung Yong et al protected the perovskite material with a polytetrafluoroethylene hydrophobic material, the fabricated device exhibited good stability to water, and tests found that after 30 days, the device still had 90% of the initial efficiency, but the polytetrafluoroethylene hydrophobic material served as a packaging material (Passivation) therein to improve its stability rather than as part of the perovskite solar cell, and did not fundamentally solve the stability problem. (Hwang I, Jeong I, Lee J. ACS Applied Materials&Interfaces,31(2015):17330-17336.)。
Disclosure of Invention
The technical problems to be solved by the invention are as follows: a hole transport layer for improving the stability of a perovskite solar cell and a preparation method thereof are provided.
The fluorine-containing triphenylamine copolymer is synthesized by adopting Suzuki coupling reaction and is applied to a hole transport layer of the perovskite solar cell. The fluorine-containing triphenylamine copolymer hole transport layer can effectively improve the stability of the perovskite solar cell.
The invention is realized by the following technical scheme:
a hole transport layer for improving the stability of a perovskite solar cell adopts a fluorine-containing triphenylamine copolymer, and has the following structural characteristics:
Figure BDA0002131566540000021
in the formula RaSelected from hydrogen atoms, C1～C4Saturated alkane of (2)Or one or more of unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl; rbSelected from the group consisting of hexafluorobutyl propionate, dodecafluoroheptyl propionate, tridecafluoroctyl propionate, trifluoroethyl methylpropionate, hexafluorobutyl methylpropionate, dodecafluoroheptyl methylpropionate, and tridecafluoroctyl methylpropionate; x is 0.01-0.99, and molecular weight is 1000-100000.
The fluorine-containing triphenylamine copolymer provided by the invention is used as a hole transport layer to prepare a perovskite solar cell device, the prepared perovskite solar cell device sequentially comprises a cathode layer, an electron transport layer, a perovskite photoactive layer, a hole transport layer and an anode layer from bottom to top, and the structure is as follows:
anode layer
Hole transport layer
Perovskite photoactive layer
Electron transport layer
Cathode layer
Wherein the cathode layer is one of etched ITO glass, FTO glass and AZO glass; the electron transport layer is compact TiO2A material; the perovskite photoactive layer is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3In the preparation of the perovskite layer, the solution method is adopted, refer to the process of preparing a perovskite layer by Anaraki et al (Anaraki E H, Kermanpur A, Steier L&Environmental Science, 10 (2016): 3128-; the anode is evaporated silver, gold orAluminum is used.
The hole transport layer is made of a fluorine-containing triphenylamine copolymer, and the thickness of the hole transport layer is 1-500 nm, preferably 3-20 nm.
Further, the preparation of the fluorine-containing triphenylamine copolymer is carried out according to the following steps:
(1) preparation of dibromo fluorine-containing fluorene monomer:
adding 2, 7-dibromofluorene, a phase transfer catalyst and a solvent into a reactor, injecting an alkali solution under the nitrogen atmosphere, reacting for 10-60 min, then using an ice water bath, dropwise adding fluorine-containing acrylate after the temperature of the system is constant, reacting for 10-60 min, heating to 15-40 ℃, and continuing to react for 5-24 h. After the reaction, the reaction solution was poured into a separatory funnel, diluted with an appropriate amount of solvent, and the organic layer was washed with saturated brine several times until the aqueous layer was clear and transparent. With anhydrous MgSO4Drying the organic layer, filtering to obtain a clear and transparent organic solution, evaporating the solvent to dryness by using a rotary evaporator, and purifying by column chromatography to obtain the product.
The phase transfer catalyst is an organic quaternary ammonium salt, and is specifically selected from one or more of tetramethylammonium chloride, tetrabutylammonium diacetate, methyltriethylammonium chloride, tetraethylammonium bromide, tetraethylammonium fluoroborate, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetrabutylammonium fluoroborate, tetrabutylammonium fluoride, tetrabutylammonium bromide, benzyltrimethylammonium chloride, hexadecyltrimethylammonium bromide or benzyltriethylammonium chloride. The dosage of the compound is 0.1 to 10 times of the weight of the 2, 7-dibromofluorene.
The solvent is an organic solvent, is specifically selected from one or more of toluene, xylene, dichloromethane, dichloroethane, chloroform, ethyl acetate, butyl acetate and benzene, and is 0.1-50 times of the weight of the 2, 7-dibromofluorene.
The alkali solution is organic or inorganic alkali solution, and is selected from one or more of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, barium hydroxide and ammonium hydroxide aqueous solution with the mass fraction of 10-90%. The dosage of the compound is 1 to 500 percent of the weight of the 2, 7-dibromofluorene.
The fluorine-containing acrylate is selected from one or more of hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl acrylate, perfluoroalkyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluorooctyl methacrylate and perfluoroalkyl methacrylate. The dosage of the compound is 1 to 50 times of the mole number of the 2, 7-dibromofluorene.
(2) Synthesis of fluorine-containing triphenylamine copolymer:
adding a dibromo fluorine-containing fluorene monomer, a diboronic acid ester, a dibromo compound, a catalyst, a ligand, a weak base and a solvent into a reactor, heating to 85-95 ℃ in a nitrogen atmosphere, reacting for 12-24 h, adding phenylboronic acid, reacting for 2-3 h, finally adding bromobenzene, and reacting for 2-3 h. After the reaction is finished, precipitating the reaction solution by using absolute methanol, filtering and drying, purifying the obtained crude product by column chromatography, concentrating the purified product solution by using a rotary evaporation instrument, precipitating again, filtering and drying the product.
The dibromo fluorine-containing fluorene monomer is one or more selected from the group consisting of 2, 7-dibromo-9, 9-bis (hexafluorobutylpropionate) fluorene, 2, 7-dibromo-9, 9-bis (dodecafluoroheptylpropionate) fluorene, 2, 7-dibromo-9, 9-bis (tridecafluorooctyl propionate) fluorene, 2, 7-dibromo-9, 9-bis (trifluoroethyl methylpropionate) fluorene, 2, 7-dibromo-9, 9-bis (hexafluorobutylpropionate) fluorene, 2, 7-dibromo-9, 9-bis (dodecafluoroheptylacrylate) fluorene and 2, 7-dibromo-9, 9-bis (tridecafluorooctyl methylpropionate) fluorene.
A diboronate ester having the formula:
Figure BDA0002131566540000051
wherein R is2Selected from hydrogen atoms, C1～C8One or more of saturated alkane or unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl.
The dibromo compound has the structural formula:
Figure BDA0002131566540000052
wherein R is3Selected from hydrogen atoms, C1～C8One or more of saturated alkane or unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl.
The ratio of the total mole number of the dibromo fluorine-containing fluorene monomer and the dibromo product to the mole number of the diboronic acid ester product is 0.5: 1-1: 1.5. The molar ratio of the dibromo fluorine-containing fluorene monomer to the dibromo-compound is 1: 100-100: 0.
The catalyst is palladium catalyst selected from Pd (OAc)2、PdCl2(dppf) or Pd (PPh)3)4One or more of the above; the dosage of the fluorine-containing.
The ligand is selected from one or more of tricyclohexylphosphine fluoborate, tripyrrolidinphosphine, triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine or triethylene diamine; the molar ratio of the ligand to the catalyst is 0.1: 1-50: 1.
The weak base is selected from one or more of tetramethyl ammonium hydroxide aqueous solution, tetraethyl ammonium hydroxide aqueous solution, tetrapropyl ammonium hydroxide aqueous solution, tetrabutyl ammonium hydroxide aqueous solution, tetrahexyl ammonium hydroxide aqueous solution, tetraoctyl ammonium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution or potassium acetate aqueous solution with the mass fraction of 5-50%; the ratio of the mole number of the weak base to the total mole number of the dibromo fluorine-containing fluorene monomer, the diboronic acid ester substance and the dibromo substance is 0.1: 1-50: 1.
The solvent is one or more of toluene, xylene, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP).
The dosage of the phenylboronic acid and the bromobenzene is 0.1-1 of the total mole number of the dibromo fluorine-containing fluorene monomer, the diboronate ester and the dibromo product.
The preparation method of the hole transport layer for improving the stability of the perovskite solar cell comprises the following steps: dissolving the fluorine-containing triphenylamine copolymer in chlorobenzene to obtain a fluorine-containing triphenylamine copolymer solution with the concentration of 0.1-50 mg/mL, and then spin-coating the fluorine-containing triphenylamine copolymer solution on a perovskite layer to obtain a hole transport layer with the thickness of 1-500 nm.
Has the advantages that:
the invention provides a hole transport layer for improving the stability of a perovskite solar cell and a preparation method thereof. Compared with a common hole transport layer, the hole transport layer material provided by the invention can obviously improve the stability of the titanium ore solar cell.
Drawings
FIG. 1 is a nuclear magnetic diagram of poly [ 4-tert-butyl triphenylamine-co-9, 9-bis (hexafluorobutyl propionate) fluorene ] prepared in example 4;
FIG. 2 is a graph comparing the stability of perovskite solar cell devices.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
Example 1
Preparation of fluorine-containing fluorene monomer, 2, 7-dibromo-9, 9-bis (hexafluorobutyl propionate) fluorene:
after a magnetic stirrer was placed in a 100mL three-necked flask equipped with a thermometer, 3.3g (10.2mmol) of 2, 7-dibromofluorene, 0.25g (0.78mmol) of tetrabutylammonium bromide and 25mL of toluene were sequentially added, vacuum was applied and nitrogen gas was introduced, an atmosphere of nitrogen gas was maintained, and then 5mL of a 50% by mass aqueous solution of potassium hydroxide was slowly dropped by a syringe. After magnetic stirring for about 30min, an ice-water bath was used, and 9.676g (41mmol) of hexafluorobutyl acrylate was added dropwise with a syringe after the temperature of the reaction system was constant. After the hexafluorobutyl acrylate is added dropwise, stirring is continued for about 1h, and the temperature is raised to 25 ℃ for reaction for 6 h. After the reaction is finished, pouring the reaction solution into a separating funnel, adding a proper amount of toluene for dilution, and washing and separating for multiple times until a water layer is clear and transparent. With anhydrous MgSO4Drying the organic layer, filtering to obtain clear transparent solution, evaporating solvent toluene with rotary evaporator, and purifying by column chromatography (stationary phase is silica gel, mobile phase is mixture of dichloromethane and petroleum ether)Solvent) to obtain a brown yellow product after rotary evaporation. The NMR chart is shown in figure 1, and the yield is 41%.
Example 2
Preparation of fluorine-containing fluorene monomer, 2, 7-dibromo-9, 9-bis (dodecafluoroheptyl propionate) fluorene:
after a magnetic stirrer was placed in a 100mL three-necked flask equipped with a thermometer, 3.3g (10.2mmol) of 2, 7-dibromofluorene, 0.16g (0.78mmol) of tetraethylammonium bromide and 25mL of dichloroethane were sequentially added, and vacuum evacuation was performed by introducing nitrogen gas while maintaining the nitrogen gas atmosphere, and then 5mL of a 50% by mass aqueous sodium hydroxide solution was slowly dropped by a syringe. After magnetic stirring for about 30min, an ice-water bath was used, and 15.832g (41mmol) of dodecafluoroheptyl acrylate was added dropwise with a syringe after the temperature of the reaction system was constant. After the addition of the dodecafluoroheptyl acrylate, the mixture is continuously stirred for about 1 hour, and the temperature is increased to 30 ℃ for reaction for 8 hours. After the reaction is finished, pouring the reaction solution into a separating funnel, adding a proper amount of dichloroethane for dilution, and washing and separating for multiple times until a water layer is clear and transparent. With anhydrous MgSO4Drying the organic layer, filtering to obtain clear and transparent solution, evaporating dichloroethane to dryness by using a rotary evaporator, purifying by column chromatography (the stationary phase is silica gel, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether), and performing rotary evaporation to obtain a brown yellow product. The yield was 21%.
Example 3
Preparation of fluorine-containing fluorene monomer, 2, 7-dibromo-9, 9-bis (tridecafluorooctyl propionate) fluorene:
after a magnetic stirrer was placed in a 100mL three-necked flask equipped with a thermometer, 3.3g (10.2mmol) of 2, 7-dibromofluorene, 0.21g (0.78mmol) of tetrapropylammonium bromide and 25mL of chloroform were sequentially added thereto, and vacuum evacuation was performed by introducing nitrogen gas while maintaining the nitrogen gas atmosphere, and then 5mL of a 50% by mass aqueous potassium hydroxide solution was slowly dropped by using a syringe. After magnetic stirring for about 30min, using an ice water bath, 17.138g (41mmol) of tridecyl octyl acrylate was added dropwise with a syringe after the temperature of the reaction system was constant. After the dropwise addition of the tridecyl octyl acrylate, the mixture is continuously stirred for about 1 hour, and the temperature is increased to 30 ℃ for reaction for 10 hours. After the reaction is finished, pouring the reaction solution into a separating funnel, adding a proper amount of chloroform for dilution, and washing and separating for multiple times until a water layer is clear and transparent. With anhydrous MgSO4Drying the organic layerFiltering to obtain clear and transparent solution, evaporating chloroform solvent to dryness by using a rotary evaporator, purifying by column chromatography (the stationary phase is silica gel, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether), and performing rotary evaporation to obtain a brown yellow product. The yield was 36%.
Example 4
Preparation of [ 4-tert-butyl triphenylamine-co-9, 9-di (hexafluorobutylpropionate) fluorene ] copolymer
After a 100mL flask with thermometer was charged with a magnetic stirrer, 0.2767g (0.5mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -tert-butyltriphenylamine, 0.3981g (0.5mmol) of 2, 7-dibromo-9, 9-bis (hexafluorobutylpropionate) fluorene, 0.0034g (0.015mmol) of Pd (OAc)2、0.0221g(0.06mmol)P(Cy)38mL of TEAOH aqueous solution with the mass fraction of 25% and 8mL of toluene are vacuumized, nitrogen is introduced, the reaction is carried out at 90 ℃ for 24 hours, light blue fluorescence appears in the solution, and the system is reddish brown. Then 0.061g of phenylboronic acid is added to react for 3 hours, and then 62 mu L of bromobenzene is added to carry out end capping, and the reaction is continued for 3 hours. After the reaction is finished, the temperature of the reaction liquid is cooled to room temperature, methanol is used for precipitation, then filtration and drying are carried out, and the obtained product is purified by column chromatography (the stationary phase is silica gel, and the mobile phase is toluene). Concentrating the filtrate obtained by chromatography by using a rotary evaporator, then precipitating by using methanol again, filtering and drying to obtain reddish copolymer. The yield was 76%. The nuclear magnetic diagram is shown in figure 1.
Example 5
Preparation of [ 4-tert-butyl triphenylamine-co-9, 9-bis (dodecafluoroheptyl propionate) fluorene ] copolymer
In a 100mL three-necked flask equipped with a thermometer and a magnetic stirrer were charged 0.0551g (0.12mmol) of 4,4 '-dibromo-4' -t-butyltriphenylamine, 0.3320g (0.6mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -t-butyltriphenylamine, 0.5262g (0.48mmol) of 2, 7-dibromo-9, 9-bis (dodecafluoroheptyl propionate) fluorene, 0.004g (0.018mmol) of Pd (OAc)20.0134g (0.12mmol) of DABCO, 8mL of 25% tetraethylammonium hydroxide aqueous solution by mass and 8mL of toluene are uniformly stirred. Vacuumizing, introducing nitrogen, and reacting at constant temperature of 90 ℃ for 12 hours. Finally 0.0732g (0.6mmol) were addedThe phenylboronic acid was reacted for 3h, and 0.0942g (0.6mmol) of bromobenzene was added thereto and reacted for 3 h. After the reaction is finished, the reaction solution is precipitated by absolute methanol, filtered and dried, and then the crude product is purified by silica gel column chromatography to obtain a reddish polymer. The yield was 77%.
Example 6
Preparation of [ 4-trifluoromethyl triphenylamine-co-9, 9-di (hexafluorobutyl propionate) fluorene ] copolymer
After a 100mL flask with thermometer was charged with a magnetic stirrer, 0.2826g (0.5mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -trifluoromethyltriphenylamine, 0.3981g (0.5mmol) of 2, 7-dibromo-9, 9-bis (hexafluorobutylpropionate) fluorene, 0.0034g (0.015mmol) of Pd (OAc)2、0.0221g(0.06mmol)P(Cy)38mL of a 25% TEAOH aqueous solution and 8mL of toluene were reacted at 90 ℃ for 24 hours under vacuum with nitrogen gas. Then 0.061g of phenylboronic acid is added to react for 3 hours, and then 62 mu L of bromobenzene is added to carry out end capping, and the reaction is continued for 3 hours. After the reaction is finished, the temperature of the reaction liquid is cooled to room temperature, methanol is used for precipitation, then filtration and drying are carried out, and the obtained product is purified by column chromatography (the stationary phase is silica gel, and the mobile phase is toluene). Concentrating the filtrate obtained by chromatography by using a rotary evaporator, then precipitating by using methanol again, filtering and drying to obtain a reddish product. The yield was 68%.
Example 7
Preparation of [ 4-tert-butyl triphenylamine-co-9, 9-bis (hexafluorobutylpropionate) fluorene (1%) ] copolymer
A100 mL flask equipped with a thermometer was charged with a magnetic stirrer, and 0.2767g (0.5mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -tert-butyl triphenylamine, 0.008g (0.01mmol) of 2, 7-dibromo-9, 9-bis (hexafluorobutylpropionate) fluorene, 0.225g (0.49mmol) of 4,4 '-dibromo-4' -tert-butyl triphenylamine, 0.0034g (0.015mmol) of Pd (OAc)2、0.0221g(0.06mmol)P(Cy)38mL of tetramethyl ammonium hydroxide aqueous solution with the mass fraction of 30% and 8mL of DMF, vacuumizing, introducing nitrogen, reacting at 90 ℃ for 24 hours, wherein the solution has light blue fluorescence and is reddish brown. Then 0.061g of phenylboronic acid was added,and reacting for 3h, then adding 62 mu L of bromobenzene for end capping, and continuing to react for 3 h. After the reaction is finished, the temperature of the reaction liquid is cooled to room temperature, methanol is used for precipitation, then filtration and drying are carried out, and the obtained product is purified by column chromatography (the stationary phase is silica gel, and the mobile phase is toluene). Concentrating the filtrate obtained by chromatography by using a rotary evaporator, then precipitating by using methanol again, filtering and drying to obtain reddish copolymer. The yield was 85%.
Example 8
Preparation of [ 4-tert-butyl triphenylamine-co-9, 9-bis (tridecafluorooctyl propionate) fluorene ] copolymer
After a 100mL flask with thermometer was charged with a magnetic stirrer, 0.2767g (0.5mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -tert-butyltriphenylamine, 0.5641g (0.5mmol) of 2, 7-dibromo-9, 9-bis (tridecafluorooctanyl propionate) fluorene, 0.0034g (0.015mmol) of Pd (OAc)2、0.0221g(0.06mmol)P(Cy)38mL of TEAOH aqueous solution with the mass fraction of 25% and 8mL of toluene are vacuumized, nitrogen is introduced, the reaction is carried out at 90 ℃ for 24 hours, light blue fluorescence appears in the solution, and the system is reddish brown. Then 0.061g of phenylboronic acid is added to react for 3 hours, and then 62 mu L of bromobenzene is added to carry out end capping, and the reaction is continued for 3 hours. After the reaction is finished, the temperature of the reaction liquid is cooled to room temperature, methanol is used for precipitation, then filtration and drying are carried out, and the obtained product is purified by column chromatography (the stationary phase is silica gel, and the mobile phase is toluene). Concentrating the filtrate obtained by chromatography by using a rotary evaporator, then precipitating by using methanol again, filtering and drying to obtain reddish copolymer. The yield was 80%.
Comparative example 1
Preparation of poly (4-tert-butyl triphenylamine)
After a 100mL flask with thermometer was charged with a magnetic stirrer, 0.2767g (0.5mmol) of 4,4 '-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-diyl) -4' -tert-butyltriphenylamine, 0.459g (0.5mmol) of 4,4 '-dibromo-4' -tert-butyltriphenylamine, 0.0034g (0.015mmol) of Pd (OAc)2、0.0221g(0.06mmol)P(Cy)38mL of tetramethyl ammonium hydroxide aqueous solution with the mass fraction of 30% and 8mL of DMF, vacuumizing and introducing nitrogen at 90 DEG CAfter 24h reaction, the solution showed light blue fluorescence and the system was reddish brown. Then 0.061g of phenylboronic acid is added to react for 3 hours, and then 62 mu L of bromobenzene is added to carry out end capping, and the reaction is continued for 3 hours. After the reaction is finished, the temperature of the reaction liquid is cooled to room temperature, methanol is used for precipitation, then filtration and drying are carried out, and the obtained product is purified by column chromatography (the stationary phase is silica gel, and the mobile phase is toluene). And (3) concentrating the filtrate obtained by chromatography by using a rotary evaporator, then precipitating by using methanol again, filtering and drying to obtain a yellow copolymer. The yield was 88%.
Example 9
The perovskite solar cell was prepared using the [ 4-tert-butyl triphenylamine-co-9, 9-bis (hexafluorobutyl propionate) fluorene ] copolymer synthesized in example 4 as a hole transport layer:
sequentially and ultrasonically cleaning FTO conductive glass with the thickness of 1.5cm multiplied by 2.5cm by using a detergent, distilled water, acetone, isopropanol and absolute ethyl alcohol for 30min, and removing impurities on the surface of the FTO conductive glass. And after cleaning, blowing the FTO conductive glass by using nitrogen, cleaning the surface of the FTO conductive glass for 15min by using an oxygen plasma cleaning machine, and performing subsequent operation after treatment.
The cleaned FTO conductive glass was immersed in 200mM TiCl4Reacting in water solution at 70 ℃ for 1h, taking out a sample after the reaction is finished, washing the sample with deionized water and absolute ethyl alcohol, and removing TiO attached to the FTO conductive glass2The aqueous solution was then dried by heating in a muffle furnace at 100 ℃ for 1 h. Preparing a perovskite precursor solution in advance, then carrying out spin coating by adopting the processes of 1000rpm 10s and 6000rpm 20s, and dropwise adding chlorobenzene 5s before finishing to promote perovskite crystallization. And after the spin coating is finished, annealing the perovskite thin film on a heating base station at the temperature of 100 ℃ for 45min to obtain the black, bright, compact and uniform perovskite thin film.
Preparing a perovskite solar cell hole transport layer: weighing a certain amount of [ 4-tert-butyl triphenylamine-co-9, 9-di (hexafluorobutyl propionate) fluorene]The copolymer was dissolved in chlorobenzene and stirred well. Spin coating prepared [ 4-tert-butyl triphenylamine-co-9, 9-bis (hexafluorobutyl propionate) fluorene on the perovskite layer]The copolymer solution was spin-coated at 3000rpm for 30 s.Depositing Au on the hole transport layer by thermal evaporation at a deposition thickness of 80nm and an evaporation rate of
Figure BDA0002131566540000121
The effective area of the device is 0.07cm2。
Example 10
The perovskite solar cell was prepared using the [ 4-tert-butyl triphenylamine-co-9, 9-bis (dodecafluoroheptyl propionate) fluorene ] copolymer synthesized in example 5 as a hole transport layer:
otherwise, the same procedure as in example 9 was repeated.
Example 11
A perovskite solar cell was prepared using the [ 4-tert-butyl triphenylamine-co-9, 9-bis (tridecafluorooctyl propionate) fluorene ] copolymer synthesized in example 8 as a hole transport layer:
otherwise, the same procedure as in example 9 was repeated.
Comparative example 2
The perovskite solar cell is prepared by taking the poly [ 4-tert-butyl triphenylamine ] synthesized in the comparative example 1 as a hole transport layer:
sequentially and ultrasonically cleaning FTO conductive glass with the thickness of 1.5cm multiplied by 2.5cm by using a detergent, distilled water, acetone, isopropanol and absolute ethyl alcohol for 30min, and removing impurities on the surface of the FTO conductive glass. And after cleaning, blowing the FTO conductive glass by using nitrogen, cleaning the surface of the FTO conductive glass for 15min by using an oxygen plasma cleaning machine, and performing subsequent operation after treatment.
The cleaned FTO conductive glass was immersed in 200mM TiCl4Reacting in water solution at 70 ℃ for 1h, taking out a sample after the reaction is finished, washing the sample with deionized water and absolute ethyl alcohol, and removing TiO attached to the FTO conductive glass2The aqueous solution was then dried by heating in a muffle furnace at 100 ℃ for 1 h. Preparing a perovskite precursor solution in advance, then carrying out spin coating by adopting the processes of 1000rpm 10s and 6000rpm 20s, and dropwise adding chlorobenzene 5s before finishing to promote perovskite crystallization. And after the spin coating is finished, annealing the perovskite thin film on a heating base station at the temperature of 100 ℃ for 45min to obtain the black, bright, compact and uniform perovskite thin film.
Preparation of perovskite solar energyCell hole transport layer: weighing a certain amount of poly [ 4-tert-butyl triphenylamine]Dissolving in chlorobenzene, and stirring. Spin coating prepared poly [ 4-tert-butyl triphenylamine on perovskite layer]The solution, the spin coating process conditions were 3000rpm, the spin coating time was 30 s. Depositing Au on the hole transport layer by thermal evaporation at a deposition thickness of 80nm and an evaporation rate of
Figure BDA0002131566540000132
The effective area of the device is 0.07cm2。
The performance parameters are shown in Table 1, and the stability is shown in FIG. 2.
TABLE 1 perovskite solar cell Performance
Figure BDA0002131566540000131
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A hole transport layer for improving the stability of a perovskite solar cell, characterized by: the hole transport layer is made of a fluorine-containing triphenylamine copolymer;
wherein, the structure of the fluorine-containing triphenylamine copolymer is as follows:
Figure FDA0003123325100000011
in the formula RaSelected from hydrogen atoms, C1～C4One or more of saturated alkyl or unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl; rbSelected from hexafluorobutylpropionate, dodecafluoroheptylpropionate, tridecafluorooctyl propionate, trifluoroethyl methylpropionateA hexafluorobutylmethacrylate group, a dodecafluoroheptylate group or a tridecafluorooctymethacrylate group; the value of X is 0.01-0.99; the molecular weight is 1000-100000.
2. The hole transport layer for improving the stability of a perovskite solar cell as claimed in claim 1, wherein: the preparation method of the fluorine-containing triphenylamine copolymer comprises the following steps:
(1) preparation of dibromo fluorine-containing fluorene monomer:
adding 2, 7-dibromofluorene, a phase transfer catalyst and a solvent into a reactor, injecting an alkali solution under the atmosphere of nitrogen, reacting for 10-60 min, then using an ice water bath, dropwise adding fluorine-containing acrylate after the temperature of the system is constant, reacting for 10-60 min, heating to 15-40 ℃, continuing to react for 5-24 h, pouring the reaction solution into a separating funnel after the reaction is finished, adding the solvent for dilution, washing an organic layer with saturated salt solution until a water layer is clear and transparent, and using anhydrous MgSO (MgSO)4Drying the organic layer, filtering to obtain a clear and transparent organic solution, evaporating the solvent to dryness by using a rotary evaporator, and purifying by column chromatography to obtain a product;
(2) synthesis of fluorine-containing triphenylamine copolymer:
adding a dibromo fluorine-containing fluorene monomer, a diboronic acid ester substance, a dibromo-compound, a catalyst, a ligand, a weak base and a solvent into a reactor, heating to 85-95 ℃ in a nitrogen atmosphere, reacting for 12-24 h, adding phenylboronic acid, reacting for 2-3 h, finally adding bromobenzene, reacting for 2-3 h, after the reaction is finished, precipitating the reaction liquid with anhydrous methanol, filtering and drying, purifying the obtained crude product through column chromatography, concentrating the purified product solution with a rotary evaporation instrument, precipitating again, filtering and drying the product;
the diboronic acid ester is triphenylamine diborate, and the structural formula of the diboronic acid ester is as follows:
Figure FDA0003123325100000021
wherein R is2Selected from hydrogen atoms, C1～C8One or more of saturated alkyl or unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl;
the dibromide is triphenylamine dibromide, and the structural formula of the dibromide is as follows:
Figure FDA0003123325100000022
wherein R is3Selected from hydrogen atoms, C1～C8One or more of saturated alkyl or unsaturated alkyl, methoxyl, ethoxyl, fluorine atom and trifluoromethyl.
3. The hole transport layer for improving the stability of a perovskite solar cell as claimed in claim 2, wherein: the phase transfer catalyst in the step (1) is organic quaternary ammonium salt, and the dosage of the organic quaternary ammonium salt is 0.1-10 times of the weight of 2, 7-dibromofluorene; the solvent is an organic solvent, and the dosage of the organic solvent is 0.1-50 times of the weight of the 2, 7-dibromofluorene; the alkaline solution is organic or inorganic alkaline solution, and the dosage of the alkaline solution is 1 to 500 percent of the weight of the 2, 7-dibromofluorene; the dosage of the fluorine-containing acrylate is 1-50 times of the mole number of the 2, 7-dibromofluorene.
4. The hole transport layer for improving the stability of a perovskite solar cell as claimed in claim 2, wherein: the ratio of the total mole number of the dibromo fluorine-containing fluorene monomer and the dibromo product to the mole number of the diboronic acid ester is 0.5: 1-1: 1.5; the molar ratio of the dibromo fluorine-containing fluorene monomer to the dibromo-compound is 1: 100-100: 0; the catalyst is a palladium catalyst, and the ratio of the catalyst to the total mol of the dibromo fluorine-containing fluorene monomer, the diboronic acid ester compound and the dibromo compound is 0.001: 1-0.2: 1; the ligand is selected from one or more of tricyclohexylphosphine fluoborate, tripyrrolidinphosphine, triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine or triethylene diamine; the molar ratio of the ligand to the catalyst is 0.1: 1-50: 1; the ratio of the mole number of the weak base to the total mole number of the dibromo fluorine-containing fluorene monomer, the diboronic acid ester substance and the dibromo substance is 0.1: 1-50: 1; the dosage of the phenylboronic acid and the bromobenzene is 0.1-1 of the total mole number of the dibromo fluorine-containing fluorene monomer, the diboronate ester and the dibromo product.
5. A method of preparing a hole transport layer according to claim 1 for improving the stability of a perovskite solar cell, characterized in that: the method comprises the following steps: dissolving the fluorine-containing triphenylamine copolymer in chlorobenzene to obtain a fluorine-containing triphenylamine copolymer solution with the concentration of 0.1-50 mg/mL, and then spin-coating the fluorine-containing triphenylamine copolymer solution on a perovskite layer to obtain a hole transport layer with the thickness of 1-500 nm.
6. A perovskite solar cell device prepared using the hole transport layer of claim 1, wherein: the perovskite solar cell device is sequentially provided with a cathode layer, an electron transmission layer, a perovskite photoactive layer, a hole transmission layer and an anode layer from bottom to top.
7. The perovskite solar cell device of claim 6, wherein: the cathode layer is one of etched ITO glass, FTO glass and AZO glass; the electron transport layer is TiO2ZnO, fullerene and derivatives thereof; the perovskite photoactive layer is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3One of (1); the hole transport layer is made of a fluorine-containing triphenylamine copolymer, and the thickness of the hole transport layer is 3-20 nm; the anode is evaporated silver, gold or aluminum.
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