CN111153896B - Thiophene-carbazole core four-arm hole transport material and preparation method and application thereof - Google Patents
Thiophene-carbazole core four-arm hole transport material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thiophene-carbazole core four-arm hole transport material and a preparation method and application thereof, wherein thiophene-carbazole is taken as a core, so that the HOMO energy level and LUMO energy level of the thiophene-carbazole core four-arm hole transport material are obviously higher than those of halogen-mixed perovskite, electrons can be prevented from being transited from a perovskite layer to a hole transport layer, and the occurrence of an interface electron recombination phenomenon is effectively inhibited; the preparation method comprises the following steps: p-iodoanisole and p-bromoaniline are subjected to coupling reaction to generate an intermediate (5); carrying out substitution reaction on the intermediate (5) and pinacol diboron to generate an intermediate (6); coupling reaction of the intermediate (6) and 2, 3-dibromothiophene to generate an intermediate (7); carrying out bromination reaction on the intermediate (7) to generate an intermediate (8); coupling reaction of the intermediate (6) and 3, 6-dibromocarbazole to generate an intermediate (9); coupling reaction of the intermediate (9) and the intermediate (8) to generate a final product CZ-1. When the hole transport material is used for the perovskite solar cell, the cell device has higher photoelectric conversion efficiency.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, relates to a doped hole transport material, and particularly relates to a thiophene-carbazole core four-arm hole transport material and a preparation method and application thereof.
Background
With the continuous development of the global economic society, the demand of the human society for energy is larger and larger, and the traditional fossil energy is more and more difficult to meet the development demand of the economic society. In addition, the extensive use of traditional fossil energy can cause serious damage to the natural environment and exacerbate the degree of greenhouse effect. Therefore, the search for new renewable pollution-free energy sources has become a problem to be faced by human society first. The solar energy is inexhaustible due to the advantages of being renewable and pollution-free, and the formation period is not very long like the traditional fossil energy. Therefore, how to utilize solar energy efficiently and at low cost is receiving more and more attention.
Solar cells have a long development history and a wide variety. The perovskite solar cell has a very wide development prospect due to the simple manufacturing process, low cost and good photoelectric conversion efficiency, so that the perovskite solar cell becomes the hottest research direction in the photovoltaic field.
The hole transport material has the functions of optimizing an interface, adjusting energy level matching and the like, and is an important component of the high-efficiency perovskite solar cell. An ideal hole transport material should have a high hole mobility; the Highest Occupied Orbital (HOMO) energy level is-5.1 to-5.3 eV; the perovskite-type lithium ion battery has high thermodynamic stability, good solubility and film forming property and hydrophobicity, so that a perovskite layer is protected better and the stability of the battery is improved.
In hybrid perovskite solar cells, the hole transport layer materials currently used are limited to 2, 2', 7, 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene (Spiro-omatad), Polytriarylamine (PTAA) and PEDOT: PSS, and the like. The hole mobility of the amorphous hole transport layer materials is generally low, wherein, Spiro-OMeTAD and PTAA require bis (trifluoromethylsulfonyl) lithium (Li-TFSI) and 4-tert-butylpyridine (TBP) as p-type doping, and the doping molecules can bring adverse effects to the stability of a battery device; and the PEDOT: although PSS does not need to be doped, polyelectrolytes have strong hygroscopicity and easily destroy the structure of the perovskite layer, and on the other hand, PEDOT: the acidity of PSS causes corrosion of ITO glass and at the same time has hygroscopic properties, resulting in a decrease in the stability of the battery device.
Therefore, selecting a suitable hole transport material to further improve the performance of the perovskite solar cell is one of the problems that the industry needs to solve urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thiophene-carbazole core four-arm hole transport material, wherein thiophene-carbazole is taken as a core of the hole transport material, so that the HOMO energy level and LUMO energy level of the thiophene-carbazole core are obviously higher than those of halogen-mixed perovskite, and electrons can be blocked from being transited from a perovskite layer to a hole transport layer, so that the occurrence of an interface electron recombination phenomenon is effectively inhibited; the invention also aims to provide a preparation method of the hole transport material and application of the hole transport material in a perovskite solar cell, wherein the short-circuit photocurrent density of a cell device reaches 23.27 mA cm -2 The open circuit voltage is 1.089V, the filling factor is 0.7452, and the photoelectric conversion efficiency is as high as 18.85%.
The invention is realized by the following technical scheme:
a thiophene-carbazole core four-arm hole transport material has a chemical mechanism formula shown as a formula (CZ-1):
the invention further improves the scheme as follows:
the method for preparing the thiophene-carbazole core four-arm hole transport material comprises the following steps:
p-iodoanisole and p-bromoaniline are subjected to coupling reaction to generate an intermediate (5); carrying out substitution reaction on the intermediate (5) and the diboron pinacol ester to generate an intermediate (6); the intermediate (6) and 2, 3-dibromothiophene are subjected to coupling reaction to generate an intermediate (7); carrying out bromination reaction on the intermediate (7) to generate an intermediate (8); the intermediate (6) and 3, 6-dibromocarbazole are subjected to coupling reaction to generate an intermediate (9); carrying out coupling reaction on the intermediate (9) and the intermediate (8) to generate a final product CZ-1;
further, the method comprises the following steps:
synthesis of intermediate (5): taking toluene as a solvent, heating and refluxing p-iodoanisole and p-bromoaniline under the combined action of a catalyst, strong base and a chelating ligand to generate an intermediate (5) in a nitrogen environment; the molar ratio of the p-iodoanisole to the p-bromoaniline to the catalyst to the strong base to the chelating ligand is 1: 0.2-0.6: 0.06-0.09: 3.0-3.4: 0.06-0.09;
synthesis of intermediate (6): taking toluene as a solvent, and heating and refluxing the intermediate (5) and the diboron pinacol ester under the action of alkali and a catalyst to react to generate an intermediate (6) in a nitrogen environment; the molar ratio of the intermediate (5), the pinacol diboron, the base and the catalyst is 1: 1-1.4: 2.8-3: 0.08-0.12;
synthesis of intermediate (7): taking N, N-dimethylformamide and water as a mixed solvent, and heating and refluxing the intermediate (6) and 2, 3-dibromothiophene under the action of alkali and a catalyst in a nitrogen environment to react to generate an intermediate (7); the molar ratio of the intermediate (6), the 2, 3-dibromothiophene, the alkali and the catalyst is 1: 0.3-0.35: 1.8-2.2: 0.02-0.05;
synthesis of intermediate (8): taking tetrahydrofuran as a solvent, and reacting the intermediate (7) with NBS to generate an intermediate (8); the molar ratio of the intermediate (7) to NBS is 1: 1-1.2;
synthesis of intermediate (9): taking N, N-dimethylformamide and water as a mixed solvent, and heating and reacting the intermediate (6) and 3, 6-dibromocarbazole under the action of alkali and a catalyst to generate an intermediate (9) in a nitrogen environment; the molar ratio of the intermediate (6), the 3, 6-dibromocarbazole, the base and the catalyst is 1: 0.3-0.5: 4-4.3: 0.03-0.05;
synthesizing a thiophene-carbazole core four-arm hole transport material: toluene is used as a solvent, under the combined action of strong base, organic phosphine ligand and palladium catalyst, the intermediate (8) and the intermediate (9) are heated and refluxed to generate a coupling reaction under the nitrogen environment to generate the thiophene-carbazole core four-arm hole transport material; the molar ratio of the intermediate (8) to the intermediate (9) to the strong base to the organic phosphine ligand to the palladium catalyst is 1: 2.3-2.8: 2.8-3.2: 0.06-0.1: 0.02-0.06.
Further, during the synthesis of the intermediate (5), the reaction is carried out for 8-12 hours at the temperature of 110-120 ℃ under heating reflux; when the intermediate (6) is synthesized, the reaction is carried out for 8 to 12 hours at the temperature of 110 to 120 ℃ under heating reflux; when the intermediate (7) is synthesized, the reaction is carried out for 10 to 14 hours at the temperature of 110 to 120 ℃ under heating reflux; during the synthesis of the intermediate (8), NBS is added into a reaction system in batches at the temperature of 0-10 ℃ under the ice bath condition, and after the addition is finished, the reaction is carried out for 3-5 hours at the room temperature of 20-25 ℃; during the synthesis of the intermediate (9), the reaction time is 8-12 hours, and the reaction temperature is 80-100 ℃; when the thiophene-carbazole core four-arm hole transport material is synthesized, the thiophene-carbazole core four-arm hole transport material is reacted for 10-14 hours at the temperature of 110-120 ℃ under heating reflux.
Further, during the synthesis of the thiophene-carbazole core four-arm hole transport material, the strong base is sodium tert-butoxide; in the synthesis of the intermediate (5), the strong base is potassium hydroxide; during the synthesis of the intermediate (6), the alkali is potassium acetate; when the intermediates (7) and (9) are synthesized, the base is potassium carbonate.
Further, when the thiophene-carbazole core four-arm hole transport material is synthesized, the organophosphorus ligand is XPhos, and when the intermediate (5) is synthesized, the chelating ligand is 1, 10-o-phenanthroline.
Further, during the synthesis of the thiophene-carbazole core four-arm hole transport material, the palladium catalyst is tris (dibenzylideneacetone) dipalladium; during the synthesis of the intermediate (5), the catalyst is cuprous chloride; during the synthesis of the intermediate (6), the catalyst is 1, 1-bis-diphenylphosphino ferrocene palladium dichloride, and during the synthesis of the intermediates (7) and (9), the catalyst is tetrakistriphenylphosphine palladium.
Further, each step of the method also comprises a separation and purification step.
The invention further improves the scheme as follows:
the thiophene-carbazole core four-arm hole transport material is applied to perovskite solar cells.
The NBS is N-bromosuccinimide; DMF is N, N-dimethylformamide; XPhos is 2-dicyclohexyl phosphonium-2 ',4',6' -triisopropyl biphenyl.
The invention has the beneficial effects that:
the hole transport material takes thiophene-carbazole as a core, so that the HOMO energy level of the material is-5.04 eV, which is obviously higher than the HOMO energy level (FAI/MABr/PbI) of the halogen-mixed perovskite 2 /PbBr 2 CsI, -5.65 eV), sufficient driving force is ensured for efficient hole separation and transport; in addition, the LUMO energy level of the hole transport material of the invention is significantly higher than that of halogen-mixed perovskite (2.40 eV)vs.4.05) capable of blocking the transition of electrons from the perovskite layer to the hole transport layer, thereby effectively inhibiting the occurrence of the interface electron recombination phenomenon.
The preparation method of the hole material has the advantages of simple synthetic route and mild reaction conditions, and is a normal-pressure reaction; all reaction temperatures are completed between 0 ℃ and 120 ℃, and the industrial production is easy to realize; the required raw materials are easily obtained and are all commercial products.
The hole transport material is used in the application field of perovskite solar cells, so that the perovskite solar cells have high photoelectric conversion efficiency, the prepared devices are tested for photoelectric conversion efficiency, and the short-circuit photocurrent density of the cell devices reaches 23.27 mA cm -2 The open-circuit voltage is 1.089V, the filling factor is 0.7452, and the photoelectric conversion efficiency is as high as 18.85%.
Drawings
FIG. 1 is a normalized graph of ultraviolet-visible absorption spectrum and fluorescence emission spectrum of a thiophene-carbazole core four-arm hole transport material
FIG. 2 is a C-V cyclic voltammogram of a thiophene-carbazole core four-arm hole transport material
FIG. 3 is a schematic diagram of a perovskite solar cell structure; in the figure: 1. the solar cell comprises a metal electrode, 2, a hole transport layer, 3, a perovskite photosensitive layer, 4, an electron transport layer, 5 and conductive glass;
FIG. 4 is an I-V curve of CZ-1 as a hole transporting material applied to a perovskite solar cell.
Detailed Description
Example (b): synthesis of thiophene-carbazole core four-arm hole transport material
Synthesis of intermediate 5:
p-iodoanisole (5.1 g, 21.78 mmol), p-bromoaniline (1.5 g, 8.71 mmol), cuprous chloride (165 mg, 1.66 mmol), potassium hydroxide (3.9 g, 69.51 mmol) and 1, 10-phenanthroline (315 mg, 1.66 mmol) were weighed into a 100 ml two-necked flask and the nitrogen gas was replaced three times by evacuation. 30 mL of toluene was added to the flask, and the mixture was stirred and heated under reflux for about 10 hours. After the reaction, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 1: 10 as eluent, the target compound was obtained, product 5 was a white solid with a yield of 80%.
Synthesis of intermediate 6:
compound 5 (2 g, 5.20 mmol), pinacol diboron (3.96 g, 6.24 mmol), potassium acetate (1.28 g, 15.20 mmol) and 1, 1-bis-diphenylphosphinoferrocene palladium dichloride (382 mg, 0.52 mmol) were weighed into a 100 ml two-necked flask and nitrogen was replaced by evacuation three times. 30 mL of toluene was added to the flask, and the mixture was stirred and heated under reflux for about 10 hours. After the reaction, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 1: 10 as eluent, the target compound was obtained in the form of product 6 as a white solid with a yield of 80%.
Synthesis of intermediate 7:
in a 100 ml two-necked flask, weighed were compound 6 (2.67 g, 6.19 mmol), 2, 3-dibromothiophene (500 mg, 2.06 mmol), potassium carbonate (1.71 g, 12.36 mmol) and palladium tetratriphenylphosphine (240 mg, 0.21 mmol), nitrogen was replaced by evacuation three times. Adding 20 mL of N, N-dimethylformamide and 6 mL of water into two bottles, stirring, heating and refluxing for about 12 hours, extracting with dichloromethane after the reaction is finished, extracting with water for 6-7 times to remove a reaction solvent, drying with anhydrous sodium sulfate, and evaporating under reduced pressure to remove dichloromethane. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 1: 3 as eluent, the target compound was obtained, product 7 was a yellow solid with a yield of 74%.
Synthesis of intermediate 8:
weighing compound 7 (1 g, 1.45 mmol) into a 100 mL round-bottom flask, adding 20 mL tetrahydrofuran, stirring and dissolving, adding NBS (285 mg, 1.60 mmol) in batches under ice bath conditions, slowly returning the reaction system to room temperature from the ice bath, reacting for 4 hours, adding water after the reaction is finished, quenching, extracting with dichloromethane, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure evaporation. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 1: 3 as eluent to obtain the target compound, and the product 8 is yellow solid with the yield of 95%.
Synthesis of intermediate 9:
in a 100 ml two-necked flask, compound 6 (1.90 g, 4.44 mmol), 3, 6-dibromocarbazole (600 mg, 1.85 mmol), potassium carbonate (2.55 g, 18.46 mmol) and tetratriphenylphosphine palladium (220 mg, 0.18 mmol) were weighed, and nitrogen was replaced by vacuum pumping three times. Adding 20 mL of N, N-dimethylformamide into the two bottles, adding 9 mL of water, reacting for 12 hours at the temperature of ninety ℃, extracting with dichloromethane after the reaction is finished, extracting with water for 6-7 times to remove the reaction solvent, drying with anhydrous sodium sulfate, and evaporating under reduced pressure to remove dichloromethane. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 1: 3 as eluent, the target compound was obtained, product 9 was a white solid with a yield of 73%.
Synthesizing a thiophene-carbazole core four-arm hole transport material:
in a 100 ml two-necked flask, compound 8 (300 mg, 0.39 mmol), compound 9 (755 mg, 0.97 mmol), sodium tert-butoxide (112 mg, 1.17 mmol), XPhos (15 mg, 0.031 mmol) and tris (dibenzylideneacetone) dipalladium (14 mg, 0.016 mmol) were weighed, and nitrogen gas was replaced by vacuum evacuation three times. 20 mL of toluene was added to the flask, and the mixture was stirred and heated under reflux for overnight. After the reaction, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purifying the crude product by silica gel column chromatography, wherein the volume ratio of dichloromethane: petroleum ether = 2: 3 as eluent to obtain the final product CZ-1, which is yellow solid with 71% yield. 1 H NMR (400 MHz, DMSO-d 6 ): δ 7.87 (d, J = 7.1 Hz, 9H), 7.26 (d, J = 3.7 Hz, 9H), 7.15 (d, J = 3.8 Hz, 6H), 7.04 (d, J = 8.9 Hz, 20H), 6.80 (d, J = 8.9 Hz, 19H), 3.76 (s, 24H)。
Test example: characterization of thiophene-carbazole core four-arm hole transport materials
The organic hole transport material CZ-1 prepared in the above example was tested by uv-vis absorption spectroscopy (fig. 1), fluorescence emission spectroscopy (fig. 1) and C-V cyclic voltammogram (fig. 2), and the results showed that: the HOMO energy level of CZ-1 is-5.04 eV, which is obviously higher than the HOMO energy level (FAI/MABr/PbI) of the halogen-mixed perovskite 2 /PbBr 2 CsI, -5.65 eV), sufficient driving force is ensured for efficient hole separation and transport; furthermore, the LUMO energy level of CZ-1 is significantly higher than that of halogen-mixed perovskites (2.40 eV)vs.-4.05) capable of blocking electronsThe transition from the perovskite layer to the hole transport layer effectively inhibits the generation of the interface electron recombination phenomenon.
The organic hole-transporting material CZ-1 prepared in the above example, was prepared according to the literature: wang, J.; Zhang, H.; Wu, B.; Wang, Z.; Sun, Z.; Xue, S.; Wu, Y.; Hagfeldt, A.; Liang, M. Angew. chem. 2019, 58 (44), 15724-. Testing a light source: AM 1.5 (solar simulator-Oriel 91160-1000, 300W), data collection used Keithley 2400 digital source tables. The test result is shown in figure 4, and the short-circuit photocurrent density of the battery device reaches 23.27 mA cm -2 The open circuit voltage is 1.089V, the filling factor is 0.7452, and the photoelectric conversion efficiency is as high as 18.85%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A thiophene-carbazole core four-arm hole transport material is characterized in that the chemical mechanism formula is shown as a formula (CZ-1):
2. a method for preparing a thiophene-carbazole core four-arm hole transport material according to claim 1, comprising the steps of:
p-iodoanisole and p-bromoaniline are subjected to coupling reaction to generate an intermediate (5); carrying out substitution reaction on the intermediate (5) and the diboron pinacol ester to generate an intermediate (6); coupling reaction is carried out on the intermediate (6) and 2, 3-dibromothiophene to generate an intermediate (7); carrying out bromination reaction on the intermediate (7) to generate an intermediate (8); coupling reaction is carried out on the intermediate (6) and 3, 6-dibromocarbazole to generate an intermediate (9); the intermediate (9) and the intermediate (8) are subjected to coupling reaction to generate a final product CZ-1;
3. the preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 2, characterized by comprising the following steps:
synthesis of intermediate (5): taking toluene as a solvent, heating and refluxing p-iodoanisole and p-bromoaniline under the combined action of a catalyst, strong base and a chelating ligand to generate an intermediate (5) in a nitrogen environment; the molar ratio of the p-iodoanisole to the p-bromoaniline to the catalyst to the strong base to the chelating ligand is 1: 0.2-0.6: 0.06-0.09: 3.0-3.4: 0.06-0.09;
synthesis of intermediate (6): taking toluene as a solvent, and heating and refluxing the intermediate (5) and the diboron pinacol ester under the action of alkali and a catalyst to react to generate an intermediate (6) in a nitrogen environment; the molar ratio of the intermediate (5), the pinacol diboron, the base and the catalyst is 1: 1-1.4: 2.8-3: 0.08-0.12;
synthesis of intermediate (7): taking N, N-dimethylformamide and water as a mixed solvent, and heating and refluxing the intermediate (6) and 2, 3-dibromothiophene under the action of alkali and a catalyst in a nitrogen environment to react to generate an intermediate (7); the molar ratio of the intermediate (6), the 2, 3-dibromothiophene, the alkali and the catalyst is 1: 0.3-0.35: 1.8-2.2: 0.02-0.05;
synthesis of intermediate (8): taking tetrahydrofuran as a solvent, and reacting the intermediate (7) with NBS to generate an intermediate (8); the molar ratio of the intermediate (7) to NBS is 1: 1-1.2;
synthesis of intermediate (9): taking N, N-dimethylformamide and water as a mixed solvent, and heating and reacting the intermediate (6) and 3, 6-dibromocarbazole under the action of alkali and a catalyst to generate an intermediate (9) in a nitrogen environment; the molar ratio of the intermediate (6), the 3, 6-dibromocarbazole, the base and the catalyst is 1: 0.3-0.5: 4-4.3: 0.03-0.05;
synthesizing a thiophene-carbazole core four-arm hole transport material: toluene is used as a solvent, under the combined action of strong base, organic phosphine ligand and palladium catalyst, the intermediate (8) and the intermediate (9) are heated and refluxed to generate a coupling reaction to generate the thiophene-carbazole core four-arm hole transport material in a nitrogen environment; the molar ratio of the intermediate (8) to the intermediate (9) to the strong base to the organic phosphine ligand to the palladium catalyst is 1: 2.3-2.8: 2.8-3.2: 0.06-0.1: 0.02-0.06.
4. The preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 3, wherein the thiophene-carbazole core four-arm hole transport material is characterized in that: when the intermediate (5) is synthesized, the reaction is carried out for 8 to 12 hours at the temperature of 110 to 120 ℃ under heating reflux; when the intermediate (6) is synthesized, the reaction is carried out for 8 to 12 hours at the temperature of 110 to 120 ℃ under heating reflux; when the intermediate (7) is synthesized, the reaction is carried out for 10 to 14 hours at the temperature of 110 to 120 ℃ under heating reflux; during the synthesis of the intermediate (8), NBS is added into a reaction system in batches at the temperature of 0-10 ℃ under the ice bath condition, and after the addition is finished, the reaction is carried out for 3-5 hours at the room temperature of 20-25 ℃; during the synthesis of the intermediate (9), the reaction time is 8-12 hours, and the reaction temperature is 80-100 ℃; during the synthesis of the thiophene-carbazole core four-arm hole transport material, the thiophene-carbazole core four-arm hole transport material is reacted for 10 to 14 hours at the temperature of 110 to 120 ℃ under heating reflux.
5. The preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 3, wherein the thiophene-carbazole core four-arm hole transport material is characterized in that: in the synthesis of the intermediate (5), the strong base is potassium hydroxide; during the synthesis of the intermediate (6), the alkali is potassium acetate; when the intermediates (7) and (9) are synthesized, the base is potassium carbonate.
6. The preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 3, wherein the thiophene-carbazole core four-arm hole transport material is characterized in that: when the thiophene-carbazole core four-arm hole transport material is synthesized, the organophosphorus ligand is XPhos, and when the intermediate (5) is synthesized, the chelating ligand is 1, 10-phenanthroline.
7. The preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 3, wherein the thiophene-carbazole core four-arm hole transport material is characterized in that: during the synthesis of the thiophene-carbazole core four-arm hole transport material, the palladium catalyst is tris (dibenzylideneacetone) dipalladium; during the synthesis of the intermediate (5), the catalyst is cuprous chloride; during the synthesis of the intermediate (6), the catalyst is 1, 1-bis-diphenylphosphino ferrocene palladium dichloride, and during the synthesis of the intermediates (7) and (9), the catalyst is tetrakistriphenylphosphine palladium.
8. The preparation method of the thiophene-carbazole core four-arm hole transport material according to claim 2, wherein the thiophene-carbazole core four-arm hole transport material is characterized in that: the method also comprises a separation and purification step in each step.
9. The use of the thiophene-carbazole core four-arm hole-transporting material of claim 1 in perovskite solar cells.
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| CN107311975A (en) * | 2017-06-15 | 2017-11-03 | 中节能万润股份有限公司 | A kind of derivative of dibenzothiophenes and its application |
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| CN107311975A (en) * | 2017-06-15 | 2017-11-03 | 中节能万润股份有限公司 | A kind of derivative of dibenzothiophenes and its application |
| CN108484569A (en) * | 2018-03-07 | 2018-09-04 | 中国科学院化学研究所 | A kind of thiophene s bridges tetramine pyrene hole mobile material and its application in perovskite solar cell |
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