CN115894501A - Undoped hole transport material taking carbazole fused ring as core, and synthesis method and application thereof - Google Patents
Undoped hole transport material taking carbazole fused ring as core, and synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 5
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention belongs to the technical field of organic semiconductor functional materials and application thereof, and discloses a non-doped hole transport material taking carbazole fused rings as cores, a synthesis method thereof and application thereof in perovskite solar cells. The undoped hole transport material takes the electron-deficient group of the benzindolocarbazole as a core structure and 4,4' -dimethoxy diphenylamine as an end group, has the characteristics of proper energy level, good hydrophobicity and excellent charge transport performance, and is applied to the perovskite solar cell to realize the improvement of the stability of a cell device and further reduce the production cost of the cell.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor functional materials and application thereof, and particularly relates to a non-doped hole transport material taking carbazole condensed rings as cores, a synthesis method thereof and application thereof in a perovskite solar cell.
Background
Perovskite solar cells are a new type of solar cells developed on the basis of dye-sensitized solar cells and organic solar cells, and have received extensive attention and research from researchers due to their advantages such as low manufacturing cost, strong light-capturing capability, and excellent photoelectric conversion performance (Farokhi, a., shahroosvand, h., monache, g.d., pilkington, m., nazeruddin, m.k., chem.soc.rev.2022,51, 5974-6064). As one of the important functional layers of the perovskite solar cell, a hole transport material is in direct contact with a perovskite active layer, has the functions of extracting and transporting holes generated by light induction, inhibiting charge recombination, preventing oxygen and moisture from invading and the like, and plays a crucial role in improving the efficiency and stability of the cell device (Jeong, M.; cho, I.W.; go E.M.; cho Y.; kim, M.; lee, B.; jeong, S.; jo Y.; choi, HW, lee, J.; bae, J.H.; kwak, S.K.; kim, D.S.; yak, science 2020,369 1615-20.). Among them, organic small molecule hole transport materials are strong candidates for efficient hole transport materials due to their many advantages such as low cost, good solubility and film-forming properties, and easy modification of chemical structure (Niu, t.; zhu, w.; zhang, y.; xue, q.; jiao, x.; wang, z.; xie, y. -m.; li, p.; chen, r.; huang, f.; li, y.; yip, h. -l.; cao, y.; joule 2021,5, 249-269.). At present, most organic small molecule hole transport materials need chemical doping to improve the hole mobility, but on one hand, the introduction of a doping agent can accelerate the degradation of a perovskite layer, so that the stability of a battery device is adversely affected; on the other hand, the manufacturing cost of the battery is increased, which is not favorable for large-area commercial application of the battery (Shen, C.; wu, Y.; zhang, H.; li, E.; zhang, W.; xu, X.; wu, W.; tian, H.; zhu, W.H., angew. Chem. Int. Ed.2019,58, 3784-3789.). Therefore, the construction of the undoped hole transport material is one of effective means for preparing the perovskite solar cell with high efficiency, stability and low cost. Relevant researches show that the pi-pi stacking effect between molecules can be effectively regulated and controlled by regulating the conjugated core structure of the organic small-molecule hole transport material, so that the hole mobility and the conductivity of the hole transport material are improved and undoped (Guo, H.; zhang, H.; shen, C.; zhang, D.; liu, S.; wu, Y.; zhu, W.H., angew.chem., int.Ed.2021,60, 2674-2679.). At present, no non-doped hole transport material taking carbazole fused rings as core structures is reported.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to develop a non-doped hole transport material which takes carbazole condensed rings with higher rigidity and conjugation degree as a core structure, has the characteristics of proper energy level, good hydrophobicity and excellent charge transport performance, is applied to a perovskite solar cell, realizes the improvement of the stability of a cell device, and further reduces the production cost of the cell.
The undoped hole transport material with the carbazole fused ring as the core structure takes benzindole carbazole as the core and 4,4' -dimethoxy diphenylamine as a terminal group. The material has the advantages of energy level matching, good hydrophobicity, excellent charge transmission performance and the like, is applied to perovskite solar cells as a hole transmission material, does not need additives and dopants such as lithium salt, cobalt salt and tert-butylpyridine, can improve the stability of the cell while keeping the high efficiency of the cell, and reduces the preparation cost of the cell.
The technical scheme adopted by the invention is as follows:
a non-doped hole transport material with carbazole fused ring as core has chemical name of N 2 ,N 2 ,N 15 ,N 15 5,12-hexa (4-methoxyphenyl) -5,12-dihydronaphthyl [1,2-b:4,3-b']Dicarbazole-2, 15-diamine, referred to as NCz-DM for short, is characterized by taking the electron-deficient group of benzindolocarbazole as a core structure and 4,4' -dimethoxydiphenylamine as an end group, and has the following structural formula:
the synthesis method of the non-doped hole transport material NCz-DM taking the carbazole fused ring as the core comprises the following steps: carrying out Suzuki coupling reaction on the 1, 2-dibromobenzene and the compound 1 to obtain an intermediate 2; carrying out intramolecular oxidation C-C coupling reaction on the intermediate 2 to obtain an intermediate 3; carrying out bromination reaction on the intermediate 3 to obtain an intermediate 4; the intermediate 4 and reactant 4,4' -dimethoxy diphenylamine are subjected to Buchwald-Hartwig coupling reaction to obtain a final product NCz-DM, and the method comprises the following specific steps:
(i) Adding 1, 2-dibromobenzene, a compound 1, chlorine (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II) (Xphos Pd G2), potassium phosphate aqueous solution and a solvent tetrahydrofuran into a dry reaction vessel to form a mixed solution, uniformly stirring under the protection of nitrogen, heating to 40-60 ℃ for reaction for 15-24h, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution by using dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a white solid compound 2.
(ii) Adding a compound 2 and a solvent dichloromethane into a dry reaction container, stirring uniformly under the conditions of ice-water bath and nitrogen protection, then slowly dropwise adding methanesulfonic acid and stirring for 2-3min, then adding dichlorodicyanobenzoquinone (DDQ) to form a mixed solution, then heating to room temperature to react for 1-5min, after the reaction is finished, adding a saturated sodium bicarbonate solution under the condition of ice-water bath, stirring for 30-60min, extracting and separating a reaction solution by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying a collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a dark blue solid compound 3.
(iii) Adding a compound 3 and a solvent tetrahydrofuran into a dry reaction container, uniformly stirring under the conditions of ice water bath and nitrogen protection, slowly dropwise adding an N, N-dimethylformamide solution of N-bromosuccinimide (NBS), heating to room temperature for reacting for 12-24h, adding ice water after the reaction is finished, stirring for 30-60min, extracting and separating a reaction solution by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying a collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a yellow solid compound 4.
(iv) Adding a compound 4, a reactant 4,4' -dimethoxydiphenylamine, palladium acetate, potassium tert-butoxide, tri-tert-butylphosphine and a solvent toluene into a dry reaction vessel to form a mixed solution, stirring uniformly under the protection of nitrogen, heating to 100-120 ℃, reacting for 12-24h, cooling the reaction liquid to room temperature after the reaction is finished, extracting and separating the reaction liquid by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain the yellow solid hole transport material NCz-DM.
The synthetic route is as follows:
(ii) in the mixed solution of the step (i), 1, 2-dibromobenzene: compound 1: chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II): 1.4-2, molar ratio of potassium phosphate 1; the concentration of the 1, 2-dibromobenzene is 0.2 to 0.3mol/L; the molar concentration of the potassium phosphate aqueous solution is 0.5mol/L; the volume ratio of the tetrahydrofuran to the potassium phosphate aqueous solution is 1.
(iii) in the mixed solution of step (ii), compound 2: methanesulfonic acid: the molar ratio of dichloro dicyano benzoquinone is 1; the concentration of the compound 2 is 0.1-0.2 mol/L; the volume ratio of the methanesulfonic acid to the dichloromethane to the saturated sodium bicarbonate solution is 1.
In step (iii), compound 3: the molar ratio of NBS is 1; the concentration of the compound 3 in tetrahydrofuran is 0.03-0.08 mol/L; the concentration of NBS in N, N-dimethylformamide is 0.6-1.2 mol/L.
(iv) in the mixed solution of step (iv), compound 4:4,4' -dimethoxydiphenylamine: potassium tert-butoxide: palladium acetate: the molar ratio of tri-tert-butylphosphine is 1; the concentration of the compound 4 is 0.01-0.04 mol/L.
The non-doped hole transport material taking the benzindozoles carbazole as the core is used as a hole transport layer to be applied to the perovskite solar cell. The perovskite solar cell is composed of a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer, a hole transmission layer and a metal electrode, and the perovskite solar cell is prepared by the following specific steps:
(1) Cutting a transparent conductive substrate into a fixed size, etching, sequentially ultrasonically cleaning the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone sterilization treatment on the substrate;
(2) Preparing a metal oxide electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method, and transferring the metal oxide electron transport layer into a glove box for later use;
(3) Transferring the conductive substrate coated with the electron transmission layer into a glove box, spin-coating perovskite precursor liquid on the electron transmission layer by a spin-coating method, and dripping chlorobenzene antisolvent in the process of spin-coating the perovskite precursor liquid to form a perovskite light absorption layer;
(4) Covering a chlorobenzene solution containing an undoped hole transport material NCz-DM on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method, and sintering at 80-100 ℃ for 5-10 minutes to form an NCz-DM hole transport layer;
(5) And depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
In the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence;
in the step (2), the electron transport layer is one of titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the preparation method of the perovskite precursor solution comprises the following steps: in a glove box, methylamine bromide, formamidine iodide, lead bromide and methylamine chloride were mixed and dissolved in N, N-dimethylformamide in a volume ratio of 4: stirring the mixed solution of dimethyl sulfoxide at room temperature to obtain a perovskite precursor solution;
in the step (4), the hole transport material solution is prepared by dissolving 5-15mg of hole transport material in 1mL of chlorobenzene;
in the step (5), the metal electrode is one of gold, silver or copper.
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
The invention has the following advantages:
the non-doped hole transport material NCz-DM provided by the invention adopts electron-deficient groups of benzindolocarbazole as a core structure and 4,4' -dimethoxy diphenylamine as end group; the material has stronger rigidity and conjugation effect, and can effectively enhance the pi-pi stacking effect among molecules, thereby greatly improving the hole mobility and the electrical conductivity of the material. Therefore, the hole transport material has the advantages of simple synthesis, low cost, stable natural conditions, excellent charge transport performance and the like, lithium salt, cobalt salt, tert-butylpyridine and other additives and dopants are not required to be adopted in the using process, the hole transport material is finally applied to the perovskite solar cell to obtain excellent photoelectric properties of the open-circuit voltage of more than 1.05V and the photoelectric conversion efficiency of more than 18%, the high efficiency is maintained, meanwhile, the reduction of the production cost and the improvement of the stability are realized, and the industrialization of the perovskite solar cell is further promoted.
Drawings
FIG. 1 is a cyclic voltammetry curve for a NCz-DM material prepared according to the invention;
FIG. 2 is a schematic structural diagram of a perovskite solar cell prepared by the invention, wherein 1 is an FTO transparent conductive layer, and 2 is SnO 2 An electron transport layer, 3 is a perovskite light absorption layer, 4 is a hole transport layer, and 5 is a gold electrode;
FIG. 3 is a J-V plot (illumination intensity 100 mW/cm) of perovskite solar cells based on undoped hole-transporting layers of different concentrations according to examples 1 and 2 of the present invention and perovskite solar cells based on conventional doped hole-transporting layers of comparative examples 2 )；
Fig. 4 is a stability test chart of a perovskite solar cell based on an undoped hole transport layer of example 1 of the present invention and a perovskite solar cell based on a conventional doped hole transport layer of a comparative example.
Detailed Description
The present invention is further described in the following examples in order to enable those skilled in the art to better understand the present invention, but the scope of the present invention is not limited to the following examples, and the scope of the present invention is defined by the claims.
Example 1:
the synthesis of a non-doped hole transport material NCz-DM taking a carbazole condensed ring as a core and the application thereof in a perovskite solar cell are as follows:
(i) To a dry reaction vessel were added 1, 2-dibromobenzene (1.95g, 8.35mmol), compound 1 (7.00g, 17.54mmol), XPhos Pd G2 (0.20g, 0.25mmol), and 0.5M K 3 PO 4 Stirring the aqueous solution (24 mL) and tetrahydrofuran (12 mL) as a solvent uniformly under the protection of nitrogen, heating the mixture to 40 ℃ for reaction for 20 hours, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution for three times by using dichloromethane solution (150 mL), collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, using petroleum ether/dichloromethane (3. 1 H NMR(400MHz,CDCl 3 ) δ =8.13 (dt, J =7.6,1.0hz, 2h), 8.06-8.03 (m, 2H), 7.57 (dd, J =5.7,3.4hz, 2h), 7.44-7.35 (m, 6H), 7.28-7.19 (m, 6H), 6.92 (d, J =8.4hz, 4h), 6.71-6.63 (m, 4H), 3.75 (s, 6H), HR-MS: calculated value C, calculated value 44 H 32 N 2 O 2 620.2464, found 620.2470.
(ii) Adding compound 2 (0.80g, 1.29mmol) and a solvent dichloromethane (10 mL) into a dry reaction container, uniformly stirring under the conditions of ice-water bath and nitrogen protection, then slowly dropwise adding methanesulfonic acid (0.84mL, 12.90mmol) and stirring for 2min, then adding dichlorodicyanobenzoquinone (1.17g, 5.16mmol), then heating to room temperature for reacting for 2min, after the reaction is finished, adding a saturated sodium bicarbonate solution (40 mL) under the condition of ice-water bath, stirring for 30min, extracting and separating a reaction solution by using a dichloromethane solution for three times, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying a collected substance by using a silica gel chromatographic column, and using petroleum ether/dichlorohydrin for separating and separating a reaction solutionMethane (2. 1 H NMR(400MHz,CDCl 3 ) δ =9.57 (s, 2H), 8.67-8.40 (m, 6H), 7.65-7.50 (m, 8H), 7.42 (dd, J =7.9,4.7hz, 4H), 7.22 (s, 4H), 4.00 (s, 6H), HR-MS calculated C 44 H 30 N 2 O 2 618.2307, found 618.2307.
(iii) Adding compound 3 (1.2g, 1.94mmol) and tetrahydrofuran (50 mL) as a solvent into a dry reaction vessel, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding 5mL of N, N-dimethylformamide solution (0.82 mol/L) of N-bromosuccinimide, then heating to room temperature for reaction for 15h, adding ice water after the reaction is finished, stirring for 30min, extracting and separating the reaction solution for three times by using dichloromethane solution (150 mL), collecting an organic layer, removing the solvent under reduced pressure, separating and extracting a collection by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (2: 11vol) as an eluent, and drying in vacuum to obtain yellow solid compound 3 (1.31 g, yield: 87%). HR-MS calculated value C 44 H 28 Br 2 N 2 O 2 776.0497, found 776.0504.
(iv) In a dry reaction vessel, compound 4 (1.10g, 1.42mmol), 4' -dimethoxydiphenylamine (0.82g, 3.54mmol), palladium acetate (0.06g, 0.28mmol), potassium tert-butoxide (0.48g, 4.26mmol), tri-tert-butylphosphine (1.15g, 0.57mmol) and solvent toluene (80 mL) were added, stirred uniformly under a nitrogen protection condition, and heated to 120 ℃ for 24 hours, after the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted and separated three times with dichloromethane solution (150 mL), the organic layer was collected, the solvent was removed under reduced pressure, and the collection was separated by a silica gel column chromatography, petroleum ether/dichloromethane (1 11vol/vol) was used as an eluent, and vacuum drying was carried out to obtain a yellow solid hole transport material NCz-DM (1.04 g, yield: 68.0%). 1 H NMR(400MHz,CDCl 3 ) δ =8.62-8.36 (m, 4H), 8.19 (s, 2H), 7.65-7.50 (m, 8H), 7.50-7.34 (m, 4H), 7.22 (d, J =8.6hz, 4H), 7.11 (d, J =8.4hz, 8H), 6.85 (d, J =8.6hz, 8H), 3.99 (s, 6H), 3.83 (s, 12H), HR-MS: calculated value C: (calculated value of C): calculated value of C: (calculated value of d, J =8.4hz, 8H) 72 H 56 N 4 O 6 1072.4200, found 1072.4204.
The synthesized hole transport material NCz-DM is applied to a perovskite solar cell, and the preparation method and the process thereof are as follows:
the perovskite solar cell has a cell structure of FTO/SnO 2 Perovskite/NCz-DM/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of size 15mm × 15mm, and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30min.
(2) Using a spin coating method, 4wt% SnO 2 The colloid solution is coated on the glass conductive substrate in a spin way, the revolution is controlled to be 3000rpm, the spin-coating time is controlled to be 30s, and then the glass conductive substrate is heated to 180 ℃ and sintered for 30min to form a layer of compact SnO 2 The film is subjected to ultraviolet ozone treatment for 5min, and then the prepared electron transport layer film is transferred into a glove box for standby.
(3) In a glove box, lead iodide (705.3mg, 1.53mmol), formamidine iodide (240.8mg, 1.40mmol), lead bromide (24.9mg, 0.068mmol), methylamine bromide (7.6mg, 0.068mmol), methylamine chloride (33.8mg, 0.5mmol) were dissolved in 1mL of N, N-dimethylformamide at a volume ratio of 4: and stirring the mixed solution of dimethyl sulfoxide at room temperature to obtain the perovskite precursor solution. Using a spin coater to coat the prepared 30 mu L of perovskite precursor liquid on SnO in a liquid-spinning way 2 On the film, the number of revolutions was controlled to 1000rpm, the spin-coating time was controlled to 10s, and then the number of revolutions was controlled to 5000rpm, and the spin-coating time was controlled to 20s, during which 200. Mu.L of chlorobenzene was dropped on the film, and the perovskite thin film was annealed and calcined at 150 ℃ for 30 minutes to obtain a dense and uniform perovskite active layer thin film.
(4) 30 μ L of NCz-DM hole transport layer solution (10 mg of NCz-DM dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the perovskite thin film by a spin coating method, the number of revolutions was controlled to 3000rpm, the spin coating time was 30s, and it was annealed and calcined at 80 ℃ for 10min to obtain an NCz-DM hole transport layer thin film.
(5) Finally, depositing 100nm Au by vacuum evaporationDepositing on the device film, and making the evaporation area of Au 20mm by a specific mold 2 。
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
Example 2:
the synthesis of a non-doped hole transport material NCz-DM taking a carbazole condensed ring as a core and the application thereof in a perovskite solar cell are as follows:
(i) To a dry reaction vessel were added 1, 2-dibromobenzene (1.95g, 8.35mmol), compound 1 (7.00g, 17.54mmol), XPhos Pd G2 (0.20g, 0.25mmol), and 0.5M K 3 PO 4 Stirring the aqueous solution (24 mL) and tetrahydrofuran (10 mL) as a solvent uniformly under the protection of nitrogen, heating the mixture to 40 ℃ for reaction for 20 hours, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution for three times by using dichloromethane solution (150 mL), collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, using petroleum ether/dichloromethane (3. 1 H NMR(400MHz,CDCl 3 ) δ =8.13 (dt, J =7.6,1.0hz, 2h), 8.06-8.03 (m, 2H), 7.57 (dd, J =5.7,3.4hz, 2h), 7.44-7.35 (m, 6H), 7.28-7.19 (m, 6H), 6.92 (d, J =8.4hz, 4h), 6.71-6.63 (m, 4H), 3.75 (s, 6H), HR-MS: calculated value C 44 H 32 N 2 O 2 620.2464, found 620.2470.
(ii) Adding compound 2 (0.88g, 1.42mmol) and solvent dichloromethane (10 mL) into a dry reaction vessel, stirring uniformly under ice-water bath and nitrogen protection, then slowly dropwise adding methanesulfonic acid (0.92mL, 14.2mmol) and stirring for 2min, then adding dichlorodicyanobenzoquinone (1.29g, 5.68mmol), then heating to room temperature for reacting for 4min, after the reaction is finished, adding saturated sodium bicarbonate solution (50 mL) under ice-water bath condition, stirring for 40min, extracting and separating reaction liquid with dichloromethane solution for three times, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column,petroleum ether/dichloromethane (2. 1 H NMR(400MHz,CDCl 3 ) δ =9.57 (s, 2H), 8.67-8.40 (m, 6H), 7.65-7.50 (m, 8H), 7.42 (dd, J =7.9,4.7hz, 4H), 7.22 (s, 4H), 4.00 (s, 6H), HR-MS calculated C 44 H 30 N 2 O 2 618.2307, found 618.2307.
(iii) Adding compound 3 (1.26g, 2.04mmol) and tetrahydrofuran (50 mL) as a solvent into a dry reaction vessel, stirring uniformly under the conditions of ice-water bath and nitrogen protection, slowly adding 4.98mL of N, N-dimethylformamide solution (0.82 mol/L) of N-bromosuccinimide dropwise, then heating to room temperature for reaction for 15h, adding ice water for stirring for 30min after the reaction is finished, extracting and separating the reaction liquid for three times by using dichloromethane solution (150 mL), collecting an organic layer, removing the solvent under reduced pressure, separating and extracting a collected substance by using a silica gel chromatographic column, taking petroleum ether/dichloromethane (2 11vol/vol) as an eluent, and drying in vacuum to obtain compound 3 (1.36 g, yield: 86%) as a yellow solid. HR-MS calculated value C 44 H 28 Br 2 N 2 O 2 776.0497, found 776.0504.
(iv) Compound 4 (2.20g, 2.84mmol), 4' -dimethoxydiphenylamine (1.64g, 7.08mmol), palladium acetate (0.12g, 0.56mmol), potassium tert-butoxide (0.96g, 8.52mmol), tri-tert-butylphosphine (2.30g, 1.14mmol) and toluene (80 mL) as a solvent were added to a dry reaction vessel, stirred uniformly under nitrogen protection, and heated to 120 ℃ for 24 hours, after the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted and separated three times with a dichloromethane solution (150 mL), the organic layer was collected, the solvent was removed under reduced pressure, and the collection was separated by a silica gel column chromatography, and petroleum ether/dichloromethane (1 11vol/vol) was used as an eluent, and vacuum-dried to obtain NCz-DM (1.74 g, yield: 57.0%) as a yellow solid hole transport material. 1 H NMR(400MHz,CDCl 3 ) δ =8.62-8.36 (m, 4H), 8.19 (s, 2H), 7.65-7.50 (m, 8H), 7.50-7.34 (m, 4H), 7.22 (d, J =8.6hz, 4H), 7.11 (d, J =8.4hz, 8H), 6.85 (d, J =8.6hz, 8H), 3.99 (s, 6H), 3.83 (s, 12H), HR-MS: calculated value C: calculated value 72 H 56 N 4 O 6 1072.4200, found 1072.4204.
The synthesized hole transport material NCz-DM is applied to a perovskite solar cell, and the preparation method and the process thereof are as follows:
the perovskite solar cell has a cell structure of FTO/SnO 2 Perovskite/NCz-DM/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of size 15mm × 15mm, and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30min.
(2) Using a spin coating method, 4wt% SnO 2 The colloid solution is coated on the glass conductive substrate in a spinning way, the rotation speed is controlled to be 3000rpm, the spinning time is controlled to be 30s, and then the glass conductive substrate is heated to 180 ℃ and sintered for 30min to form a layer of compact SnO 2 The film is subjected to ultraviolet ozone treatment for 5min, and then the prepared electron transport layer film is transferred into a glove box for standby.
(3) In a glove box, lead iodide (705.3mg, 1.53mmol), formamidine iodide (240.8mg, 1.40mmol), lead bromide (24.9mg, 0.068mmol), methylamine bromide (7.6mg, 0.068mmol), methylamine chloride (33.8mg, 0.5mmol) were dissolved in 1mL of N, N-dimethylformamide at a volume ratio of 4: and stirring the mixed solution of dimethyl sulfoxide at room temperature to obtain the perovskite precursor solution. Using a spin coater to coat the prepared 30 mu L of perovskite precursor liquid on SnO in a liquid-spinning way 2 On the film, the number of revolutions was controlled to 1000rpm, the spin-coating time was controlled to 10s, and then the number of revolutions was controlled to 5000rpm, and the spin-coating time was controlled to 20s, during which 200. Mu.L of chlorobenzene was dropped on the film, and the perovskite thin film was annealed and calcined at 150 ℃ for 30 minutes to obtain a dense and uniform perovskite active layer thin film.
(4) mu.L of NCz-DM hole transport layer solution (15 mg of NCz-DM dissolved in 1mL of chlorobenzene) was spin-coated onto the surface of the perovskite thin film by a spin coating method, the rotation number was controlled to 3000rpm, the spin coating time was 30s, and the film was annealed and calcined at 80 ℃ for 10min to obtain an NCz-DM hole transport layer thin film.
(5) Finally, 100nm of Au was passed throughDepositing the film on the device film by a vacuum evaporation method, and enabling the evaporation area of Au to be 20mm through a special die 2 。
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
Comparative example 1:
the method is characterized in that a traditional hole transport material Spiro-OMeTAD is selected as a hole transport material, and traditional additives and dopants are adopted, and the method is applied to perovskite solar cells, and the preparation method and the process are as follows:
the perovskite solar cell has a cell structure of FTO/SnO 2 Perovskite/cyclone-OMeTAD/Au, and the preparation process of the Perovskite solar cell comprises the following steps:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into glass substrates of size 15mm × 15mm, and etched using an etcher. And ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min in sequence, and then treating the glass substrate in an ultraviolet ozone machine for 30min.
(2) Using spin coating, 4wt% SnO 2 The colloid solution is coated on the glass conductive substrate in a spinning way, the rotation speed is controlled to be 3000rpm, the spinning time is controlled to be 30s, and then the glass conductive substrate is heated to 180 ℃ and sintered for 30min to form a layer of compact SnO 2 The film is subjected to ultraviolet ozone treatment for 5min, and then the prepared electron transport layer film is transferred into a glove box for standby.
(3) In a glove box, lead iodide (705.3mg, 1.53mmol), formamidine iodide (240.8mg, 1.40mmol), lead bromide (24.9mg, 0.068mmol), methylamine bromide (7.6mg, 0.068mmol), methylamine chloride (33.8mg, 0.5mmol) were dissolved in 1mL of N, N-dimethylformamide at a volume ratio of 4: and stirring the mixed solution of dimethyl sulfoxide at room temperature to obtain the perovskite precursor solution. Using a spin coater to coat the prepared 30 mu L of perovskite precursor liquid on SnO in a liquid-spinning way 2 On the film, the revolution was controlled at 1000rpm for 10s, and then the revolution was controlled at 5000rpm for 20s, during which 200. Mu.L of chlorobenzene was dropped on the film, and the perovskite film was annealed and calcined at 150 ℃ for 30 minutes to obtain a dense and uniform perovskite active layer film.
(4) A doped Spiro-OMeTAD hole transport layer thin film was obtained by spin-coating 30. Mu.L of a Spiro-OMeTAD hole transport layer solution (73 mg of Spiro-OMeTAD, 32.6mM LiTFSI, 205mM TBP, and 5.79mM FK209 dissolved in 1mL of chlorobenzene) onto the surface of the perovskite thin film by a spin-coating method with the number of revolutions controlled at 3000rpm for 30 s.
(5) Finally, 100nm Au is deposited on the device film by a vacuum evaporation method, and the evaporation area of the Au is 20mm by a special die 2 。
(3) And (4) the operation steps are all completed in a glove box filled with nitrogen.
FIG. 1 is a cyclic voltammetry curve for the NCz-DM material prepared in accordance with the present invention. As can be calculated from the figure, the hole transport material NCz-DM has a proper HOMO energy level (-5.17 eV), and can effectively extract and transport charges;
FIG. 2 is a schematic structural diagram of a perovskite solar cell prepared by the present invention (1 is FTO transparent conductive layer, 2 is SnO) 2 An electron transport layer, 3 is a perovskite photoactive layer, 4 is a hole transport layer, and 5 is a gold electrode);
FIG. 3 is a J-V plot (illumination intensity 100 mW/cm) of perovskite solar cells based on undoped hole-transporting layers of different concentrations according to examples 1 and 2 of the present invention and perovskite solar cells based on conventional doped hole-transporting layers of comparative examples 2 ) (ii) a As can be seen from the graph, the perovskite solar cells based on examples 1,2 and comparative example obtained photoelectric conversion efficiencies of 18.19%, 13.48% and 20.34%, respectively.
Fig. 4 is a stability test chart of a perovskite solar cell based on an undoped hole transport layer of example 1 of the present invention and a perovskite solar cell based on a conventional doped hole transport layer of a comparative example. As can be seen from the graph, the cell device based on example 1 still maintained the initial efficiency of 83% after undergoing 1000h aging, and the perovskite solar cell based on the conventional doped hole transport material maintained only 45.32% of the initial efficiency after undergoing 1000h aging experiments, which shows that the cell based on example 1 has excellent stability.
Claims (10)
1. The undoped hole transport material with carbazole condensed ring as core is characterized in that electron-deficient group of benzindole carbazole is used as core structure, 4' -dimethoxy diphenylamine is used as end group, and the chemical name of the material is N 2 ,N 2 ,N 15 ,N 15 5,12-hexa (4-methoxyphenyl) -5,12-dihydronaphthyl [1,2-b:4,3-b']Dicarbazole-2, 15-diamine, having the formula:
2. the method for synthesizing the undoped hole-transporting material with the carbazole fused ring as the core according to claim 1, wherein the method comprises the following steps: carrying out Suzuki coupling reaction on the 1, 2-dibromobenzene and the compound 1 to obtain an intermediate 2; carrying out intramolecular oxidation C-C coupling reaction on the intermediate 2 to obtain an intermediate 3; carrying out bromination reaction on the intermediate 3 to obtain an intermediate 4; the intermediate 4 and a reactant 4,4' -dimethoxy diphenylamine undergo Buchwald-Hartwig coupling reaction to obtain a final product, namely a non-doped hole transport material taking a carbazole condensed ring as a core, which is called NCz-DM for short;
the synthetic route is as follows:
3. the synthetic method according to claim 2, comprising the specific steps of:
(i) Adding 1, 2-dibromobenzene, a compound 1, chlorine (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II), potassium phosphate aqueous solution and a solvent tetrahydrofuran into a dry reaction vessel to form a mixed solution, stirring uniformly under the protection of nitrogen, heating to 40-60 ℃ for reaction for 15-24h, cooling the reaction solution to room temperature after the reaction is finished, extracting and separating the reaction solution by using dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a white solid compound 2;
(ii) Adding a compound 2 and a solvent dichloromethane into a dry reaction container, uniformly stirring under the conditions of ice-water bath and nitrogen protection, slowly dropwise adding methanesulfonic acid and stirring for 2-3min, then adding dichlorodicyanobenzoquinone DDQ to form a mixed solution, heating to room temperature for reacting for 1-5min, after the reaction is finished, adding a saturated sodium bicarbonate solution under the condition of ice-water bath, stirring for 30-60min, extracting and separating a reaction solution by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying a collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a dark blue solid compound 3;
(iii) Adding a compound 3 and a solvent tetrahydrofuran into a dry reaction container, uniformly stirring under the conditions of ice water bath and nitrogen protection, slowly dropwise adding an N, N-dimethylformamide solution of N-bromosuccinimide NBS, heating to room temperature for reacting for 12-24 hours, adding ice water after the reaction is finished, stirring for 30-60min, extracting and separating a reaction solution by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain a yellow solid compound 4;
(iv) Adding a compound 4, a reactant 4,4' -dimethoxydiphenylamine, palladium acetate, potassium tert-butoxide, tri-tert-butylphosphine and a solvent toluene into a dry reaction vessel to form a mixed solution, uniformly stirring under the protection of nitrogen, heating to 100-120 ℃, reacting for 12-24h, cooling a reaction liquid to room temperature after the reaction is finished, extracting and separating the reaction liquid by using a dichloromethane solution, collecting an organic layer, removing the solvent under reduced pressure, separating and purifying the collected substance by using a silica gel chromatographic column, and drying in vacuum to obtain the yellow solid hole transport material NCz-DM.
4. The method of claim 2, wherein in the mixed solution of step (i), the ratio of 1, 2-dibromobenzene: compound 1: chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II): 1.4-2, molar ratio of potassium phosphate 1; the concentration of the 1, 2-dibromobenzene is 0.2-0.3 mol/L; the molar concentration of the potassium phosphate aqueous solution is 0.5mol/L; the volume ratio of the tetrahydrofuran to the potassium phosphate aqueous solution is 1.
5. The method of claim 2, wherein in the mixed solution of step (ii), the ratio of compound 2: methanesulfonic acid: the molar ratio of dichloro dicyano benzoquinone is 1; the concentration of the compound 2 is 0.1-0.2 mol/L; the volume ratio of the methanesulfonic acid to the dichloromethane to the saturated sodium bicarbonate solution is 1.
6. The method of synthesis of claim 2, wherein in step (iii), compound 3: the molar ratio of NBS is 1; the concentration of the compound 3 in tetrahydrofuran is 0.03-0.08 mol/L; the concentration of NBS in N, N-dimethylformamide is 0.6-1.2 mol/L.
7. The method of claim 2, wherein in the mixed solution of step (iv), the ratio of compound 4:4,4' -dimethoxydiphenylamine: potassium tert-butoxide: palladium acetate: the molar ratio of tri-tert-butylphosphine is 1; the concentration of the compound 4 is 0.01-0.04 mol/L.
8. The application of the non-doped hole transport material with carbazole fused rings as cores in claim 1 as a hole transport layer in perovskite solar cells.
9. The use according to claim 8, wherein the perovskite solar cell is composed of a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode, and is prepared by the following specific steps:
(1) Cutting a transparent conductive substrate into a fixed size, etching, sequentially ultrasonically cleaning the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone sterilization treatment on the substrate;
(2) Preparing a metal oxide electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method, and transferring the metal oxide electron transport layer into a glove box for later use;
(3) Transferring the conductive substrate coated with the electron transmission layer into a glove box, spin-coating the perovskite precursor liquid on the electron transmission layer by a spin-coating method, and dropwise adding a chlorobenzene antisolvent in the process of spin-coating the perovskite precursor liquid to form a perovskite light absorption layer;
(4) Covering the perovskite light absorption layer prepared in the step (3) with chlorobenzene solution containing non-doped hole transport material NCz-DM taking carbazole condensed rings as cores by a spin coating method or a vacuum evaporation method, and sintering at 80-100 ℃ for 5-10 minutes to form an NCz-DM hole transport layer;
(5) And depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
10. The use according to claim 9,
in the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence;
in the step (2), the electron transport layer is one of titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the preparation method of the perovskite precursor solution comprises the following steps: in a glove box, methylamine bromide, formamidine iodide, lead bromide and methylamine chloride were mixed and dissolved in N, N-dimethylformamide in a volume ratio of 4: stirring the mixed solution of dimethyl sulfoxide at room temperature to obtain a perovskite precursor solution;
in the step (4), the chlorobenzene solution of NCz-DM is prepared by dissolving 5-15mg of non-doped hole transport material taking carbazole condensed rings as cores in 1mL of chlorobenzene;
in the step (5), the metal electrode is one of gold, silver or copper.
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| CN114805324A (en) * | 2022-03-31 | 2022-07-29 | 江苏大学 | Carbazole hole transport material and synthesis method and application thereof |
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| CN114805324A (en) * | 2022-03-31 | 2022-07-29 | 江苏大学 | Carbazole hole transport material and synthesis method and application thereof |
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