A polymer superbase for the preparation of organic perovskite solar cells

Abstract

The present invention relates to the field of organic chemical materials, and more specifically to a polymer superbase, its preparation method, and its application in organic perovskite solar cells. This polymer superbase improves photoelectric conversion efficiency through novel molecular design and synthesis. It also improves the stability and lifespan of perovskite solar cells by stabilizing and optimizing the properties of the charge transport layer. This polymer superbase has great potential for application in perovskite solar cells.

Description

Technical Field

[0001] The present invention relates to the field of organic chemical materials, and in particular to a polymer superbase, a preparation method and application in organic perovskite solar cells. Background Art

[0002] Perovskite solar cells, a third-generation photovoltaic technology, have seen rapid development in recent years, with efficiency increasing from 3.8% to 25.57%. Defect passivation of the perovskite surface has been an effective means of further improving device efficiency and stability. Conventional passivation techniques typically involve doping the perovskite precursor with small molecules of Lewis acids or bases. However, these small molecules lack charge transport properties, significantly limiting device performance improvements. Summary of the Invention

[0003] In response to the above-mentioned shortcomings of existing perovskite surface passivation technology, the present invention provides a class of polymer superbases, which are composed of a large conjugated planar system and pyrimidine units, which can not only passivate defects on the perovskite surface, but also transfer charges.

[0004] The technical solution of the present invention is achieved by providing a polymer superbase for preparing organic perovskite solar cells, the general structural formula of which is as follows:

[0005]

[0006] Wherein, R is a conjugated aromatic ring, and the value of n ranges from 15 to 100; the conjugated aromatic ring includes benzene ring, naphthalene ring, diphenylamine, diphenylphosphine, carbazole, thiophene, furan, pyridine, pyrrole, C 60 .

[0007] Preferably, in one embodiment of the present invention, the conjugated aromatic ring includes the following groups and their derivatives:

[0008]

[0009] Preferably, in one embodiment of the present invention, the polymer super base is selected from the following:

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] In another aspect, the present invention also provides a polymer superbase, a preparation method, and its use in organic perovskite solar cells. During the preparation of perovskite solar cells, the polymer superbase is used to passivate surface defects. This effect is achieved by preparing a perovskite precursor solution and then doping it with the polymer superbase.

[0025] The beneficial effects are as follows: Through the design and synthesis of a new super base molecule, the present invention can suppress electron backflow and charge recombination by adjusting the surface chemical properties of the charge transport layer, thereby improving the photoelectric conversion efficiency. At the same time, it can also improve the stability of perovskite solar cells and extend their life by stabilizing and optimizing the properties of the charge transport layer. This has great application prospects in perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Schematic diagram of the structure of a perovskite solar cell device. DETAILED DESCRIPTION

[0027] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention and corresponding drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] The present invention is further described in detail below with reference to the accompanying drawings and examples.

[0029] Example 1

[0030]

[0031] Synthesis of Intermediate M1: 2,6-Dibromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (18.14 g, 50 mmol), 3-bromothiophene (9.78 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0032] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (15.95 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (17.42 g, 80% yield).

[0033] The product from the previous step (21.78 g, 50 mmol) and NBS (19.58 g, 110 mmol) were placed in a 500 mL round-bottom flask and stirred overnight in an ice-water bath. After the reaction, the mixture was washed with 1N sodium thiosulfate solution, extracted with chloroform, washed three times with water, and dried over anhydrous magnesium sulfate. The crude product was purified by silica gel column chromatography to obtain intermediate M1 (29.67 g, 95% yield). 1H NMR(400MHz,Chloroform-d)δ7.93(d,1H),7.69(d,1H),7.55(t,1H).13C NMR(100MHz,Chloroform-d)δ141.52,136.48,125.14,123.05,119.67,109.59.HRMS:[C6H4BrS2]+calculated:218.8938,found:218.8935.

[0034] Synthesis of Formula 1: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M1 (9.08 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (6.53 g, 92% yield). GPC: Mn = 1.2 kDa, Mw / Mn = 1.10.

[0035] Example 2

[0036] The synthesis method is as follows:

[0037]

[0038] Synthesis of Intermediate M16: 2,6-Dibromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (18.14 g, 50 mmol), 6-bromo-4-phenyl-4H-thieno[3,2-b]pyrrole (16.69 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0039] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (21.71 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (23.41 g, 85% yield).

[0040] The product from the previous step (27.54 g, 50 mmol) and NBS (19.58 g, 110 mmol) were placed in a 500 mL round-bottom flask and stirred overnight in an ice-water bath. After the reaction, the mixture was washed with 1N sodium thiosulfate solution, extracted with chloroform, washed three times with water, and dried over anhydrous magnesium sulfate. The crude product was purified by silica gel column chromatography to obtain intermediate M2 (34.36 g, 97% yield).

[0041] Synthesis of Formula 16: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (10.84 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (7.53 g, 85% yield). Mn = 2.4 kDa, Mw / Mn = 1.13.

[0042] Example 3

[0043] The synthesis method is as follows:

[0044]

[0045] Synthesis of Intermediate M33: 2,4,6-tribromopyridine (15.79 g, 50 mmol), 2,7-dibromo-9H-carbazole (19.5 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0046] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (27.99 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (27.73 g, 82% yield).

[0047] Synthesis of Molecular Formula 33: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (10.35 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (7.44 g, 89% yield). GPC: Mn = 1.6 kDa, Mw / Mn = 1.08.

[0048] Example 4

[0049] The synthesis method is as follows:

[0050]

[0051] Synthesis of Intermediate M40: 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), 2,6-dibromo-4-(propan-1-yl-1-yl)pyridine (13.75 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (16.64 g, 85% yield).

[0052] Synthesis of Formula 40: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (5.99 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (5.30 g, 85% yield). GPC: Mn = 5.8 kDa, Mw / Mn = 1.15.

[0053] Example 5

[0054] The synthesis method is as follows:

[0055]

[0056] Synthesis of Intermediate M2: 2,6-Dibromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (18.14 g, 50 mmol), 3-bromofuran (8.82 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0057] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (15.15 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (17.20 g, 82% yield).

[0058] The product from the previous step (20.98 g, 50 mmol) and NBS (19.58 g, 110 mmol) were placed in a 500 mL round-bottom flask and stirred overnight in an ice-water bath. After the reaction, the mixture was washed with 1N sodium thiosulfate solution, extracted with chloroform, washed three times with water, and dried over anhydrous magnesium sulfate. The crude product was purified by silica gel column chromatography to obtain intermediate M1 (28.29 g, 98% yield).

[0059] Synthesis of Formula 2: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M1 (8.83 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (6.16 g, 90% yield). GPC: Mn = 7.4 kDa, Mw / Mn = 1.25.

[0060] Example 6

[0061] The synthesis method is as follows:

[0062]

[0063] Synthesis of Intermediate M3: 2,6-Dibromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (18.14 g, 50 mmol), 3-bromoselenol (12.59 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0064] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (18.30 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (20.5 g, 85% yield).

[0065] The product from the previous step (24.13 g, 50 mmol) and NBS (19.58 g, 110 mmol) were placed in a 500 mL round-bottom flask and stirred overnight in an ice-water bath. After the reaction, the mixture was washed with 1N sodium thiosulfate solution, extracted with chloroform, washed three times with water, and dried over anhydrous magnesium sulfate. The crude product was purified by silica gel column chromatography to obtain intermediate M1 (30.41 g, 95% yield).

[0066] Synthesis of Formula 3: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M1 (9.80 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (6.80 g, 87% yield). GPC: Mn = 6.3 kDa, Mw / Mn = 1.21.

[0067] Example 7

[0068] The synthesis method is as follows:

[0069]

[0070] Synthesis of Intermediate M34: 2,6-Dibromo-4-iodopyridine (18.14 g, 50 mmol), bis(4-bromophenyl)amine (19.62 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0071] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (28.09 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (27.82 g, 82% yield).

[0072] Synthesis of Formula 34: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (10.38 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (7.14 g, 85% yield). GPC: Mn = 7.9 kDa, Mw / Mn = 1.23.

[0073] Example 8

[0074] The synthesis method is as follows:

[0075]

[0076] Synthesis of Intermediate M35: 2,6-Dibromo-4-iodopyridine (18.14 g, 50 mmol), bis(4-bromophenyl)phosphine (20.64 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0077] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (28.94 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (29.90 g, 86% yield).

[0078] Synthesis of Formula 35: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (10.64 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (7.53 g, 87% yield). GPC: Mn = 5.4 kDa, Mw / Mn = 1.38.

[0079] Example 9

[0080] The synthesis method is as follows:

[0081]

[0082] Synthesis of Intermediate M109: 2,6-Dibromo-4-iodopyridine (18.14 g, 50 mmol), 2-bromo-5-(2-bromo-1-phenylvinyl)thiophene-3-amine (21.54 g, 60 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with nitrogen and the mixture was stirred and refluxed at 120°C for 3.5 h. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the crude product, which was directly used in the next step without purification.

[0083] 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine (20.88 g, 150 mmol), the crude product obtained above (28.95 g, 50 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. The atmosphere was replaced with argon and the mixture was stirred and refluxed at 90°C for 3.5 hours. After completion of the reaction, the mixture was cooled to room temperature and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, the mixture was stirred thoroughly, filtered, and dried to obtain the product (28.86 g, 83% yield).

[0084] Synthesis of Molecular Formula 109: Butylmagnesium chloride (7.49 mL of a 2M solution in THF, 15 mmol) was added to intermediate M33 (10.64 g, 15.3 mmol) in anhydrous THF (60 mL) at 10-15°C and purged with nitrogen. The mixture was stirred at 10-15°C for 30 minutes and then heated under gentle reflux for 1 hour. 1,2-Bis(diphenylphosphino)ethane (103.6 mg, 0.26 mmol) and bis(1,5-cyclooctadiene)-nickel(0) (30.4 mg, 0.1 mmol) were then added, and the mixture was refluxed for at least 24 hours. The mixture was cooled to room temperature and poured into methanol to form a precipitate. The precipitate was filtered and washed with methanol and hexane. Purification by Soxhlet extraction in hexane for 2 days finally gave the desired product (7.53 g, 87% yield). GPC: Mn = 5.7 kDa, Mw / Mn = 1.05.

[0085] Example 10

[0086] Perovskite device preparation: Indium tungsten (ITO) conductive glass was ultrasonically cleaned with acetone, deionized water, and isopropyl alcohol, followed by vacuum drying at 80°C for 12 hours. A hole injection layer was evaporated onto the ITO, followed by spin coating of PTAA as a hole transport layer. A perovskite precursor solution was prepared, and 1% superbase was added to the precursor solution, dissolved in DMSO, and spin-coated onto the PTAA film. Annealing was performed at 100°C for 10 minutes. An electron transport layer solution was prepared by dissolving PCBM in chlorobenzene at a concentration of 10 mg / ml and spin-coating the perovskite film. A methanol solution of boron pyrophosphate (BCP) was then spin-coated onto the PCBM, followed by vacuum evaporation of a silver electrode.

[0087] The structural diagram of the final perovskite solar cell device is shown in the figure. Figure 1 , the performance is shown in Table 1 below:

[0088]

[0089]

[0090] The polymer structures listed above are only partial representatives, and other conjugated group-substituted molecules containing the same concept are all within the scope of protection of this patent.

[0091] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A polymer superbase for preparing organic perovskite solar cells, characterized in that: The general structural formula is as follows: Wherein, R is a conjugated aromatic ring, the value of n ranges from 15 to 100, and the conjugated aromatic ring includes benzene ring, naphthalene ring, diphenylamine, diphenylphosphine, carbazole, thiophene, furan, pyridine, pyrrole, C 60 .

2. The polymer superbase for preparing organic perovskite solar cells according to claim 1, characterized in that At least one selected from the following:

3. Use of the polymer superbase for preparing organic perovskite solar cells according to any one of claims 1 to 2 in the process of preparing perovskite solar cells.

4. The use according to claim 3, wherein the polymer super base is doped after the perovskite precursor solution is prepared.

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