Carbazole derivative modified by sulfur-containing functional group as well as preparation method and application of carbazole derivative

Abstract

The invention discloses a sulfur-containing functional group modified carbazole derivative and a preparation method and application thereof, and belongs to the technical field of perovskite solar cell materials. The carbazole derivative modified by the sulfur-containing functional group prepared by the invention is modified by a specific type of group, and ion migration in a perovskite photoactive layer material can be inhibited. After the carbazole derivative modified by the sulfur-containing functional group is applied to a trans-perovskite solar cell as a hole transport layer material, the hole transport capability of the solar cell is obviously improved, the energy conversion efficiency is higher, and the energy loss is smaller. The carbazole derivative modified by the sulfur-containing functional group also has the advantages that the preparation method is simple, and high-precision equipment and technology are not needed.

Description

Technical Field

[0001] The invention belongs to the technical field of perovskite solar cell materials and relates to a carbazole derivative modified with a sulfur-containing functional group and a preparation method and application thereof. Background Art

[0002] Perovskite solar cells are solar cells with organic metal halide perovskite structural materials as core materials. They belong to the third generation of solar cells, also known as new concept solar cells, and have the characteristics of high extinction coefficient, suitable band gap width, high carrier mobility and long diffusion length. At present, the manufacturing cost of single-cell perovskite solar cells is low, the preparation process is simple, the raw materials are abundant, the device structure is simple, and high-efficiency flexible devices can be prepared, which has great application potential in the solar cell market.

[0003] Perovskite solar cells are mainly composed of perovskite light-absorbing layer, electron transport material, electrode and conductive proton decoupling structure. When sunlight shines on the perovskite light-absorbing layer, electron-hole pairs are excited, where electrons flow from the light-absorbing layer through the electron transport material to the electrode, forming a current to generate electrical energy. Electron transport materials are an important component of perovskite solar cells, playing the role of transmitting electrons and blocking holes. Currently, commonly used electron transport materials include metal oxides, organic compounds and composite materials. However, these electron transport materials may decompose or degrade under long-term illumination, high temperature or humidity conditions, resulting in decreased battery stability; their photoelectric conversion efficiency also has certain defects, which limits the further improvement of the performance of perovskite solar cells; and the preparation process of some electron transport materials is relatively complex, requiring high-precision equipment and technology, which increases production costs and preparation difficulties.

[0004] Self-assembled monolayers (SAMs) refer to two-dimensional monolayers spontaneously formed on the solid surface through physical and chemical interactions between molecules and substrate surfaces and between molecules. This film structure has the characteristics of uniformity, close arrangement and low defects. Currently reported SAMs materials are mostly carbazole derivative systems, but there are few reports on carbazole derivatives modified with sulfur-containing functional groups as SAMs materials. Therefore, providing a SAMs material based on carbazole derivatives modified with sulfur-containing functional groups is of great significance to the performance improvement of perovskite solar cells. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a sulfur-containing functional group-modified carbazole derivative and a preparation method and application thereof. The sulfur-containing functional group-modified carbazole derivative is used as a hole transport material in an inverse perovskite solar cell to improve the performance of the device and increase the photoelectric conversion efficiency. The sulfur-containing functional group-modified carbazole derivative of the present invention has a simple preparation process and low production difficulty.

[0006] To achieve the technical purpose of the present invention, on the one hand, the present invention provides a carbazole derivative modified with a sulfur-containing functional group, having a structure as shown in formula (I),

[0007]

[0008] R1 in formula (I) is selected from an alkyl group and a phenyl group, and the alkyl group is any one of a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group;

[0009] R2 in formula (I) is selected from one of a C2-C10 straight-chain alkyl group and an aryl group, and the aryl group is any one of a phenyl group, a furan group, and a thiophene group;

[0010] R3 in formula (I) is selected from one of -COOH and -PO(OH)2; the connection position of the -S-R1 group and carbazole is 2, 7 or 3, 6.

[0011] Furthermore, the sulfur-containing functional group-modified carbazole derivative of the present invention has the structure shown below:

[0012]

[0013]

[0014] On the other hand, the present invention claims a method for preparing a carbazole derivative modified with a sulfur-containing functional group, including method one, method two, method three and method four;

[0015] When R2 is a C2-C10 straight-chain alkyl group and R3 is -PO(OH)2, method 1 is adopted;

[0016] When R2 is a C2-C10 straight-chain alkyl group and R3 is -COOH, the second method is adopted;

[0017] When R2 is an aromatic group and R3 is -PO(OH)2, method 3 is adopted;

[0018] When R2 is an aromatic group and R3 is -COOH, method 4 is adopted.

[0019] Furthermore, the method 1 comprises:

[0020] S1: using dibromocarbazole as a raw material, adding tert-butyldimethylsilyl chloride to protect the nitrogen atom of the dibromocarbazole, and generating silylated dibromocarbazole under the action of a first strong base;

[0021] The first strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; preferably, the first strong base is sodium hydride;

[0022] The synthetic route of S1 is shown in a;

[0023]

[0024] S2: the silylated dibromocarbazole reacts with the thioether compound under the action of a second strong base to generate a silylated carbazole derivative modified with a -S-R1 group;

[0025] The second strong base is selected from any one of n-butyl lithium, tert-butyl lithium and sec-butyl lithium; preferably, the second strong base is n-butyl lithium;

[0026] The synthesis route of S2 is shown in b;

[0027]

[0028] S3: deprotecting the -S-R1 group-modified carbazole silylation derivative under the action of tetrabutylammonium fluoride to generate a -S-R1 group-disubstituted carbazole compound; the synthesis route of S3 is shown in c;

[0029]

[0030] S4: Under the action of a third strong base and a phase transfer catalyst, the -S-R1 group disubstituted carbazole compound reacts with a dibrominated straight-chain alkane to generate a -S-R1 group disubstituted carbazole alkyl bromide derivative; the straight-chain alkane in the dibrominated straight-chain alkane is a C2-C10 straight-chain alkane;

[0031] The third strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; preferably, the third strong base is sodium hydroxide;

[0032] The phase transfer catalyst is selected from any one of tetrabutylammonium bromide, tetrabutylammonium iodide and tetrabutylammonium hydroxide; preferably, the phase transfer catalyst is tetrabutylammonium bromide;

[0033] The synthetic route of S4 is shown in d;

[0034]

[0035] S5: the -S-R1 group disubstituted carbazole alkyl bromide derivative is refluxed with triethyl phosphite to generate a -S-R1 group disubstituted carbazole alkyl phosphite compound; the synthesis route of S5 is shown in e;

[0036]

[0037] S6: the -S-R1 group disubstituted carbazole alkyl phosphite compound reacts with a hydrolysis agent to generate a -S-R1 group disubstituted carbazole alkyl phosphite compound;

[0038] The hydrolysis reagent is trimethylsilyl bromide;

[0039] The synthetic route of S6 is shown in f;

[0040]

[0041] Furthermore, the second method comprises:

[0042] S1: Same as S1 in method 1;

[0043] S2: Same as S2 in method 1;

[0044] S3: Same as S3 in method 1;

[0045] S4: Under the action of a fourth strong base, the -S-R1 group disubstituted carbazole compound is docked with bromoalkane acid methyl ester, accompanied by ester hydrolysis, and then subjected to acidification treatment to generate a -S-R1 group disubstituted carbazole alkyl carboxylic acid compound;

[0046] The fourth strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; preferably, the fourth strong base is sodium hydroxide;

[0047] The alkane in the methyl bromide is a C2-C10 straight-chain alkane;

[0048] The acidification treatment uses dilute hydrochloric acid with a mass fraction of 10%;

[0049] The synthetic route of S4 is shown in g;

[0050]

[0051] Furthermore, the method three comprises:

[0052] S1: Same as S1 in method 1;

[0053] S2: Same as S2 in method 1;

[0054] S3: Same as S3 in method 1;

[0055] S4: the -S-R1 group disubstituted carbazole compound and dibromoaryl hydrocarbon undergo carbon-nitrogen coupling under the catalysis of CuI and the action of the fifth strong base to generate a -S-R1 group disubstituted carbazole aryl bromide derivative;

[0056] The fifth strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; preferably, the fifth strong base is potassium carbonate;

[0057] The synthetic route of S4 is shown in h;

[0058] S5: The -S-R1 group disubstituted carbazole aryl bromide derivative is heated with triethyl phosphite

[0059]

[0060] Reflux to generate a -S-R1 group disubstituted carbazole aryl phosphite compound; the synthesis route of S5 is shown in i;

[0061]

[0062] S6: the -S-R1 group disubstituted carbazole aryl phosphate compound is hydrolyzed with a hydrolysis agent to generate a -S-R1 group disubstituted carbazole aryl phosphate compound;

[0063] The hydrolysis reagent is trimethylsilyl bromide;

[0064] The synthetic route of S6 is shown in j;

[0065]

[0066] Furthermore, the method 4 comprises:

[0067] S1: Same as S1 in method 3;

[0068] S2: Same as S2 in method 3;

[0069] S3: Same as S3 in method 3;

[0070] S4: Same as S4 in method 3;

[0071] S5: the -S-R1 group disubstituted carbazole aryl bromide derivative reacts with diethyl oxalate in the presence of a sixth strong base via a palladium-catalyzed reaction to generate a -S-R1 group disubstituted carbazole aryl formic acid compound;

[0072] The sixth strong base is selected from any one of n-butyl lithium, tert-butyl lithium and sec-butyl lithium; preferably, the sixth strong base is n-butyl lithium;

[0073] The palladium catalyst used in the palladium-catalyzed reaction is selected from any one of tetrakistriphenylphosphine palladium, bistriphenylphosphine palladium dichloride, and 1,1'-bisdiphenylphosphinoferrocene palladium dichloride;

[0074] The synthesis route of S5 is shown in k;

[0075]

[0076] On the other hand, the present invention claims the use of the above-mentioned sulfur-containing functional group-modified carbazole derivatives in trans-perovskite solar cells.

[0077] In addition, the present invention seeks to protect an inverse perovskite solar cell comprising a hole transport layer, wherein the material of the hole transport layer is the above-mentioned carbazole derivative modified with a sulfur-containing functional group.

[0078] Furthermore, after the prepared sulfur-containing functional group-modified carbazole derivative is applied as a hole transport layer material to an inverted perovskite solar cell, the hole transport capacity of the solar cell is significantly improved. The sulfur-containing functional group-modified carbazole compound of the present invention is applied as a hole transport material in a perovskite solar cell, has a high energy conversion efficiency, can better convert light energy into electrical energy, can generate more current when exposed to light, and the efficiency of the battery is high at maximum output power, and the energy loss is small.

[0079] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0080] (1) The sulfur-containing functional group-modified carbazole derivatives prepared by the present invention are applied as hole transport materials to trans-perovskite solar cells, which can improve the hole transport capacity of the solar cells. Compared with solar cells composed of existing hole transport materials, the open circuit voltage, short circuit current, fill factor, and photoelectric conversion efficiency of solar cells using the sulfur-containing functional group-modified carbazole derivatives of the present invention are all improved. It can be seen that the sulfur-containing functional group-modified carbazole compounds of the present invention are applied as hole transport materials in trans-perovskite solar cells, have high energy conversion efficiency, can better convert light energy into electrical energy, can generate more current when exposed to light, and the efficiency of the battery is high at maximum output power, and the energy loss is small.

[0081] (2) The sulfur-containing functional group-modified carbazole derivative prepared by the present invention is a SAMs material that can inhibit ion migration in the perovskite photoactive layer material. The sulfur-containing functional group-modified carbazole derivative of the present invention also has the advantages of simple preparation method and no need for high-precision equipment and technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0082] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention.

[0083] Figure 1 is the H NMR spectrum of compound 14.

[0084] Figure 2 is the H NMR spectrum of compound 18.

[0085] Figure 3 is the H NMR spectrum of compound 15.

[0086] Figure 4 is the H NMR spectrum of compound 19.

[0087] Figure 5 is the H NMR spectrum of compound 21.

[0088] Figure 6 is the H NMR spectrum of compound 47.

[0089] Figure 7 is the H NMR spectrum of compound 24.

[0090] Figure 8 is the H NMR spectrum of compound 50.

[0091] Fig. 9 Schematic diagram of the structure of an inverted perovskite solar cell. DETAILED DESCRIPTION

[0092] The technical scheme of the present invention is described below in conjunction with the embodiments, but the present invention is not limited to the following embodiments. The experimental methods and detection methods described in each embodiment are conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.

[0093] Example 1

[0094] This example provides the synthesis of compound 14, wherein R2 of compound 14 is a multi-carbon straight-chain alkane and R3 is -PO(OH)2, and the preparation method 1 specifically comprises the following steps:

[0095]

[0096] S1: Add dibromocarbazole (10 g, 30.76 mmol) and tetrahydrofuran (100 mL) into a three-necked flask, dissolve and add sodium hydride (1.54 g, 64.17 mmol) in batches, add TBSCl (10.57 g, 64.17 mmol) dropwise, and react at 25°C for 4 h. Extract with dichloromethane, wash with water until neutral, pass the organic layer through a column, and concentrate the column liquid under reduced pressure to obtain intermediate 14-1 (12.43 g, yield 92%), a white solid with a purity of 99%. Mass spectrum: C 18 H 21 Br2NSi, theoretical value: 439.27, measured value: 439.24. 1 H NMR(400MHz,DMSO-d6)δ0.28-0.38(6H,0.33(s),0.33(s)),0.81(9H,s),7.13(2H,d d, J=8.4, 1.8Hz), 7.47-7.70 (4H, 7.54 (dd, J=8.4, 0.4Hz), 7.64 (dt, J=1.8, 0.4Hz).

[0097]

[0098] S2: Add 60 mL of tetrahydrofuran and intermediate 14-1 (12.43 g, 28.29 mmol) to a three-necked flask, cool to -60°C, drop 24.9 mL (62.24 mmol) of n-butyl lithium, react at -60°C for 1 hour, drop diisopropyl disulfide (17.00 g, 113.16 mmol), and react at -60°C for 2 hours after the addition is complete. The reaction solution is quenched with water, extracted with dichloromethane, washed with water until neutral, and passed through a column to obtain intermediate 14-2 (9.12 g, yield 75%), a white solid with a purity of 99.3%. Mass spectrum: C 24 H 35 NS2Si, theoretical value: 429.76, measured value: 429.73. 1 H NMR(400MHz, DMSO-d6)δ0.28-0.38(6H,0.33(s),0.33(s)),0.77(9H,s),1.05(12H,d,J=6.6Hz),4.08(2 H,sept,J=6.6Hz), 6.93(2H,dd,J=8.4,1.8Hz), 7.40(2H,dd,J=8.4,0.5Hz), 7.72(2H,dt,J=1.8,0.5Hz).

[0099]

[0100] S3: Add intermediate 14-2 (9.12 g, 21.22 mmol) and 50 mL of tetrahydrofuran to a three-necked flask, add tetrabutylammonium fluoride (8.32 g, 31.83 mmol) after dissolving, and react at 25°C for 1 h. After quenching with saturated ammonium chloride, extract with toluene, wash with water until neutral, and concentrate the organic layer to obtain intermediate 14-3 (5.02 g, yield 75%), an off-white solid with a purity of 98%. Mass spectrum: C 18 H 21 NS2, theoretical value: 315.49, measured value: 315.43. 1 H NMR (400MHz, DMSO-d6) δ2.68 (6H, s), 7.22 (2H, dd, J = 8.4, 1.8Hz), 7.67-7.80 (4H, 7.72 (dt, J = 1.8, 0.5Hz), 7.73 (dd, J = 8.4, 0.5Hz)).

[0101]

[0102] S4: Add 24 mL of toluene, intermediate 14-3 (5.02 g, 15.88 mmol), tetrabutylammonium bromide (0.05 g, 0.16 mmol), 1.4-dibromobutane (17.14 g, 79.40 mmol) to a three-necked flask, and dropwise add sodium hydroxide aqueous solution (2.54 g, 63.52 mmol). After the dropwise addition, heat to 60 °C and react for 6 h. The reaction solution is extracted with ethyl acetate, washed with water until neutral, and passed through a column to obtain intermediate 14-4 (5.37 g, yield 75%), an off-white solid with a purity of 92.5%. Mass spectrum: C 22 H 28 BrNS2, theoretical value: 450.50, measured value: 450.48. 1 H NMR(400MHz, DMSO-d6)δ1.00(12H,d,J=6.6Hz),1.89-2.08(4H,1.95(quint,J=7.4Hz),2.02(tt,J=7.4,6.9Hz)),3.29(2H,t,J=6.9Hz) ,4.09(2H,sept,J=6.6Hz), 4.58(2H,t,J=7.4Hz), 6.94(2H,dd,J=8.4,1.8Hz), 7.46(2H,dd,J=8.4,0.5Hz), 7.73(2H,dt,J=1.8,0.5Hz).

[0103]

[0104] S5: Add triethyl phosphite (15.84 g, 95.33 mmol) and intermediate 14-4 (5.37 g, 11.91 mmol) into a three-necked flask, and heat to 140°C for 4 h. Remove the remaining triethyl phosphite from the reaction solution directly with an oil pump to obtain intermediate 14-5 (5.75 g, yield 95%), a brown liquid with a purity of 90%. Mass spectrum: C 26 H 38 O3NPS2, theoretical value: 507.69, measured value: 507.67. 1 HNMR (400MHz, DMSO-d6) δ1.00 (12H, d, J = 6.6Hz), 1.26 (6H, t, J = 7.1Hz), 1.76 (2H, quint, J = 7.4Hz), 1.96 (2H, quint, J = 7.4Hz), 2.49 (2H, t, J = 7.4Hz), 4.03-4. 19(6H,4.09(sept,J=6.6Hz),4.13(q,J=7.1Hz)),4.59(2H,t,J=7.4Hz),6.94( 2H,dd,J=8.4,1.8Hz), 7.46(2H,dd,J=8.4,0.5Hz), 7.73(2H,dt,J=1.8,0.5Hz).

[0105]

[0106] S6: Add 40 mL of dioxane, intermediate 14-5 (5.75 g, 11.31 mmol), and trimethylsilyl bromide (13.85 g, 90.48 mmol) to a three-necked flask and react at 25°C for 2 h. The reaction solution was quenched with methanol and poured into water, filtered, and the filter cake was slurried with water until neutral, and recrystallized and purified to obtain compound 14 (0.89 g, yield 20%), an off-white solid with a purity of 98%. Mass spectrum: C 22 H 30 O3NPS2, theoretical value: 451.58, measured value: 451.54. The H NMR spectrum of compound 14 is shown in Figure 1 shown. 1 HNMR (400MHz, DMSO-d6) δ8.34(s,2H),7.71(d,J=2.1Hz,2H),7.36(d,J=7.6Hz,1H),7.29(d,J=7.5Hz,1H),7.20(dd,J=7 .5,2.1Hz,2H),4.14(t,J=5.1Hz,2H),3.64-3.55(m,2H),1.93-1.74(m,4H),1.73-1.60(m,2H),1.28(d,J=5.6Hz,12H).

[0107] Example 2

[0108] This example provides the synthesis of compound 18, wherein R2 of compound 18 is a multi-carbon straight-chain alkane and R3 is -PO(OH)2, and the preparation method 1 specifically comprises the following steps:

[0109] S1: The synthesis of intermediate 18-1 is the same as the synthesis of intermediate 14-1 in Example 1.

[0110]

[0111] S2: Add DMF 120mL, intermediate 18-1 (12g, 27.31mmol), zinc powder (8.93g, 136.55mmol), S-phenylthiophenyl sulfone (27.35g, 109.24mmol), nickel bromide (0.30g, 1.36mmol), 1,10-phenanthroline (0.30g, 1.64mmol) into a three-necked flask, and heat to 50°C for 6h. The reaction solution was quenched with water, extracted with ethyl acetate, washed with water until neutral, and passed through a column to obtain intermediate 18-2 (10.88g, yield 80%), an off-white solid with a purity of 99.1%. Mass spectrum: C 30 H 31 NS2Si, theoretical value: 497.79, measured value: 497.76. 1 H NMR(400MHz, DMSO-d6)δ0.45-0.55(6H,0.50(s),0.50(s)),0.77(9H,s),6.98-7.38(12H,7.04(dddd,J=7.9,1.6,1.2,0.5Hz),7.14( tt,J=7.9,1.6Hz),7.24(tdd,J=7.9,1.5,0.5Hz),7.31(dd,J=8.4,1.8Hz)),7.51(2H,dd,J=8.4,0.4Hz),7.69(2H,dt,J=1.8,0.4Hz).

[0112]

[0113] S3: Add intermediate 18-2 (10.88 g, 21.86 mmol) and 50 mL of tetrahydrofuran to a three-necked flask, add tetrabutylammonium fluoride (8.57 g, 32.79 mmol) after dissolving, and react at 25°C for 1 h. After quenching with saturated ammonium chloride, extract with toluene, wash with water until neutral, and concentrate the organic layer to obtain intermediate 18-3 (6.28 g, yield 75%), an off-white solid with a purity of 98%. Mass spectrum: C 24 H 17 NS2, theoretical value: 383.53, measured value: 383.51. 1H NMR (400MHz, DMSO-d6) δ6.98-7.33(12H,7.04(dddd,J=7.9,1.6,1.2,0.5Hz),7.14(tt,J=7.9,1.6Hz),7.24(tdd, J=7.9,1.5,0.5Hz),7.27(dd,J=8.4,1.8Hz)),7.70-7.84(4H,7.76(dt,J=1.8,0.4Hz),7.78(dd,J=8.4,0.4Hz)).

[0114]

[0115] S4: Add 30 mL of toluene, intermediate 18-3 (6.28 g, 16.37 mmol), tetrabutylammonium bromide (0.05 g, 0.16 mmol), 1.4-dibromobutane (17.67 g, 81.85 mmol) to a three-necked flask, and dropwise add sodium hydroxide aqueous solution (2.62 g, 65.48 mmol). After the dropwise addition, heat to 60 °C and react for 6 h. The reaction solution is extracted with ethyl acetate, washed with water until neutral, and passed through a column to obtain intermediate 18-4 (6.36 g, yield 75%), an off-white solid with a purity of 93.0%. Mass spectrum: C 28 H 24 BrNS2, theoretical value: 518.53, measured value: 518.50. 1 H NMR (400MHz, DMSO-d6) δ1.95-2.13(4H,2.02(tt,J=6.9,6.8Hz),2.06(tt,J=6.8,6 .2Hz)),3.29(2H,t,J=6.9Hz),4.53(2H,t,J=6.2Hz),6.98-7.31(12H,7.04(dddd, J=7.9,1.6,1.2,0.5Hz),7.14(tt,J=7.9,1.6Hz),7.19(dd,J=8.4,1.8Hz),7.24(t dd,J=7.9,1.5,0.5Hz)), 7.55(2H,dd,J=8.4,0.5Hz), 7.70(2H,dt,J=1.8,0.5Hz).

[0116]

[0117] S5: Add triethyl phosphite (16.30 g, 98.12 mmol) and intermediate 18-4 (6.36 g, 12.26 mmol) into a three-necked flask, and heat to 140°C for 4 h. Remove the remaining triethyl phosphite from the reaction solution directly with an oil pump to obtain intermediate 18-5 (6.71 g, yield 95%), a brown liquid with a purity of 91.3%. Mass spectrum: C32 H 34 O3NPS2, theoretical value: 575.72, measured value: 575.70. 1 HNMR(400MHz,DMSO-d6)δ1.26(6H,t,J=7.1Hz),1.76(2H,tt,J=7.4,7.3Hz),2.02(2H,tt,J =7.3,6.2Hz),2.49(2H,t,J=7.4Hz),4.13(4H,q,J=7.1Hz),4.53(2H,t,J=6.2Hz),6.98-7.3 1(12H,7.04(dddd,J=7.9,1.6,1.2,0.5Hz),7.14(tt,J=7.9,1.6Hz),7.19(dd,J=8.4,1.8Hz ), 7.24 (tdd, J = 7.9, 1.5, 0.5Hz)), 7.55 (2H, dd, J = 8.4, 0.5Hz), 7.70 (2H, dt, J = 1.8, 0.5Hz).

[0118]

[0119] S6: Add 40 mL of dioxane, intermediate 18-5 (6.71 g, 11.66 mmol), and trimethylsilyl bromide (14.28 g, 93.27 mmol) to a three-necked flask and react at 25°C for 2 h. The reaction solution was quenched with methanol and poured into water, filtered, and the filter cake was slurried with water until neutral, and purified by recrystallization to obtain compound 18 (1.51 g, yield 25%), an off-white solid with a purity of 98%. Mass spectrum: C 28 H 26 O3NPS2, theoretical value: 519.61, measured value: 519.60. The H NMR spectrum of compound 18 is shown in Figure 2 shown. 1 HNMR (400MHz, DMSO-d6) δ8.34(s,2H),7.94(d,J=2.1Hz,2H),7.43(d,J=7.1Hz,1H),7.37(ddd,J=7.8,3.6,1.9Hz,5H),7. 32(ddt,J=6.6,5.7,1.2Hz,6H),7.25(dd,J=7.1,2.1Hz,2H),4.14(t,J=5.1Hz,2H),1.93-1.74(m,4H),1.73-1.60(m,2H).

[0120] Example 3

[0121] This example provides the synthesis of compound 15, wherein R2 of compound 15 is a multi-carbon straight-chain alkane and R3 is -COOH, and the preparation method 2 is adopted, which specifically comprises the following steps:

[0122] S1~S3: The synthesis of intermediates 15-1~intermediate 15-3 is the same as the synthesis of intermediates 14-1~intermediate 14-3 in Example 1.

[0123]

[0124] S4: Add 40 mL of toluene, intermediate 15-3 (4.86 g, 15.42 mmol), ethyl 3-bromopropionate (8.37 g, 46.26 mmol), tetrabutylammonium bromide (0.05 g, 0.15 mmol) to a three-necked flask, and dropwise add aqueous sodium hydroxide solution (1.54 g, 38.55 mmol). After the dropwise addition, heat to 60 °C and react for 3 h. The reaction solution was quenched with 10% hydrochloric acid, washed with water until neutral, and passed through a column to obtain compound 15 (2.98 g, yield 50%), an off-white solid with a purity of 99.0%. Mass spectrum: C 21 H 25 O2NS2, theoretical value: 387.56, measured value: 387.54. The H NMR spectrum of compound 15 is shown in Figure 3 shown. 1 H NMR (400MHz, DMSO-d6) δ7.71 (d, J = 2.1Hz, 2H), 7.33-7.17 (m, 4H), 4.43 (t, J = 6. 7Hz, 2H), 3.57 (m, J = 5.6Hz, 2H), 2.72 (t, J = 6.7Hz, 2H), 1.28 (d, J = 5.6Hz, 12H).

[0125] Example 4

[0126] This example provides the synthesis of compound 19, wherein R2 of compound 19 is a multi-carbon straight-chain alkane and R3 is -COOH, and the preparation method 2 is adopted, which specifically comprises the following steps:

[0127] S1~S3: The synthesis of intermediates 19-1~intermediate 19-3 is the same as the synthesis of intermediates 18-1~intermediate 18-3 in Example 2.

[0128]

[0129] S4: Add 40 mL of toluene, intermediate 19-3 (3.00 g, 7.82 mmol), ethyl 3-bromopropionate (4.25 g, 23.46 mmol), tetrabutylammonium bromide (0.025 g, 0.078 mmol) to a three-necked flask, and dropwise add aqueous sodium hydroxide solution (0.78 g, 19.55 mmol). After the dropwise addition, heat to 60 ° C and react for 3 h. The reaction solution was quenched with 10% hydrochloric acid, washed with water until neutral, and passed through a column to obtain compound 19 (1.85 g, yield 52%), an off-white solid with a purity of 99.1%. Mass spectrum: C 27 H 21 O2NS2, theoretical value: 455.59, measured value: 455.58. The H NMR spectrum of compound 19 is shown in Figure 4 shown. 1 H NMR (400MHz, DMSO-d6) δ12.09(s,1H),7.94(d,J=2.1Hz,2H),7.43(d,J=7.1Hz,1H),7.37(ddd,J=7.8,3.6,1.9Hz, 5H), 7.32 (ddt, J=6.6, 5.7, 1.2Hz, 6H), 7.25 (dd, J=7.1, 2.1Hz, 2H), 4.43 (t, J=6.7Hz, 2H), 2.72 (t, J=6.7Hz, 2H).

[0130] Example 5

[0131] This example provides the synthesis of compound 21, wherein R2 of compound 21 is phenyl and R3 is -PO(OH)2, and the preparation method 3 is adopted, which specifically comprises the following steps:

[0132] S1: The synthesis of intermediate 21-1 is the same as the synthesis of intermediate 14-1 in Example 1.

[0133]

[0134] S2: Add 60 mL of tetrahydrofuran and intermediate 21-1 (12.43 g, 28.29 mmol) to a three-necked flask, cool to -60°C, drop 24.9 mL of n-butyl lithium (62.24 mmol), react at -60°C for 1 hour, drop dimethyl disulfide (10.65 g, 113.16 mmol), and react at -60°C for 2 hours after the addition is complete. The reaction solution is quenched with water, extracted with dichloromethane, washed with water until neutral, and passed through a column to obtain intermediate 21-2 (7.93 g, yield 75%), an off-white solid with a purity of 99.3%. Mass spectrum: C 20 H 27 NS2Si, theoretical value: 373.65, measured value: 373.61. 1H NMR(400MHz, DMSO-d6)δ=0.50-0.60(6H,0.55(s),0.55(s)),0.77(9H,s),2.70(6H,s) ,7.12(2H,dd,J=8.4,1.8Hz), 7.39(2H,dd,J=8.4,0.5Hz), 7.65(2H,dt,J=1.8,0.5Hz).

[0135]

[0136] S3: Add intermediate 21-2 (7.93 g, 21.22 mmol) and 50 mL of tetrahydrofuran to a three-necked flask, add tetrabutylammonium fluoride (8.32 g, 31.83 mmol) after dissolving, and react at 25°C for 1 h. After quenching with saturated ammonium chloride, extract with toluene, wash with water until neutral, and concentrate the organic layer to obtain intermediate 21-3 (4.12 g, yield 75%), an off-white solid with a purity of 98%. Mass spectrum: C 14 H 13 NS2, theoretical value: 259.38, measured value: 259.33. 1 H NMR (400MHz, DMSO-d6) δ = 2.68 (6H, s), 7.22 (2H, dd, J = 8.4, 1.8Hz), 7.67-7.80 (4H, 7.72 (dt, J = 1.8, 0.5Hz), 7.73 (dd, J = 8.4, 0.5Hz).

[0137]

[0138] S4: Add 40 mL of toluene, intermediate 21-3 (3.00 g, 12.28 mmol), p-dibromobenzene (2.89 g, 12.28 mmol), cuprous iodide (0.09 g, 0.49 mmol), potassium carbonate (3.39 g, 24.56 mmol), 1.10-phenanthroline (0.09 g, 0.50 mmol) into a three-necked flask, and heat to reflux for 80 h. The reaction solution was washed with water until neutral, concentrated under reduced pressure to remove the organic solvent, and recrystallized to obtain intermediate 21-4 (4.37 g, yield 86%), an off-white solid with a purity of 98.3%. Mass spectrum: C 20 H 16 BrNS2, theoretical value: 414.38, measured value: 414.35. 1H NMR (400MHz, DMSO-d6) δ = 2.82 (6H, s), 7.21 (2H, dd, J = 8.5, 1.8Hz), 7.47 (2H, ddd, J = 8.3, 1.6, 0.4Hz), 7.71-7.84(4H,7.78(ddd,J=8.3,1.5,0.4Hz),7.79(dt,J=1.8,0.5Hz)),7.99(2H,dd,J=8.5,0.4Hz).

[0139]

[0140] S5: Add triethyl phosphite (14.01 g, 84.32 mmol) and intermediate 21-4 (4.38 g, 10.54 mmol) into a three-necked flask, and heat to 140°C for 4 h. Remove the remaining triethyl phosphite from the reaction solution directly with an oil pump to obtain intermediate 21-5 (4.73 g, yield 95%), a brown liquid with a purity of 90.9%. Mass spectrum: C 24 H 26 O3NPS2, theoretical value: 471.57, measured value: 471.55. 1 HNMR (400MHz, DMSO-d6) δ = 1.26 (6H, t, J = 7.1Hz), 2.90 (6H, s), 4.02 (4H, q, J = 7.1Hz), 7.31 (2H, dd, J = 8.5, 1.8Hz), 7.79 (2H, ddd,J=8.6,1.8,0.5Hz),7.87-8.03(6H,7.93(ddd,J=8.6,2.2,0.5Hz),7.94(dt,J=1.8,0.5Hz),7.97(dd,J=8.5,0.4Hz)).

[0141]

[0142] S6: Add 40 mL of dioxane, intermediate 21-5 (4.73 g, 10.03 mmol), and trimethylsilyl bromide (12.28 g, 80.24 mmol) to a three-necked flask and react at 25°C for 2 h. The reaction solution was quenched with methanol and poured into water, filtered, and the filter cake was slurried with water until neutral, and purified by recrystallization to obtain compound 21 (0.96 g, yield 23%), an off-white solid with a purity of 98.2%. Mass spectrum: C 20 H 18 O3NPS2, theoretical value: 415.46, measured value: 415.44. The H NMR spectrum of compound 21 is shown in Figure 5 shown. 1HNMR (400MHz, DMSO-d6) δ9.26 (s, 2H), 7.83 (d, J = 2.1 Hz, 2H), 7.76-7.64 (m, 5H), 7.61 (d, J = 7.1 Hz, 1H), 7.16 (dd, J = 7.1, 2.2 Hz, 2H), 2.51 (s, 6H).

[0143] Example 6

[0144] This example provides the synthesis of compound 47, wherein R2 of compound 47 is furan and R3 is -PO(OH)2, and the preparation method 3 is adopted, which specifically comprises the following steps:

[0145] S1~S3: The synthesis of intermediates 47-1~47-3 is the same as the synthesis of intermediates 18-1~18-3 in Example 2.

[0146]

[0147] S4: Add 40 mL of toluene, intermediate 47-3 (4.00 g, 10.80 mmol), 2,5-dibromofuran (2.44 g, 10.80 mmol), cuprous iodide (0.08 g, 0.43 mmol), potassium carbonate (2.99 g, 21.60 mmol), 1,10-phenanthroline (0.08 g, 0.45 mmol) into a three-necked flask, and heat to reflux for 80 h. The reaction solution was washed with water until neutral, concentrated under reduced pressure to remove the organic solvent, and recrystallized to obtain intermediate 47-4 (4.56 g, yield 80%), an off-white solid with a purity of 98.0%. Mass spectrum: C 28 H 18 OBrNS2, theoretical value: 528.48, measured value: 528.45. 1 H NMR (400MHz, DMSO-d6) δ6.35-6.47(2H,6.41(d,J=3.5Hz),6.42(d,J=3.5Hz)),6.98-7.43(12H,7.04(dddd,J=7.9,1.6,1.2,0.5Hz),7.14(tt ,J=7.9,1.6Hz),7.24(tdd,J=7.9,1.5,0.5Hz),7.36(dd,J=8.3,1.8Hz)),7.76-7.94(4H,7.82(dd,J=8.3,0.4Hz),7.89(dt,J=1.8,0.4Hz)).

[0148]

[0149] S5: Add triethyl phosphite (11.46 g, 68.96 mmol) and intermediate 47-4 (4.56 g, 8.62 mmol) into a three-necked flask, and heat to 140°C for 4 h. Remove the remaining triethyl phosphite from the reaction solution directly with an oil pump to obtain intermediate 47-5 (4.70 g, yield 93%), a brown liquid with a purity of 90.4%. Mass spectrum: C 32 H 28 O4NPS2, theoretical value: 585.67, measured value: 585.63. 1 HNMR(400MHz,DMSO-d6)δ1.20-1.31(6H,1.26(t,J=7.1Hz),1.26(t,J=7.1Hz)),3.97-4.08(4H,4.0 3(q,J=7.1Hz),4.03(q,J=7.1Hz)),6.38(1H,d,J=3.4Hz),6.98-7.31(10H,7.04(dddd,J=7.9,1.6, 1.2,0.5Hz),7.14(tt,J=7.9,1.6Hz),7.24(tdd,J=7.9,1.5,0.5Hz)),7.37-7.49(3H,7.43(dd,J=8 .3, 1.8Hz), 7.43 (d, J = 3.4Hz)), 7.85-8.05 (4H, 7.91 (dd, J = 8.3, 0.4Hz), 8.00 (dt, J = 1.8, 0.4Hz)).

[0150]

[0151] S6: Add 40 mL of dioxane, intermediate 47-5 (4.70 g, 8.02 mmol), and trimethylsilyl bromide (9.82 g, 64.16 mmol) to a three-necked flask and react at 25°C for 2 h. The reaction solution was quenched with methanol and poured into water, filtered, and the filter cake was slurried with water until neutral, and purified by recrystallization to obtain compound 47 (0.85 g, yield 20%), an off-white solid with a purity of 98.3%. Mass spectrum: C 28 H 20 O4NPS2, theoretical value: 529.56, measured value: 529.55. The H NMR spectrum of compound 47 is shown in Figure 6 shown. 1 HNMR (400MHz, DMSO-d6) δ8.38 (s, 2H), 7.79 (d, J = 2.1Hz, 2H), 7.61 (d, J = 7.1Hz, 1H), 7.53 (d, J = 6.9Hz, 1H), 7.41-7.25 (m, 12H), 6.93 (q, J = 4.6Hz, 2H).

[0152] Example 7

[0153] This example provides the synthesis of compound 24, wherein R2 of compound 24 is phenyl and R3 is -COOH, and the preparation method 4 is adopted, which specifically comprises the following steps:

[0154] S1~S4: The synthesis of intermediates 24-1~24-4 is the same as the synthesis of intermediates 21-1~21-4 in Example 5.

[0155]

[0156] S5: Add 80 mL of tetrahydrofuran and intermediate 24-4 (4.00 g, 9.65 mmol) to a three-necked flask, cool to -50°C, and then drop n-butyl lithium (4.6 mL, 11.58 mmol). After the temperature is maintained for 2 hours, slowly introduce carbon dioxide gas and react at -55°C for 4 hours. After the reaction solution slowly rises to room temperature naturally, it is quenched with 10% dilute hydrochloric acid, filtered, and the filter cake is slurried with water until neutral, and purified by recrystallization to obtain compound 24 (1.93 g, yield 55%), an off-white solid with a purity of 98.8%. Mass spectrum: C 21 H 17 O2NS2, theoretical value: 364.46, measured value: 364.44. The H NMR spectrum of compound 24 is shown in Figure 7 shown. 1 H NMR(400MHz,DMSO-d6)δ13.02(s,1H),7.95–7.88(m,2H),7.83(d,J=2.1Hz,2H),7.65 (dd,J=25.0,7.1Hz,2H),7.58–7.50(m,2H),7.16(dd,J=7.1,2.2Hz,1H),2.51(s,6H).

[0157] Example 8

[0158] This example provides the synthesis of compound 50, wherein R2 of compound 50 is furan and R3 is -COOH, and the preparation method 4 is adopted, which specifically comprises the following steps:

[0159] S1~S4: The synthesis of intermediates 50-1~intermediate 50-4 is the same as the synthesis of intermediates 47-1~intermediate 47-4 in Example 6.

[0160]

[0161] S5: Add 80 mL of tetrahydrofuran and intermediate 50-4 (4.00 g, 7.57 mmol) to a three-necked flask, cool to -50°C, and then drop n-butyl lithium (3.6 mL, 9.08 mmol). After the temperature is maintained for 2 hours, slowly introduce carbon dioxide gas and react at -55°C for 4 hours. After the reaction solution slowly rises to room temperature naturally, it is quenched with 10% dilute hydrochloric acid, filtered, and the filter cake is slurried with water until neutral, and purified by recrystallization to obtain compound 50 (1.98 g, yield 53%), an off-white solid with a purity of 98.2%. Mass spectrum: C 29 H 19 O3NS2, theoretical value: 493.60, measured value: 493.54. The H NMR spectrum of compound 50 is shown in Figure 8 shown. 1 H NMR (400MHz, DMSO-d6) δ 12.36 (s, 1H), 7.79 (d, J = 2.1Hz, 2H), 7.66 (d, J = 7.0Hz, 1H), 7.58 (d, J = 6.9Hz, 1H), 7.43-7.22 (m, 13H), 6.83 (d, J = 5.4Hz, 1H).

[0162] Example 9

[0163] This example tests the performance of the self-assembled hole transport material having the structure of general formula (I).

[0164] The material having the general formula (I) is used as a self-assembled hole transport material and combined with other functional layers of an inverse perovskite solar cell to make an inverse perovskite solar cell, the structure of which is as follows: Fig. 9 As shown, the inverse perovskite solar cell comprises, from bottom to top, a transparent conductive electrode (ITO / FTO) 10 grown on a substrate layer (not shown in the figure); a hole transport layer (NiOx) 20; a SAM layer 30 composed of a carbazole derivative modified with a sulfur-containing functional group of the present invention; a perovskite layer 40; an electron transport layer (C 60 / PCBM) 50; buffer layer (SnO2) 60; metal electrode (Ag) 70. The SAM layer material of the inverse perovskite solar cell uses compounds 14, 18, 15, 19, 21, 47, 24, and 50 prepared in Examples 1 to 8, and the existing 2PACz is used as the SAM layer material as a control. The sample perovskite solar cell is operated at AM1.5G, 100mW / cm 2 The JV performance curve of the battery was tested under light, and the following parameters were obtained: open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE). The specific test results are shown in Table 1.

[0165] Table 1: Performance parameters of inverse perovskite solar cells

[0166]

[0167] As shown in Table 1, the application of the compound prepared in the present invention as a hole transport material in an inverse perovskite solar cell significantly improves the hole transport capacity of the solar cell, and the open circuit voltage of the solar cell is increased from 1.08 V to 1.12-1.15 V, and the short circuit current is increased from 22.67 mA / cm 2 Increased to a maximum of 24.08mA / cm 2 , the fill factor increased from 74.51% to 75.99-77.42%, and the photoelectric conversion efficiency increased from 19.41% to 20.12-21.35%. It can be seen that the sulfur-containing functional group-modified carbazole compound of the present invention is used as a hole transport material in an inverse perovskite solar cell, has a high energy conversion efficiency, can better convert light energy into electrical energy, can generate more current when exposed to light, and the efficiency of the battery is high at the maximum output power, and the energy loss is small.

[0168] The embodiments described above are part of the embodiments of the present invention, but not all of them. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but only represents selected embodiments of the present invention. All other embodiments obtained without creative work and related deductions and substitutions made by ordinary technicians in the field under the conditions of the concept of the present invention belong to the scope of protection of the present invention.

Claims

1. A carbazole derivative modified with a sulfur-containing functional group, characterized in that: Having a structure as shown in formula (I), R1 in the formula (I) is selected from one of an alkyl group and a phenyl group; R2 in the formula (I) is selected from one of a C2-C10 straight-chain alkyl group and an aryl group; R3 in the formula (I) is selected from one of -COOH and -PO(OH)2.

2. The carbazole derivative modified with a sulfur-containing functional group according to claim 1, characterized in that: The alkyl group is any one of methyl, ethyl, isopropyl and tert-butyl; The aryl group is any one of phenyl, furan, and thiophene; The connection position of the -S-R1 group and carbazole is 2, 7 or 3, 6.

3. The carbazole derivative modified with a sulfur-containing functional group according to claim 1, characterized in that: Has the structure shown below, 4. The method for preparing a carbazole derivative modified with a sulfur-containing functional group according to any one of claims 1 to 3, characterized in that: Including method one, method two, method three and method four; When R2 is a C2-C10 straight-chain alkyl group and R3 is -PO(OH)2, method 1 is adopted; When R2 is a C2-C10 straight-chain alkyl group and R3 is -COOH, the second method is adopted; When R2 is an aromatic group and R3 is -PO(OH)2, method 3 is adopted; When R2 is an aromatic group and R3 is -COOH, method 4 is adopted.

5. The preparation method according to claim 4, characterized in that: The method 1 comprises: S1: using dibromocarbazole as a raw material, adding tert-butyldimethylsilyl chloride to protect the nitrogen atom of the dibromocarbazole, and generating silylated dibromocarbazole under the action of a first strong base; the synthesis route of S1 is shown in a; S2: The silylated dibromocarbazole reacts with a thioether compound under the action of a second strong base to generate a silylated carbazole derivative modified with a -S-R1 group; the synthesis route of S2 is shown in b; S3: deprotecting the -S-R1 group-modified carbazole silylation derivative under the action of tetrabutylammonium fluoride to generate a -S-R1 group-disubstituted carbazole compound; the synthesis route of S3 is shown in c; S4: Under the action of a third strong base and a phase transfer catalyst, the -S-R1 group disubstituted carbazole compound reacts with a dibrominated straight-chain alkane to generate a -S-R1 group disubstituted carbazole alkyl bromide derivative; the straight-chain alkane in the dibrominated straight-chain alkane is a C2-C10 straight-chain alkane; the synthesis route of S4 is shown in d; S5: the -S-R1 group disubstituted carbazole alkyl bromide derivative is refluxed with triethyl phosphite to generate a -S-R1 group disubstituted carbazole alkyl phosphite compound; the synthesis route of S5 is shown in e; S6: the -S-R1 group disubstituted carbazole alkyl phosphite compound reacts with a hydrolysis agent to generate a -S-R1 group disubstituted carbazole alkyl phosphite compound; the synthesis route of S6 is shown in f; 6. The preparation method according to claim 5, characterized in that: The first strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; The second strong base is selected from any one of n-butyl lithium, tert-butyl lithium and sec-butyl lithium; The third strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; The phase transfer catalyst is selected from any one of tetrabutylammonium bromide, tetrabutylammonium iodide and tetrabutylammonium hydroxide; The hydrolysis agent is trimethylsilyl bromide.

7. The preparation method according to claim 4, characterized in that: The second method comprises: S1: the same as S1 described in claim 5; S2: the same as S2 described in claim 5; S3: the same as S3 described in claim 5; S4: Under the action of a fourth strong base, the -S-R1 group disubstituted carbazole compound is docked with bromoalkane acid methyl ester, accompanied by ester hydrolysis, and then subjected to acidification treatment to generate a -S-R1 group disubstituted carbazole alkyl carboxylic acid compound; The fourth strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; The alkane in the methyl bromide is a C2-C10 straight-chain alkane; The acidification treatment uses dilute hydrochloric acid with a mass fraction of 10%; The synthetic route of S4 is shown in g; 8. The preparation method according to claim 4, characterized in that: The third method comprises: S1: the same as S1 described in claim 5; S2: the same as S2 described in claim 5; S3: the same as S3 described in claim 5; S4: the -S-R1 group disubstituted carbazole compound and dibromoaryl hydrocarbon undergo carbon-nitrogen coupling under CuI catalysis and the action of a fifth strong base to generate a -S-R1 group disubstituted carbazole aryl bromide derivative; The fifth strong base is selected from any one of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; The synthetic route of S4 is shown in h; S5: The -S-R1 group disubstituted carbazole aryl bromide derivative is heated to reflux with triethyl phosphite to generate a -S-R1 group disubstituted carbazole aryl phosphite compound; the synthesis route of S5 is shown in i; S6: the -S-R1 group disubstituted carbazole aryl phosphate compound is hydrolyzed with a hydrolysis agent to generate a -S-R1 group disubstituted carbazole aryl phosphate compound; The hydrolysis reagent is trimethylsilyl bromide; The synthetic route of S6 is shown in j; 9. The preparation method according to claim 4, characterized in that: The fourth method comprises: S1: the same as S1 described in claim 7; S2: the same as S2 described in claim 7; S3: the same as S3 described in claim 7; S4: the same as S4 described in claim 7; S5: the -S-R1 group disubstituted carbazole aryl bromide derivative reacts with diethyl oxalate in the presence of a sixth strong base via a palladium-catalyzed reaction to generate a -S-R1 group disubstituted carbazole aryl formic acid compound; The sixth strong base is selected from any one of n-butyl lithium, tert-butyl lithium and sec-butyl lithium; The palladium catalyst used in the palladium-catalyzed reaction is selected from any one of tetrakistriphenylphosphine palladium, bistriphenylphosphine palladium dichloride, and 1,1'-bisdiphenylphosphinoferrocene palladium dichloride; The synthetic route of S5 is shown in k; 10. Use of the carbazole derivative modified with a sulfur-containing functional group according to any one of claims 1 to 3 in a trans-perovskite solar cell.

11. An inverse perovskite solar cell comprising a hole transport layer, characterized in that: The material of the hole transport layer is the carbazole derivative modified with sulfur-containing functional groups as claimed in any one of claims 1 to 3.

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