Phenylcarbazole derivative as well as preparation method and application thereof

Abstract

The invention provides a phenylcarbazole derivative as well as a preparation method and application thereof. The phenylcarbazole derivative has a structure as shown in a formula I or a formula II. According to the invention, phenyl carbazole with a rigid conjugate large plane is used as a parent nucleus, so that ordered accumulation of molecules is optimized, and the hole mobility is remarkably improved; the phosphate group at the tail end is an anchoring group, can effectively passivate perovskite interface defects, reduce energy loss at the interface, realize monomolecular self-assembly and improve cell performance, and as a self-assembly monomolecular layer hole transport material, the perovskite solar cell has relatively high photoelectric conversion efficiency, and the photoelectric conversion efficiency of the perovskite solar cell is improved. And the service life and the stability are relatively long.

Description

Technical Field

[0001] This invention belongs to the field of perovskite solar cell technology, and particularly relates to a phenylcarbazole derivative, its preparation method, and its application. Background Technology

[0002] Perovskite solar cells (PSCs) are a new type of photovoltaic cell that relies on perovskite structure materials for photoelectric conversion. They belong to the third generation of solar cells and have advantages such as simple manufacturing process, easy material tuning, and low cost. The latest certified efficiency has reached 26.7% (National Renewable Energy Laboratory, NREL, 2024).

[0003] Perovskite solar cells are mainly classified into two structural types: forward-facing nip structures and reverse-facing pin structures. Compared to nip structures, pin structures are more suitable for the fabrication of large-area, tandem solar cells because they can be produced using low-temperature processes and can accommodate a wider variety of carrier extraction layers, thus possessing greater commercial application prospects. However, pin structures also face a key challenge: how to improve the interface quality and stability between the hole-selective layer and the perovskite.

[0004] Currently, the hole transport materials (HTMs) commonly used in inverting devices include inorganic materials such as nickel oxide (NiO). x ) and organic polymer materials poly[double(4 Phenyl(2,4,6) [Trimethylphenylamine](PTAA). However, the energy level mismatch and defect states between nickel oxide and perovskite lead to voltage loss and interface degradation. Furthermore, the high cost, batch instability, and low film wettability of PTAA limit further improvements in device performance. Therefore, developing high-performance, novel hole transport materials for inversion devices is crucial for enhancing device performance.

[0005] Self-assembled monolayers (SAMs), as hole transport materials, are characterized by their simple structure and flexible design, enabling effective tuning of interfacial energy levels and reduction of defect states through molecular engineering. Furthermore, these materials exhibit unique advantages such as low parasitic absorption, low material consumption, compatibility with tandem perovskite solar cells, and simplified fabrication of large-area devices, making them a popular choice for fabricating high-efficiency perovskite solar cells.

[0006] Hole transport materials (HTMs) are an important component of battery cell (PSC) and play a crucial role in the efficiency and stability of the battery. PTAA is currently the most commonly used hole transport material in high-efficiency inverted PSCs, but several problems with PTAA itself seriously hinder the industrialization of inverted PSCs: First, the price of PTAA is as high as $1980 / g, dozens of times that of gold, preventing its large-scale application; second, PTAA itself has a low hole mobility (~10). -5 cm 2 V -1 s -1 To improve hole transport performance, dopants such as lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone need to be added. However, these water-absorbing dopants can cause the decomposition of perovskite, which greatly affects the long-term stability of the battery. Finally, as a polymer, PTAA's molecular weight and photovoltaic performance can change with each synthesis batch, which is not conducive to industrial application.

[0007] Therefore, developing a new type of SAM material that is simple in structure, low in cost, and has excellent performance is an urgent problem to be solved in order to promote the industrialization of PSCs. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a phenylcarbazole derivative, its preparation method, and its applications. By designing the structure of the compound and using it as a self-assembled monolayer hole transport material, this invention enables perovskite solar cells to exhibit high photoelectric conversion efficiency, long lifespan, and stability.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a phenylcarbazole derivative having the structure shown in Formula I or Formula II:

[0011] ;

[0012] Ar1 is selected from C6-C12 aryl, and Ar2 is selected from hydrogen or C6-C12 aryl.

[0013] The phenylcarbazole derivative in this invention uses phenylcarbazole with a rigid conjugated large plane as the parent core, which optimizes the ordered molecular stacking and significantly improves the hole mobility. The terminal phosphate group is an anchoring group, which can effectively passivate perovskite interface defects, reduce energy loss at the interface, and realize single-molecule self-assembly, thereby improving battery performance. As a self-assembled monolayer hole transport material, it enables perovskite solar cells to have high photoelectric conversion efficiency, long service life and stability.

[0014] Wherein, C6-C12 can be C6, C8, C10 or C12, etc.

[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0016] Preferably, the C6-C12 aryl group includes phenyl, biphenyl, or naphthyl.

[0017] Preferably, the phenylcarbazole derivative has the following structure:

[0018] .

[0019] In a second aspect, the present invention provides a method for preparing the phenylcarbazole derivative as described in the first aspect, the method comprising the following steps:

[0020] (1) The starting material reacts with allyl phosphate diethyl ester to obtain intermediate I;

[0021] The starting material has the structure shown in formula III-1 or formula III-2 as follows:

[0022] ;

[0023] The intermediate I has the structure shown in formula IV-1 or IV-2 as follows:

[0024] ;

[0025] (2) Intermediate I reacts with sodium borohydride to give intermediate II;

[0026] The intermediate II has the structure shown in formula V-1 or formula V-2 as follows:

[0027] ;

[0028] (3) Intermediate II undergoes a hydrolysis reaction to obtain the phenylcarbazole derivative;

[0029] Preferably, when the starting material has the structure of Formula III, the synthetic route for the phenylcarbazole derivative is as follows:

[0030] .

[0031] Preferably, when the starting material is of formula IV, the synthetic route for the phenylcarbazole derivative is as follows:

[0032] .

[0033] Ar1 and Ar2 have the same choices as described above.

[0034] Preferably, in step (1), the molar ratio of the starting material to diethyl allyl phosphate is 1:(1-1.25), for example, it can be 1:1.05, 1:1.1, 1:1.15, 1:1.2 or 1:1.25, etc.

[0035] Preferably, in step (1), the reaction is carried out in a solvent.

[0036] Preferably, in step (1), the solvent includes triethylamine.

[0037] Preferably, in step (1), the reaction is carried out in the presence of a catalyst.

[0038] Preferably, in step (1), the catalyst comprises tris(o-tolyl)phosphine and / or palladium(II) acetate.

[0039] Preferably, in step (1), the reaction temperature is 85-100℃, for example, it can be 85℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃ or 100℃.

[0040] Preferably, in step (1), the reaction time is 12-24h, for example, it can be 12h, 14h, 16h, 18h, 20h, 22h or 24h.

[0041] Preferably, in step (2), the molar ratio of intermediate I to sodium borohydride is 1:(2-12), for example, it can be 1:2, 1:4, 1:6, 1:8, 1:10 or 1:12, etc.

[0042] Preferably, in step (2), the reaction is carried out in a solvent.

[0043] Preferably, in step (2), the solvent includes methanol.

[0044] Preferably, in step (2), the reaction is carried out in the presence of a catalyst.

[0045] Preferably, in step (2), the catalyst comprises cobalt chloride.

[0046] Preferably, in step (2), the reaction temperature is room temperature.

[0047] Preferably, in step (2), the reaction time is 1-2 hours, for example, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours.

[0048] Preferably, in step (3), the hydrolysis reaction is carried out in the presence of a Lewis acid.

[0049] Preferably, the Lewis acid comprises trimethylbromosilane.

[0050] Preferably, the molar ratio of intermediate II to Lewis acid is 1:(3-5), for example, it can be 1:3.5, 1:4, 1:4.5 or 1:5, etc.

[0051] Preferably, in step (3), the hydrolysis reaction is carried out in a solvent.

[0052] Preferably, in step (3), the solvent includes 1,4-dioxane.

[0053] Preferably, in step (3), the hydrolysis reaction is carried out at room temperature.

[0054] Preferably, in step (3), the hydrolysis reaction time is 10-15h, for example, 10h, 11h, 12h, 13h, 14h or 15h.

[0055] Thirdly, the present invention provides a perovskite solar cell, the perovskite solar cell comprising a self-assembled monolayer, the self-assembled monolayer comprising a self-assembled monolayer hole transport material.

[0056] Preferably, the self-assembled monolayer hole transport material comprises the phenylcarbazole derivative described in the first aspect.

[0057] Preferably, the perovskite solar cell is an inverted perovskite solar cell.

[0058] Preferably, the perovskite solar cell includes a cathode layer, an electron transport layer, a passivation layer, a perovskite light-absorbing layer, a self-assembled monolayer, and an anode layer.

[0059] Preferably, the perovskite solar cell further includes a hole transport layer located between the self-assembled monolayer and the anode layer.

[0060] Preferably, the self-assembled monolayer is obtained by coating a solution of the self-assembled monolayer hole transport material onto the surface of the hole transport layer and then performing thermal annealing.

[0061] Preferably, the temperature of the heat annealing is 80-120℃ (e.g., 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃, etc.), and the heat annealing time is 5-20min (e.g., 5min, 10min, 15min or 20min, etc.).

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] This invention uses phenylcarbazole with a rigid conjugated large plane as the parent core, which optimizes the ordered molecular stacking and significantly improves the hole mobility. The terminal phosphate group is an anchoring group, which can effectively passivate perovskite interface defects, reduce energy loss at the interface, and realize single-molecule self-assembly, thereby improving battery performance. As a self-assembled monolayer hole transport material, it enables perovskite solar cells to have high photoelectric conversion efficiency, long service life and stability. Attached Figure Description

[0064] Figure 1 The 1H NMR spectrum of intermediate 1 prepared in Example 1;

[0065] Figure 2 The 1H NMR spectrum of intermediate 2 prepared in Example 1;

[0066] Figure 3 The 1H NMR spectrum of compound A1 prepared in Example 1;

[0067] Figure 4 The 1H NMR spectrum of intermediate 3 prepared in Example 2;

[0068] Figure 5 The 1H NMR spectrum of intermediate 4 prepared in Example 2;

[0069] Figure 6 The 1H NMR spectrum of compound A2 prepared in Example 2;

[0070] Figure 7 The 1H NMR spectrum of intermediate 5 prepared in Example 3;

[0071] Figure 8 The 1H NMR spectrum of intermediate 6 prepared in Example 3;

[0072] Figure 9 The 1H NMR spectrum of compound A3 prepared in Example 3;

[0073] Figure 10 IV curves of perovskite solar cells fabricated using compound A1 as a hole transport material;

[0074] Figure 11 IV curves of perovskite solar cells fabricated using compound A2 as a hole transport material;

[0075] Figure 12 IV curves of perovskite solar cells fabricated using compound A3 as a hole transport material;

[0076] Figure 13 This is a schematic diagram of the perovskite solar cell structure in this invention. Detailed Implementation

[0077] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0078] Example 1

[0079] The synthetic route for compound A1 is as follows:

[0080]

[0081] (1) Under nitrogen protection, diethyl allyl phosphate (0.98 g, 5.1 mmol), tris(o-tolyl)phosphine (0.16 g, 0.52 mmol), and palladium(II) acetate (0.020 g, 0.087 mmol) were added sequentially to a solution of triethylamine (10 mL) containing 1.5 g (4.1 mmol) of the starting material. The reaction mixture was stirred at 100°C under nitrogen protection for 12 h. The reaction solution was cooled to below 15°C, and 1 mol / L HCl solution (100 mL) was added, followed by diethyl ether (100 mL), and stirred for 10 min. The aqueous phase was separated, and the organic layers were combined, dried over anhydrous Na2SO4, and filtered. The crude product was separated by silica gel column chromatography to obtain intermediate 1 in 71% yield.

[0082] Intermediate 1 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 1 As shown, its NMR data is as follows:

[0083] 1 H NMR (400 MHz, DMSO-d6) δ 8.50 (dd, J = 7.3, 1.5 Hz, 1H), 8.44 (d, J= 2.2 Hz, 1H), 7.98-7.91 (m, 1H), 7.86-7.74 (m, 3H), 7.61-7.30 (m, 8H), 6.50-6.42 (m, 1H), 5.95 (dt, J = 8.9, 7.5 Hz, 1H), 3.99 (dq, J = 8.5, 7.2 Hz, 4H), 2.86-2.76 (m, 2H), 1.33 (td, J = 7.2, 0.7 Hz, 6H).

[0084] (2) Under nitrogen protection, sodium borohydride (1.0 g, 24.1 mmol) was slowly added to a methanol solution of intermediate 1 (1.0 g, 2.1 mmol) and cobalt chloride (0.36 g, 2.8 mmol) in a 100 mL single-necked round-bottom flask and stirred for 1 hour. The mixture was diluted with ether (100 mL), washed with H2O and saturated NH4Cl, dried with anhydrous Na2SO4 and filtered. The solvent was removed under vacuum to obtain the crude product. The crude product was separated by chromatographic column chromatography with hexane / ethyl acetate as eluent (15:1, v:v) to obtain colorless oily liquid intermediate 2 with a yield of 87%.

[0085] Intermediate 2 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 2 As shown, its NMR data is as follows:

[0086] 1 H NMR (400 MHz, DMSO-d6) δ 8.51 (dd, J = 7.2, 1.5 Hz, 1H), 7.98-7.89(m, 2H), 7.81 (q, J = 6.8 Hz, 2H), 7.56-7.47 (m, 4H), 7.44 (d, J = 5.1 Hz,1H), 7.43-7.33 (m, 3H), 7.10-6.77 (m, 1H), 3.99 (dq, J = 8.5, 7.3 Hz, 4H), 2.74 (s, 2H), 2.04-1.79 (m, 4H), 1.30 (td, J = 7.2, 0.7 Hz, 6H).

[0087] (3) In a 50 mL dry round-bottom flask, intermediate 2 (0.49 g, 1 mmol) was dissolved in 20 mL of 1,4-dioxane. Trimethylbromosilane (0.612 g, 4 mmol) was added dropwise at room temperature. After 12 hours, the mixture was transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. Then, a magnetic stir bar and 20 mL of methanol were added sequentially, and the mixture was stirred at room temperature for 4 hours. The mixture was filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was recrystallized from methanol / dichloromethane / diethyl ether to obtain a white solid compound A1 with a yield of 67%.

[0088] Compound A1 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 3 As shown, its NMR data is as follows:

[0089] 1H NMR (400 MHz, DMSO-d6) δ 8.51 (dd, J = 7.2, 1.5 Hz, 1H), 8.30 (s,2H), 7.98-7.89 (m, 2H), 7.81 (q, J = 6.8 Hz, 2H), 7.61-7.53 (m, 2H), 7.53-7.47 (m, 2H), 7.47-7.43 (m, 1H), 7.43-7.33 (m, 3H), 6.99-6.92 (m, 1H), 2.79-2.68 (m, 2H), 2.01-1.85 (m, 4H).

[0090] Mass spectrometry data of compound A1: MS m / z: [M+H] + Theoretical value: [C] 25 H 22 NO3P] + 416.14, measured value: 416.00.

[0091] Example 2

[0092] The synthetic route for compound A2 is as follows:

[0093] .

[0094] (1) Under nitrogen protection, diethyl allyl phosphate (0.98 g, 5.1 mmol), tris(o-tolyl)phosphine (0.16 g, 0.52 mmol), and palladium(II) acetate (0.020 g, 0.087 mmol) were added sequentially to a solution of triethylamine (10 mL) containing 1.6 g (4 mmol) of the starting material. The reaction mixture was stirred at 85°C under nitrogen protection for 18 h. The reaction solution was cooled to below 15°C, and 1 mol / L HCl solution (100 mL) was added, followed by diethyl ether (100 mL), and stirred for 10 min. The aqueous phase was separated, and the organic layers were combined, dried over anhydrous Na2SO4, and filtered. The crude product was separated by silica gel column chromatography to obtain intermediate 3 in 71% yield.

[0095] Intermediate 3 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 4 As shown, its NMR data is as follows:

[0096] 1H NMR (400 MHz, DMSO-d6) δ 8.39 (dd, J = 2.2, 0.7 Hz, 1H), 8.09 (d, J= 2.3 Hz, 1H), 7.79-7.73 (m, 1H), 7.68-7.58 (m, 3H), 7.56-7.29 (m, 10H), 6.50-6.42 (m, 1H), 5.95 (dt, J = 8.9, 7.5 Hz, 1H), 3.99 (dq, J = 8.5, 7.2 Hz, 4H), 2.86-2.76 (m, 2H), 1.33 (td, J = 7.2, 0.7 Hz, 6H).

[0097] (2) Under nitrogen protection, sodium borohydride (1.0 g, 24.1 mmol) was slowly added to a methanol solution of intermediate 3 (1.0 g, 1.7 mmol) and cobalt chloride (0.36 g, 2.8 mmol) in a 100 mL single-necked round-bottom flask and stirred for 2 hours. The mixture was diluted with ether (100 mL), washed with H2O and saturated NH4Cl, dried with anhydrous Na2SO4 and filtered. The solvent was removed under vacuum to obtain the crude product. The crude product was separated by chromatographic column chromatography with hexane / ethyl acetate as eluent (15:1, v:v) to obtain colorless oily liquid intermediate 4 with a yield of 90%.

[0098] Intermediate 4 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 5 As shown, its NMR data is as follows:

[0099] 1 H NMR (400 MHz, DMSO-d6) δ 8.09 (dd, J = 2.4, 0.7 Hz, 1H), 7.89 (dd,J = 2.4, 1.0 Hz, 1H), 7.68-7.58 (m, 4H), 7.56-7.32 (m, 9H), 7.10-6.72 (m,1H), 3.99 (dq, J = 8.5, 7.3 Hz, 4H), 2.74 (s, 2H), 2.04-1.79 (m, 4H), 1.30 (td, J = 7.3, 0.7 Hz, 6H).

[0100] (3) In a 50 mL dry round-bottom flask, intermediate 4 (0.52 g, 1 mmol) was dissolved in 20 mL of 1,4-dioxane. Trimethylbromosilane (0.612 g, 4 mmol) was added dropwise at room temperature. After 15 hours, the mixture was transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. Then, a magnetic stir bar and 20 mL of methanol were added sequentially, and the mixture was stirred at room temperature for 4 hours. The mixture was filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was recrystallized from methanol / dichloromethane / diethyl ether to obtain a white solid compound A2 with a yield of 65%.

[0101] Compound A2 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 6 As shown, its NMR data is as follows:

[0102] 1 H NMR (400 MHz, DMSO-d6) δ 8.30 (s, 2H), 8.09 (dd, J = 2.4, 0.7 Hz,1H), 7.89 (dd, J = 2.3, 1.0 Hz, 1H), 7.68-7.58 (m, 4H), 7.56-7.32 (m, 9H), 6.99-6.91 (m, 1H), 2.74 (s, 2H), 2.00-1.85 (m, 4H).

[0103] Mass spectrometry data for compound A2: MS m / z: [M+H] + Theoretical value: [C] 27 H 24 NO3P] + 442.16, measured value: 442.13.

[0104] Example 3

[0105] The synthetic route for compound A3 is as follows:

[0106]

[0107] (1) Under nitrogen protection, diethyl allyl phosphate (0.98 g, 5.1 mmol), tris(o-tolyl)phosphine (0.16 g, 0.52 mmol), and palladium(II) acetate (0.020 g, 0.087 mmol) were added sequentially to a solution of triethylamine (10 mL) containing 1.6 g (4 mmol) of the starting material. The reaction mixture was stirred at 100°C under nitrogen protection for 24 h. The reaction solution was cooled to below 15°C, and 1 mol / L HCl solution (100 mL) was added, followed by diethyl ether (100 mL), and stirred for 10 min. The aqueous phase was separated, and the organic layers were combined, dried over anhydrous Na2SO4, and filtered. The crude product was separated by silica gel column chromatography to obtain intermediate 5 in 69% yield.

[0108] Intermediate 5 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 7 As shown, its NMR data is as follows:

[0109] 1 H NMR (400 MHz, DMSO-d6) δ 8.21-8.13 (m, 2H), 7.84-7.77 (m, 2H), 7.74-7.57 (m, 6H), 7.53-7.28 (m, 6H), 6.59-6.50 (m, 1H), 6.24 (dt, J = 14.3,7.5 Hz, 1H), 3.99 (dq, J = 8.5, 7.2 Hz, 4H), 2.72-2.63 (m, 2H), 1.33 (td, J =7.2, 0.7 Hz, 6H).

[0110] (2) Under nitrogen protection, sodium borohydride (1.0 g, 24.1 mmol) was slowly added to a methanol solution of intermediate 5 (1.0 g, 1.7 mmol) and cobalt chloride (0.36 g, 2.8 mmol) in a 100 mL single-necked round-bottom flask and stirred for 1.5 hours. The mixture was diluted with ether (100 mL), washed with H2O and saturated NH4Cl, dried with anhydrous Na2SO4 and filtered. The solvent was removed under vacuum to obtain the crude product. The crude product was separated by chromatographic column chromatography with hexane / ethyl acetate as eluent (15:1, v:v) to obtain colorless oily liquid intermediate 6 with a yield of 81%.

[0111] Intermediate 6 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 8 As shown, its NMR data is as follows:

[0112] 1H NMR (400 MHz, DMSO-d6) δ 8.31-8.05 (m, 1H), 7.90 (dd, J = 7.8, 0.8Hz, 1H), 7.85-7.77 (m, 2H), 7.72-7.57 (m, 5H), 7.53-7.48 (m, 1H), 7.48-7.28(m, 5H), 7.03 (ddt, J = 7.8, 1.9, 0.9 Hz, 1H), 3.99 (dq, J = 8.5, 7.2 Hz,4H), 2.70 (s, 2H), 2.04-1.79 (m, 4H), 1.30 (td, J = 7.2, 0.7 Hz, 6H).

[0113] (3) In a 50 mL dry round-bottom flask, intermediate 6 (0.52 g, 1 mmol) was dissolved in 20 mL of 1,4-dioxane. Trimethylbromosilane (0.612 g, 4 mmol) was added dropwise at room temperature. After 10 hours, the mixture was transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. Then, a magnetic stir bar and 20 mL of methanol were added sequentially, and the mixture was stirred at room temperature for 4 hours. The mixture was filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was recrystallized from methanol / dichloromethane / diethyl ether to obtain a white solid compound A3 with a yield of 70%.

[0114] Compound A3 was characterized by 1H NMR spectroscopy, and the results are as follows: Figure 9 As shown, its NMR data is as follows:

[0115] 1 H NMR (400 MHz, DMSO-d6) δ 8.30 (s, 2H), 8.22-8.13 (m, 1H), 7.90 (dd,J = 7.8, 0.8 Hz, 1H), 7.84-7.77 (m, 2H), 7.72-7.57 (m, 5H), 7.53-7.48 (m,1H), 7.48-7.37 (m, 2H), 7.37-7.28 (m, 3H), 7.03 (ddt, J = 7.8, 1.9, 0.9 Hz,1H), 2.69 (s, 2H), 1.99-1.85 (m, 4H).

[0116] Mass spectrometry data for compound A3: MS m / z: [M+H] + Theoretical value: [C] 27 H 24 NO3P] +442.16, measured value: 442.02.

[0117] Application Example 1

[0118] This application example uses a self-assembled monolayer material containing compound A1 as a hole transport layer to fabricate a perovskite solar cell, such as... Figure 13 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0119] The preparation process is as follows:

[0120] (1) Pretreatment of FTO conductive glass substrate: The FTO glass was ultrasonically cleaned in detergent, deionized water, ethanol and acetone for 15 minutes each, then dried in a 75°C oven and treated with ultraviolet ozone for 10 minutes.

[0121] (2) Preparation of NiOx layer by spin coating: 5 mg / mL NiOx aqueous solution was filtered through a 0.22 μm PTFE filter membrane and then dropped onto the surface of FTO substrate. The substrate was then rotated at 5000 rpm for 30 s on a spin coater and then heat-annealed at 120°C for 15 minutes.

[0122] (3) Preparation of self-assembled monolayer (SAM): After the NiOx substrate is prepared, it is transferred to a nitrogen glove box. 110 μL of ethanol solution of compound A1 with a concentration of 0.35 mg / mL is dropped onto the center of the substrate. The substrate is spin-coated at 5000 rpm for 30 s and then heat-annealed at 100°C for 10 min.

[0123] (4) Two-step spin-coating method for depositing perovskite layer: 110 μL of perovskite precursor solution (FA) was applied to the perovskite precursor solution. 0.9 MA 0.05 Cs 0.05 PbI3 (1.5M, DMF:DMSO = 4:1) was added dropwise to the center of the substrate. The first step was to spin-coat at 2000 rpm for 20 s, and the second step was to spin-coat at 4500 rpm for 35 s. 10 s before the end of the second spin-coating step, 110 μL of anisole was added dropwise at a uniform rate to the center of the substrate, followed by heat annealing at 110°C for 20 minutes.

[0124] (5) Preparation of passivation layer: At room temperature, drop 110 μL of 0.5 mg / mL PDADI2 isopropanol solution onto the center of the substrate, rotate it at 5000 rpm for 30 s on a spin coater, and anneal it on a constant temperature hot plate at 100℃ for 5 minutes.

[0125] (6) The battery was transferred to the vapor deposition system, and a 21 nm C60 layer was deposited on the perovskite layer by vacuum thermal evaporation; then, a 25 nm SnO layer was deposited at 90°C by atomic layer deposition (ALD). Finally, after scraping off the excess film layer at the common end, an Ag electrode with a thickness of 100 nm is deposited by vacuum evaporation under masked conditions.

[0126] Figure 10 This is the current-voltage (J-V) characteristic curve of the perovskite solar cell device in this application example, where the open-circuit voltage is 1.033V and the short-circuit current density is 24.08mA / cm². 2 .

[0127] Application Example 2

[0128] The only difference between this application example and application example 1 is that compound A1 is replaced with an equal amount of compound A2, while the rest of the preparation methods are the same as in application example 1.

[0129] Figure 11 This is the current-voltage (J-V) characteristic curve of the perovskite solar cell device in this application example, where the open-circuit voltage is 1.145V and the short-circuit current density is 24.53mA / cm². 2 .

[0130] Application Example 3

[0131] The only difference between this application example and application example 1 is that compound A1 is replaced with an equal amount of compound A3, while the rest of the preparation methods are the same as in application example 1.

[0132] Figure 12 This is the current-voltage (J-V) characteristic curve of the perovskite solar cell device in this application example, where the open-circuit voltage is 1.08V and the short-circuit current density is 24.32mA / cm². 2 .

[0133] Comparative Application Example 1

[0134] The only difference between this comparative application example and application example 1 is that compound A1 is replaced with an equal amount of compound B, while the rest of the preparation method is the same as in application example 1. Compound B has the following structure:

[0135]

[0136] Table 1 shows the performance data of the perovskite solar cell devices in Application Examples 1-3 and Comparative Application Example 1:

[0137] Table 1

[0138]

[0139] As shown in Table 1, this invention uses phenylcarbazole with a rigid conjugated large plane as the parent core, which optimizes the ordered molecular stacking and significantly improves the hole mobility. The terminal phosphate group is an anchoring group, which can effectively passivate perovskite interface defects, reduce energy loss at the interface, and realize single-molecule self-assembly, thereby improving battery performance. As a self-assembled monolayer hole transport material, it enables perovskite solar cells to have a high photoelectric conversion efficiency of up to 21.63%, while also having a long service life and stability.

[0140] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A phenylcarbazole derivative, characterized in that, The phenylcarbazole derivative has the following structure of formula I or formula II: ； Ar1 is selected from C6-C12 aryl, and Ar2 is selected from hydrogen or C6-C12 aryl.

2. The phenylcarbazole derivative according to claim 1, characterized by The C6-C12 aryl includes phenyl, biphenyl or naphthyl.

3. The phenylcarbazole derivative according to claim 1, characterized by The phenylcarbazole derivative has the following structure: 。 4. A process for producing the phenylcarbazole derivative according to any one of claims 1 to 3, characterized by, The preparation method comprises the following steps: (1) reacting a starting material with allyl diethyl phosphate to obtain an intermediate I; The starting material has the following structure of formula III-1 or formula III-2: ； The intermediate I has the following structure of formula IV-1 or formula IV-2: ； (2) reacting the intermediate I with sodium borohydride to obtain an intermediate II; The intermediate II has the following structure of formula V-1 or formula V-2: ； (3) performing hydrolysis reaction on the intermediate II to obtain the phenylcarbazole derivative; Ar1 and Ar2 have the same selection as in claim 1.

5. The preparation method according to claim 4, characterized in that, In step (1), the molar ratio of the starting material to allyl diethyl phosphate is 1:(1-1.25); In step (1), the reaction is performed in a solvent; In step (1), the solvent includes triethylamine; In step (1), the reaction is performed in the presence of a catalyst; In step (1), the catalyst includes tris(o-tolyl)phosphine and / or palladium(II) acetate; In step (1), the reaction temperature is 85-100°C; In step (1), the reaction time is 12-24h.

6. The preparation method according to claim 4, characterized in that, In step (2), the molar ratio of the intermediate I to sodium borohydride is 1:(2-12); In step (2), the reaction is performed in a solvent; In step (2), the solvent includes methanol; In step (2), the reaction is performed in the presence of a catalyst; In step (2), the catalyst includes cobalt chloride; In step (2), the reaction temperature is room temperature; In step (2), the reaction time is 1-2h.

7. The preparation method according to claim 4, characterized in that, In step (3), the hydrolysis reaction is performed in the presence of a Lewis acid; The Lewis acid includes trimethylbromosilane; The molar ratio of the intermediate II to the Lewis acid is 1:(3-5).

8. The preparation method according to claim 4, characterized in that, In step (3), the hydrolysis reaction is performed in a solvent; In step (3), the solvent includes 1,4-dioxane; In step (3), the hydrolysis reaction temperature is room temperature; In step (3), the hydrolysis reaction time is 10-15h.

9. A perovskite solar cell, characterized by, The perovskite solar cell comprises a self-assembled monolayer, and the self-assembled monolayer comprises a self-assembled monolayer hole transport material; The self-assembled monolayer hole transport material comprises the phenylcarbazole derivative according to any one of claims 1-3.

10. The perovskite solar cell according to claim 9, characterized in that, The perovskite solar cell is a transverse perovskite solar cell; The perovskite solar cell comprises a cathode layer, an electron transport layer, a passivation layer, a perovskite light absorption layer, a self-assembled monolayer and an anode layer; The perovskite solar cell further comprises a hole transport layer, and the hole transport layer is located between the self-assembled monolayer and the anode layer; The self-assembled monolayer is obtained by coating a solution of the self-assembled monolayer hole transport material onto the surface of the hole transport layer and performing thermal annealing; The temperature of the heat annealing is 80-120℃, and the time of the heat annealing is 5-20min.

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