A self-assembled monolayer hole transport material based on polycarbazole derivatives, its preparation method and application

Abstract

This invention provides a self-assembled monolayer hole transport material based on a polycarbazole derivative, its preparation method, and its applications. The material has the structure shown in Formula I. This self-assembled monolayer hole transport material exhibits a simple structure, high hole transport capacity, strong interface passivation ability, and high thermal stability, and is suitable for large-scale applications. It uses a polycarbazole derivative as the parent core, alkyl / aryl chains as linking groups, and phosphate as the anchoring group. Using a rigid, conjugated, large-planar polycarbazole with a specific structure as the parent core improves molecular packing and enhances the hole transport performance of the material. The phosphate group at the end enables single-molecule self-assembly and passivation of the perovskite interface, reducing energy loss at the interface and improving battery performance.

Description

Technical Field

[0001] This invention belongs to the field of solar energy technology, and relates to a self-assembled monolayer hole transport material based on polycarbazole derivatives, its preparation method and application. Background Technology

[0002] As a new generation of photovoltaic technology, perovskite solar cells (PSCs) have advantages such as simple fabrication processes, easily modulated materials, and low cost. The latest certified efficiency has reached 26.2% (National Renewable Energy Laboratory, NREL, 2023). Perovskite solar cells have two main structural types: one is forward-facing... The structure is either reversed or... Structure. Compared to structure, This structure is better suited for fabricating large-area, tandem solar cells because it can utilize low-temperature processes and a wider variety of carrier extraction layers, giving it greater commercial potential. However, The structure also faces a challenge: how to improve the interface quality and stability between the hole-selective layer and the perovskite. Currently, commonly used hole transport materials (HTMs) for inverting devices include inorganic materials such as nickel oxide (NiOx) and organic polymer materials such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). Among them, nickel oxide has energy level mismatches and defect states with the perovskite, leading to voltage loss and interface degradation; PTAA is expensive, has unstable batch production, and low film wettability, all of which limit further improvement in device performance. Therefore, developing high-performance, novel hole transport materials for inverting devices is crucial to device performance. Self-assembled monolayers (SAMs) as hole transport materials have the characteristics of simple structure and flexible design, and can effectively adjust interface energy levels and reduce defect states based on molecular engineering. At the same time, these materials also 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.

[0003] Hole transport materials (HTMs) are an important component of power cell batteries (PSCs) and play a crucial role in battery efficiency and stability. Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) is currently the most commonly used HTM 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 (F4TCNQ) 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.

[0004] Therefore, developing new SAM materials with simple structure, low cost, and excellent performance is a key issue that urgently needs to be addressed to promote the industrialization of PSCs. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a self-assembled monolayer hole transport material based on polycarbazole derivatives, its preparation method, and its applications.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On the one hand, the present invention provides a self-assembled monolayer hole transport material based on a polycarbazole derivative, which has the structure shown in Formula I:

[0008] ;

[0009] Ar1 and Ar2 are extended conjugated groups, selected from any one of the following groups:

[0010] ;

[0011] The asterisk represents the linking site of the functional group.

[0012] Where R1 is a linking group, selected from any one of L1 to L3:

[0013] ;

[0014] in This represents the connection site with the linking group.

[0015] The self-assembled monolayer hole transport material of this invention features a simple structure, high hole transport capacity, strong interface passivation ability, and high thermal stability, making it suitable for large-scale applications. It uses a polycarbazole derivative as the core, alkyl / aryl chains as linking groups, and phosphate as the anchoring group. The use of a rigid, conjugated, large-planar polycarbazole core with a specific structure improves molecular packing and enhances the material's hole transport performance. The phosphate group at the end enables single-molecule self-assembly and passivation of the perovskite interface, reducing energy loss at the interface and improving battery performance.

[0016] Preferably, Ar1 is selected from G1, Ar2 is selected from G1, G3, G9, G10 or G12, and L is selected from L1.

[0017] Preferably, Ar1 is selected from G2, Ar2 is selected from G2, G3, G4, G5, G6, G7, G11 or G12, and L is selected from L1.

[0018] Preferably, Ar1 is selected from G2, Ar2 is selected from G6, and L is selected from L2 or L3.

[0019] Preferably, Ar1 is selected from G3, Ar2 is selected from G5, G6, G8, G9, G10 or G12, and L is selected from L1.

[0020] As a preferred embodiment of the present invention, the self-assembled monolayer hole transport material based on polycarbazole derivatives is any one of the following compounds A1-A21:

[0021] .

[0022] On the other hand, the present invention provides a method for preparing a self-assembled monolayer hole transport material based on a polycarbazole derivative as described above, the method comprising the following steps:

[0023] (1) The compound of formula II reacts with the compound of formula III to give the compound of formula IV, and the reaction formula is as follows:

[0024] ;

[0025] (2) The compound shown in Formula IV undergoes a hydrolysis reaction to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in Formula I. The reaction formula is as follows:

[0026] ;

[0027] (1) Synthesis of self-assembled monolayer hole transport materials with L = L1:

[0028] S1-1. The reaction between compound II and compound III yields compound IV, as shown in the following reaction formula:

[0029] ;

[0030] The compounds S1-2 and IV are subjected to hydrolysis to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in Formula I. The reaction formula is as follows:

[0031] ;

[0032] (2) Synthesis of self-assembled monolayer hole transport materials with L = L2:

[0033] S2-1. The compound shown in formula B reacts with the compound shown in formula C to give the compound shown in formula D. The reaction formula is as follows:

[0034] ;

[0035] S2-2. The compound shown in formula D reacts with the compound shown in formula E to give the compound shown in formula F. The reaction formula is as follows:

[0036] ;

[0037] S2-3. The compound shown in formula E undergoes a hydrogenation reduction reaction to obtain the compound shown in formula E, as shown in the following reaction formula:

[0038] ;

[0039] S2-4 and the compound shown in formula H undergo hydrolysis to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in formula I. The reaction formula is as follows:

[0040] ;

[0041] (3) Synthesis of self-assembled monolayer hole transport materials with L=L3:

[0042] S3-1. Compound B reacts with compound c to give compound d, as shown in the following reaction equation:

[0043] ;

[0044] S3-2. The compound shown in formula d reacts with the compound shown in formula e to give the compound shown in formula f. The reaction formula is as follows:

[0045] ;

[0046] S3-3. The compound shown in formula f undergoes a hydrolysis reaction to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in formula I. The reaction formula is as follows:

[0047] ;

[0048] R1 and R2 are independently selected from alkyl groups of C1-C5 (e.g., C1, C2, C3, C4 or C5), and X is selected from halogens.

[0049] Preferably, the molar ratio of the compound of formula II to the compound of formula III in step S1-1 is 1:1-1.5, for example 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5.

[0050] Preferably, the reaction in step S1-1 is carried out in the presence of a catalyst selected from cuprous iodide.

[0051] Preferably, the reaction in step S1-1 is carried out in the presence of an alkaline substance, which is selected from potassium carbonate and sodium carbonate.

[0052] Preferably, the reaction in step S1-1 is carried out in an organic solvent selected from N,N'-dimethylacetamide.

[0053] Preferably, the reaction temperature in step S1-1 is 160~180℃, for example 160℃, 165℃, 170℃, 175℃ or 180℃, and the reaction time is 20~24 h, for example 20h, 21h, 22h, 23h or 24h.

[0054] Preferably, the hydrolysis reaction in steps S1-2 is carried out in the presence of trimethylbromosilane.

[0055] Preferably, the molar ratio of the trimethylbromosilane to the compound shown in Formula IV is 2:1 to 4:1, for example, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1.

[0056] Preferably, the hydrolysis reaction in steps S1-2 is carried out in an organic solvent, wherein the organic solvent is selected from dichloromethane and / or trichloromethane.

[0057] Preferably, the hydrolysis reaction described in steps S1-2 is carried out at room temperature (15-30°C, for example 15°C, 20°C, 25°C or 30°C) for 12-18 hours (for example 12 hours, 13 hours, 15 hours, 17 hours or 18 hours).

[0058] Preferably, the molar ratio of the compound shown in Formula B to the compound shown in Formula C in step S2-1 is 1:5 to 1:7 (e.g., 1:5, 1:5.5, 1:6, 1:6.5 or 1:7, etc.).

[0059] Preferably, the reaction in step S2-1 is carried out in the presence of an alkaline substance, which is selected from potassium phosphate or sodium phosphate.

[0060] Preferably, the reaction in step S2-1 is carried out in an organic solvent selected from N-methylpyrrolidone.

[0061] Preferably, the reaction temperature in step S2-1 is 160~180℃, for example 160℃, 165℃, 170℃, 175℃ or 180℃, and the reaction time is 40~48 h, for example 40h, 42h, 44h, 46h or 48h.

[0062] Preferably, the reaction described in step S2-1 is carried out under the protection of an inert gas.

[0063] Preferably, the molar ratio of the compound shown in formula D to the compound shown in formula E in step S2-2 is 1:3 to 1:4 (e.g., 1:3, 1:3.2, 1:3.5, 1:3.7 or 1:4, etc.).

[0064] Preferably, the reaction in step S2-2 is carried out in the presence of an alkaline substance, wherein the alkaline substance is triethylamine.

[0065] Preferably, the reaction in step S2-2 is carried out in the presence of a ligand selected from tris(o-tolyl)phosphine.

[0066] Preferably, the reaction in step S2-2 is carried out in the presence of a catalyst, wherein the catalyst is palladium acetate.

[0067] Preferably, the reaction temperature in step S2-2 is 100~120℃ (e.g., 100℃, 105℃, 110℃, 115℃ or 120℃, etc.), and the reaction time is 12~20 h (e.g., 12h, 14h, 16h, 18h or 20h, etc.).

[0068] Preferably, the reducing agent in the hydrogenation reduction reaction described in steps S2-3 is sodium borohydride.

[0069] Preferably, the hydrogenation reduction reaction in step S2-3 is carried out in the presence of a catalyst, which is cobalt chloride.

[0070] Preferably, the hydrogenation reduction reaction in steps S2-3 is carried out in an organic solvent, wherein the organic solvent is methanol.

[0071] Preferably, the hydrogenation reduction reaction in steps S2-3 is carried out under nitrogen protection.

[0072] Preferably, the hydrogenation reduction reaction described in steps S2-3 is carried out at room temperature for a time of 1 to 2 hours (e.g., 1 hour, 1.2 hours, 1.5 hours, 1.7 hours, or 2 hours).

[0073] Preferably, the hydrolysis reaction described in steps S2-4 is carried out in the presence of trimethylbromosilane.

[0074] Preferably, the molar ratio of the trimethylbromosilane to the compound represented by formula H is 2:1 to 4:1, for example 2:1, 2.5:1, 3:1, 3.5:1 or 4:1.

[0075] Preferably, the hydrolysis reaction in steps S2-4 is carried out in an organic solvent, wherein the organic solvent is selected from 1,4-dioxane.

[0076] Preferably, the hydrolysis reaction described in steps S2-4 is carried out at room temperature for a reaction time of 12 to 18 hours (e.g., 12 hours, 13 hours, 15 hours, 17 hours or 18 hours).

[0077] Preferably, the molar ratio of the compound shown in formula B to the compound shown in formula c in step S3-1 is 1:3.5 to 1:5, for example, 1:3.5, 1:3.7, 1:3.9, 1:4.1, 1:4.3, 1:4.5, 1:4.7, 1:4.9 or 1:5, etc.

[0078] Preferably, the reaction in step S3-1 is carried out in the presence of an alkaline substance, which is selected from potassium carbonate or sodium carbonate.

[0079] Preferably, the reaction in step S3-1 is carried out in the presence of a catalyst selected from cuprous iodide.

[0080] Preferably, the reaction in step S3-1 is carried out in an organic solvent selected from N,N-dimethylacetamide.

[0081] Preferably, the reaction temperature in step S3-1 is 160~200℃ (e.g., 160℃, 170℃, 180℃, 190℃ or 200℃, etc.), and the reaction time is 20~30h (e.g., 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h or 30h, etc.).

[0082] Preferably, the molar ratio of the compound shown in formula d to the compound shown in formula e in step S3-2 is 1:1.5 to 1:3 (e.g., 1:1.5, 1:1.7, 1:1.9, 1:2.1, 1:2.3, 1:2.5, 1:2.7, 1:2.9 or 1:3, etc.).

[0083] Preferably, the reaction in step S3-2 is carried out in the presence of a catalyst, wherein the catalyst is palladium acetate.

[0084] Preferably, the reaction in step S3-2 is carried out in the presence of a ligand selected from 1,1'-bis(diphenylphosphine)ferrocene.

[0085] Preferably, the reaction in step S3-2 is carried out in the presence of an alkaline substance, wherein the alkaline substance is potassium acetate.

[0086] Preferably, the reaction temperature in step S3-2 is 100~120℃ (e.g., 100℃, 105℃, 110℃, 115℃ or 120℃, etc.), and the reaction time is 20~30 hours (e.g., 20 hours, 22 hours, 25 hours, 27 hours or 30 hours, etc.).

[0087] Preferably, the reaction described in step S3-2 is carried out under nitrogen protection.

[0088] Preferably, the hydrolysis reaction in step S3-3 is carried out in the presence of trimethylbromosilane.

[0089] Preferably, the molar ratio of the trimethylbromosilane to the compound shown in formula f is 2:1 to 4:1, for example 2:1, 2.5:1, 3:1, 3.5:1 or 4:1.

[0090] Preferably, the hydrolysis reaction in steps S1-2 is carried out in an organic solvent, wherein the organic solvent is selected from dichloromethane and / or trichloromethane.

[0091] Preferably, the hydrolysis reaction described in steps S1-2 is carried out at room temperature for a reaction time of 12 to 18 hours (e.g., 12 hours, 13 hours, 15 hours, 17 hours or 18 hours).

[0092] On the other hand, the present invention provides a perovskite solar cell comprising a self-assembled monolayer, wherein the self-assembled monolayer comprises a hole transport material based on a polycarbazole derivative as described above.

[0093] Preferably, the perovskite solar cell is an inverted perovskite solar cell.

[0094] Preferably, the perovskite solar cell comprises, from top to bottom, a cathode layer, an electron transport layer, a passivation layer, a perovskite light-absorbing layer, a self-assembled monolayer, a hole transport layer, and an anode layer arranged sequentially.

[0095] Preferably, the self-assembled monolayer is obtained by coating a solution of the self-assembled monolayer hole transport material based on the polycarbazole derivative as described above onto the surface of the hole transport layer and then performing thermal annealing.

[0096] In this invention, the perovskite light-absorbing layer is prepared by coating (e.g., spin-coating) a perovskite solution onto the surface of a self-assembled monolayer.

[0097] Preferably, the temperature of the heat annealing is 80~120℃, for example 80℃, 90℃, 100℃, 110℃ or 120℃, and the heat annealing time is 5~20 minutes, for example 5 minutes, 10 minutes, 15 minutes or 20 minutes.

[0098] Compared with the prior art, the present invention has the following beneficial effects:

[0099] The self-assembled monolayer hole transport material based on polycarbazole derivatives of this invention uses a rigid, conjugated, large-planar polycarbazole core with a specific structure as the parent core, which can improve molecular packing and enhance the hole transport performance of the material. With phosphate groups as terminals, single-molecule self-assembly and passivation of the perovskite interface can be achieved, reducing energy loss at the interface and improving battery performance. When the synthesized material is used as the hole transport layer of an inverted perovskite solar cell, a photoelectric conversion efficiency of >22% can be obtained without doping, while significantly improving the lifetime and stability of the perovskite solar cell, which is expected to help industrialize perovskite solar cells. Attached Figure Description

[0100] Figure 1 The 1H NMR spectrum of intermediate 1.

[0101] Figure 2 The NMR spectrum of compound A1 is shown in Figure 1.

[0102] Figure 3 The 1H NMR spectrum of intermediate 2.

[0103] Figure 4 This is the 1H NMR spectrum of compound A2.

[0104] Figure 5 The 1H NMR spectrum of intermediate 3.

[0105] Figure 6 This is the 1H NMR spectrum of compound A3.

[0106] Figure 7 The 1H NMR spectrum of intermediate 4.

[0107] Figure 8 The 1H NMR spectrum of intermediate 5.

[0108] Figure 9 The 1H NMR spectrum of intermediate 6.

[0109] Figure 10 This is the 1H NMR spectrum of compound A20.

[0110] Figure 11 The 1H NMR spectrum of intermediate 7.

[0111] Figure 12 The 1H NMR spectrum of intermediate 8.

[0112] Figure 13 This is the 1H NMR spectrum of compound A21.

[0113] Figure 14 IV curves of solar cells fabricated using compound A1 as a hole transport material.

[0114] Figure 15 IV curves of solar cells fabricated using compound A2 as a hole transport material.

[0115] Figure 16 IV curves of solar cells fabricated using compound A3 as a hole transport material.

[0116] Figure 17 IV curves of solar cells fabricated using compound A20 as a hole transport material.

[0117] Figure 18 IV curves of solar cells fabricated using compound A21 as a hole transport material.

[0118] Figure 19 This is a schematic diagram of the perovskite solar cell structure of the present invention.

[0119] Figure 20 The adsorption model and density of states for Comparative Example 1 of the compound are shown.

[0120] Figure 21 The adsorption model and density of states for compound comparative example 2 are given.

[0121] Figure 22 The adsorption model and density of states of compound 3 are shown in the comparative example.

[0122] Figure 23 The adsorption model and density of states for compound comparison example 4 are given.

[0123] Figure 24 The adsorption model and density of states of compound 5 are shown.

[0124] Figure 25 The adsorption model and density of states for compound Comparative Example 6 are given.

[0125] Figure 26 The adsorption model and density of states of compound A1 are given.

[0126] Figure 27 The adsorption model and density of states of compound A2 are given.

[0127] Figure 28 The adsorption model and density of states of compound A3.

[0128] Figure 29 The adsorption model and density of states of compound A4 are given.

[0129] Figure 30 The adsorption model and density of states of compound A5 are given.

[0130] Figure 31 The adsorption model and density of states of compound A6 are given.

[0131] Figure 32 The adsorption model and density of states of compound A7 are given.

[0132] Figure 33 The adsorption model and density of states of compound A8 are given.

[0133] Figure 34 The adsorption model and density of states of compound A9 are given.

[0134] Figure 35 The adsorption model and density of states of compound A10 are given.

[0135] Figure 36 The adsorption model and density of states of compound A11 are given.

[0136] Figure 37 The adsorption model and density of states of compound A12 are given.

[0137] Figure 38 The adsorption model and density of states of compound A13 are given.

[0138] Figure 39 The adsorption model and density of states of compound A14 are given.

[0139] Figure 40 The adsorption model and density of states of compound A15 are given.

[0140] Figure 41 The adsorption model and density of states of compound A16 are given.

[0141] Figure 42 The adsorption model and density of states of compound A17 are given.

[0142] Figure 43The adsorption model and density of states of compound A18 are given.

[0143] Figure 44 The adsorption model and density of states of compound A19 are given.

[0144] Figure 45 The adsorption model and density of states of compound A20 are given.

[0145] Figure 46 The adsorption model and density of states of compound A21 are given. Detailed Implementation

[0146] 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.

[0147] Example 1

[0148] Synthesis of compound A1

[0149]

[0150] Step 1: Synthesis of Intermediate 1

[0151] Under a nitrogen atmosphere, starting material 1 (1.46 g, 3.0 mmol) and starting material 2 (0.91 g, 3.1 mmol) were dissolved in 25 mL of N,N'-dimethylacetamide, followed by the addition of K₂CO₃ (0.83 g, 6.0 mmol) and cuprous iodide (0.06 g, 6.0 mmol). The reaction mixture was heated at 180 °C. o The reaction was carried out at C for 24 h. After the reaction was completed, the mixture was cooled to room temperature. The solution was diluted with water and then extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. The crude product was separated by silica gel column chromatography to give a white solid (0.92 g, 66%).

[0152] The 1H NMR spectrum of intermediate 1 is as follows Figure 1 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.97-8.34 (m,1H), 8.15-8.03 (m, 3H), 7.69-7.28 (m, 19H), 4.14 (t, J = 5.1 Hz, 2H), 3.99(dq, J =8.5, 7.3 Hz, 4H), 1.92 (dtd, J = 11.8, 8.7, 0.6 Hz, 2H), 1.84-1.73(m, 2H), 1.68-1.56 (m, 2H), 1.30 (td, J = 7.3, 0.7 Hz, 6H).

[0153] Step 2: Synthesis of compound A1

[0154] In a 50 mL dry round-bottom flask, intermediate 1 (0.68 g, 1 mmol) was dissolved in 20 mL of dichloromethane. Trimethylbromosilane (0.612 g, 0.528 mL, 4 mmol) was added dropwise to the well-stirred mixture at room temperature. After 12 hours, the mixture was carefully transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. A magnetic stir bar and 20 mL of methanol were then added sequentially. The mixture was stirred at room temperature for 4 hours, filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to give a solid as the crude product. Recrystallization from methanol / dichloromethane / diethyl ether gave a white solid (0.36 g, 58%).

[0155] The 1H NMR spectrum of compound A1 is as follows Figure 2 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.85-8.41 (m,1H), 8.34 (s, 2H), 8.15-8.03 (m, 3H), 7.69-7.28 (m, 19H), 4.14 (t, J = 5.1Hz, 2H), 1.93-1.74 (m, 4H), 1.73-1.60 (m, 2H).

[0156] MS m / z: [MH] - C 40 H 32 N2O3P - Calculated value: 619.22; Test value: 619.11.

[0157] Example 2

[0158] Synthesis of compound A2

[0159]

[0160] Step 1: Synthesis of Intermediate 2

[0161] Under a nitrogen atmosphere, reactant 3 (1.95 g, 3.0 mmol) and reactant 2 (0.91 g, 3.1 mmol) were dissolved in 25 mL of N,N'-dimethylacetamide, followed by the addition of K₂CO₃ (0.83 g, 6.0 mmol) and cuprous iodide (0.06 g, 6.0 mmol). The reaction mixture was heated at 180 °C. oThe reaction was carried out at C for 24 h. After the reaction was completed, the mixture was cooled to room temperature. The solution was diluted with water and then extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. The crude product was separated by silica gel column chromatography to give a white solid (1.07 g, 58%).

[0162] The 1H NMR spectrum of intermediate 2 is as follows Figure 3 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.34 (d, J =2.2 Hz, 2H), 8.16-8.07 (m, 4H), 7.71-7.59 (m, 5H), 7.57-7.28 (m, 19H), 4.14(t, J = 5.1 Hz, 2H), 3.99 (dq, J = 8.5, 7.2 Hz, 4H), 1.92 (dtd, J = 11.9,8.7, 0.6 Hz, 2H), 1.84-1.73 (m, 2H), 1.68-1.56 (m, 2H), 1.30 (td, J = 7.2,0.7 Hz, 6H).

[0163] Step 2: Synthesis of compound A2

[0164] Intermediate 2 (0.82 g, 1 mmol) was dissolved in 20 mL of dichloromethane in a 50 mL dried round-bottom flask. Trimethylbromosilane (0.612 g, 0.528 mL, 4 mmol) was added dropwise to the well-stirred mixture at room temperature. After 12 hours, the mixture was carefully transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. A magnetic stir bar and 20 mL of methanol were then added sequentially. The mixture was stirred at room temperature for 4 hours, filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to give a solid as the crude product. Recrystallization from methanol / dichloromethane / diethyl ether gave a white solid (0.4 g, 56%).

[0165] The 1H NMR spectrum of compound A2 is as follows: Figure 4 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.34 (d, J =3.6 Hz, 4H), 8.16-8.07 (m, 4H), 7.71-7.59 (m, 5H), 7.57-7.39 (m, 11H), 7.39-7.28 (m, 8H), 4.14 (t, J = 5.1 Hz, 2H), 1.93-1.74 (m, 4H), 1.73-1.60 (m, 2H).

[0166] MS m / z: [MH] - C 52 H 39 N3O3P - Calculated value: 784.27, Test value: 784.38.

[0167] Example 3

[0168] Synthesis of compound A3

[0169]

[0170] Step 1: Synthesis of Intermediate 3

[0171] Under a nitrogen atmosphere, reactant 4 (1.95 g, 3.0 mmol) and reactant 2 (0.91 g, 3.1 mmol) were dissolved in 25 mL of N,N'-dimethylacetamide, followed by the addition of K₂CO₃ (0.83 g, 6.0 mmol) and cuprous iodide (0.06 g, 6.0 mmol). The reaction mixture was heated at 180 °C. o The reaction was carried out at C for 24 h. After the reaction was completed, the mixture was cooled to room temperature. It was diluted with water and then extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. The crude product was separated by silica gel column chromatography to give a white solid (1.02 g, 57%).

[0172] The 1H NMR spectrum of intermediate 3 is as follows Figure 5 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.38 (d, J =2.4 Hz, 2H), 8.20-8.12 (m, 4H), 7.85-7.78 (m, 4H), 7.70-7.59 (m, 9H), 7.56-7.39 (m, 5H), 7.39-7.28 (m, 6H), 4.14 (t, J = 5.1 Hz, 2H), 3.99 (dq, J = 8.5,7.3 Hz, 4H), 1.92 (dtd, J = 11.8, 8.7, 0.6 Hz, 2H), 1.84-1.73 (m, 2H), 1.68-1.56 (m, 2H), 1.30 (td, J = 7.2, 0.7 Hz, 6H).

[0173] Step 2: Synthesis of compound A3

[0174] Intermediate 3 (0.85 g, 1 mmol) was dissolved in 20 mL of dichloromethane in a 50 mL dried round-bottom flask. Trimethylbromosilane (0.612 g, 0.528 mL, 4 mmol) was added dropwise to the well-stirred mixture at room temperature. After 12 hours, the mixture was carefully transferred to a 100 mL round-bottom flask and concentrated under reduced pressure. A magnetic stir bar and 20 mL of methanol were then added sequentially. The mixture was stirred at room temperature for 4 hours, filtered, washed with methanol (3 × 5 mL), and the combined filtrate was concentrated under reduced pressure to give a solid as the crude product. Recrystallization from methanol / dichloromethane / diethyl ether gave a white solid (0.38 g, 54%).

[0175] The 1H NMR spectrum of compound A3 is as follows: Figure 6 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.41-8.32 (m,4H), 8.21-8.12 (m, 4H), 7.85-7.78 (m, 4H), 7.70-7.59 (m, 9H), 7.56-7.44 (m,3H), 7.44-7.28 (m, 8H), 4.14 (t, J = 5.1 Hz, 2H), 1.93-1.74 (m, 4H), 1.73-1.60 (m, 2H).

[0176] MS m / z: [MH] - C 52 H 39 N3O3P - Calculated value: 784.27, Test value: 784.23.

[0177] Example 4

[0178] Synthesis of compound A20

[0179]

[0180] Step 1: Synthesis of Intermediate 4

[0181] Starting material 1 (1 g, 2.06 mmol), starting material 5 (2.92 g, 12.36 mmol), and potassium phosphate (1.32 g, 6.18 mmol) were dissolved in dry NMP (12 mL), and the reaction was carried out under an argon atmosphere. The reaction mixture was heated to 160 °C. oThe mixture was stirred at C for 40 hours. After the reaction was complete, the mixture was added to saturated brine (100 mL) and extracted with dichloromethane (3 × 100 mL). The extracts were combined, concentrated under reduced pressure, and the product was separated by column chromatography (silica gel: 200-300 mesh; n-hexane: dichloromethane 4:1 (v / v) as eluent) to give a white solid (1.05 g, 80%).

[0182] The 1H NMR spectrum of intermediate 4 is as follows Figure 7 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 8.45 – 8.40 (m, 1H), 8.16 – 8.05 (m, 3H), 7.76 – 7.28 (m, 23H).

[0183] Step 2: Synthesis of Intermediate 5

[0184] Under nitrogen protection, diethyl vinyl phosphate (0.77 g, 4.68 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 triethylamine (10 mL) solution of intermediate 4 (1 g, 1.56 mmol). 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 the mixture was 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 give intermediate 5 (0.823 g, 73%).

[0185] The 1H NMR spectrum of intermediate 5 is as follows Figure 8 Shown, 1H NMR (400 MHz, DMSO-d6) δ 8.75 – 8.28(m, 1H), 8.16 – 8.05 (m, 3H), 7.76 – 7.28 (m, 24H), 6.18 (dd, J = 25.9, 17.0Hz, 1H), 4.04 (dq, J = 8.5, 6.7 Hz, 4H), 1.30 (td, J = 6.6, 0.7 Hz, 6H).

[0186] Step 3: Synthesis of Intermediate 6

[0187] Under nitrogen protection, sodium borohydride (1.0 g, 24.1 mmol) was slowly added to a methanol solution of intermediate 5 (0.7 g, 0.97 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 diethyl ether (100 mL), washed with H2O and saturated NH4Cl, dried over anhydrous Na2SO4, and filtered. The solvent was removed under vacuum to obtain the crude product. The crude product was separated by column chromatography with hexane / ethyl acetate as eluent (15:1, v:v) to give a colorless oily liquid intermediate 6 (0.59 g, 85%).

[0188] The 1H NMR spectrum of intermediate 6 is as follows Figure 9 As shown, the ¹H NMR (400 MHz, DMSO-d⁶) values ​​are: δ 8.57 – 8.27 (m, 1H), 8.20 – 7.99 (m, 3H), 7.84 – 7.06 (m, 23H), 3.97 (dq, J = 8.5, 7.2Hz, 4H), 2.83 (d, J = 8.1 Hz, 2H), 2.27 (dt, J = 12.0, 9.1 Hz, 2H), and 1.30 (td, J = 7.3, 0.8 Hz, 6H).

[0189] Step 4: Synthesis of compound A20

[0190] In a 50 mL dry round-bottom flask, intermediate 6 (0.5 g, 0.69 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. Recrystallization from methanol / dichloromethane / diethyl ether gave a white solid compound A20 (0.32 g, 69%).

[0191] The 1H NMR spectrum of compound A20 is as follows: Figure 10 As shown, the ¹H NMR (400 MHz, DMSO-d⁶) values ​​are: δ 9.13 (s, 2H), 8.60 – 8.34 (m, 1H), 8.18 – 7.92 (m, 3H), 7.75 – 7.58 (m, 7H), 7.57 – 7.20 (m, 16H), 2.84 (d, J = 10.8 Hz, 2H), 2.18 (dt, J = 11.9, 9.9 Hz, 2H).

[0192] MS m / z: [MH] - C 44 H 32 N2O3P - Calculated value: 667.73; Test value: 667.85.

[0193] Example 5

[0194] Synthesis of compound A21

[0195]

[0196] Step 1: Synthesis of Intermediate 7

[0197] Starting material 1 (1 g, 2.06 mmol) and starting material 6 (2.36 g, 8.24 mmol) were dissolved in 25 mL of N,N-dimethylacetamide (DMAc), followed by the addition of potassium carbonate (1.60 g, 11.60 mmol) and cuprous iodide (0.40 g, 2.12 mmol). The mixture was stirred at 180°C for 24 hours. After cooling to room temperature, the resulting mixture was washed with water and extracted with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate. After evaporation of the solvent under reduced pressure, the crude product was purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 4:1) to give colorless crystals (0.98 g, 69%).

[0198] The 1H NMR spectrum of intermediate 7 is as follows Figure 11 As shown, the ¹H NMR (400 MHz, DMSO-d⁶) values ​​are: δ 8.43 (d, J = 2.5 Hz, ¹H), 8.15 – 8.05 (m, 3H), 8.01 (dd, J = 2.4, 1.8 Hz, ¹H), 7.93 (dd, J = 6.9, 2.1 Hz, ¹H), 7.89 – 7.78 (m, 3H), and 7.75 – 7.27 (m, 20H).

[0199] Step 2: Synthesis of Intermediate 8

[0200] Intermediate 7 (0.69 g, 1 mmol), diethyl phosphite (0.3 mL, 2.13 mmol), Pd(OAc)₂ (0.016 g, 0.071 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.08 g, 0.144 mmol), and potassium acetate (0.42 g, 4.26 mmol) were dissolved in 25 mL of anhydrous toluene and reacted under nitrogen protection. The mixture was heated to 110°C and reacted for 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting mixture was washed with saturated brine and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (eluent: CH₂Cl₂:CH₃OH = 50:1) to give a colorless solid (0.542 g, 82%).

[0201] The 1H NMR spectrum of intermediate 8 is as follows Figure 12 As shown, the ¹H NMR (400 MHz, DMSO-d⁶) values ​​are: δ 8.48 – 8.38 (m, ¹H), 8.22 (t, J = 2.3 Hz, ¹H), 8.14 – 7.99 (m, 5H), 7.87 (t, J = 2.3 Hz, 1H), 7.77 – 7.26 (m, 2¹H), 4.13 (dq, J = 8.5, 6.9 Hz, 4H), and 1.31 (td, J = 6.9, 0.7 Hz, 6H).

[0202] Step 3: Synthesis of compound A21

[0203] Intermediate 8 (0.4 g, 0.536 mmol) was dissolved in 30 mL of dichloromethane. Trimethylbromosilane (0.6 mL, 5.30 mmol) was slowly added dropwise. The mixture was stirred at room temperature for 12 hours. After the reaction was complete, the reaction was quenched with 10 mL of methanol, and then 20 mL of dichloromethane was added, followed by stirring for 1 hour. The solvent was removed by vacuum distillation. After filtration, the solid was washed with deionized water and diethyl ether to give a white solid (0.281 g, 76%).

[0204] The 1H NMR spectrum of compound A21 is as follows: Figure 13Shown, 1H NMR (400 MHz, DMSO-d6) δ 9.01 (s,2H), 8.43 (d, J = 2.5 Hz, 1H), 8.36 (dt, J = 2.6, 1.3 Hz, 1H), 8.15 – 8.02(m, 4H), 7.96 – 7.85 (m, 2H), 7.76 – 7.70 (m, 2H), 7.69 – 7.59 (m, 6H), 7.59 – 7.37 (m, 9H), 7.38 – 7.27 (m, 4H).

[0205] MS m / z: [MH] - C 46 H 30 N2O3P - The calculated value is 689.74, and the tested value is 689.54.

[0206] Example 6

[0207] Perovskite solar cells were fabricated using the self-assembled monolayer material A1 prepared in Example 1, such as... Figure 19 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0208] The specific device fabrication process is as follows:

[0209] First, the FTO conductive glass substrate was pretreated: the FTO glass was ultrasonically cleaned sequentially in detergent, deionized water, ethanol, and acetone for 15 minutes each, and then dried in a 75°C oven. Before use, the glass was treated with UV ozone for 10 minutes. Then, a NiOx layer was prepared in air via spin coating: a 5 mg / mL NiOx aqueous solution was filtered through a 0.22 μm PTFE membrane and dropped onto the FTO substrate surface. The solution was then spin-coated at 5000 rpm for 30 s, followed by heat annealing at 120°C for 15 minutes. The NiOx-coated substrate was then transferred to a nitrogen glove box for further preparation of a self-assembled monolayer (SAM): 110 μL of a 0.35 mg / mL Al ethanol solution was dropped onto the center of the substrate, spin-coated at 5000 rpm for 30 s, and then heat-annealed at 100°C for 10 minutes. The perovskite layer was deposited using a two-step spin-coating method, applying 110 μL of perovskite precursor solution (FA). 0.9 MA 0.05 Cs. 0.05A 1.5M PbI3 (DMF:DMSO = 4:1) solution was dropped onto the center of the substrate. The first spin coating was performed at 2000 rpm for 20 seconds, followed by a second spin coating at 4500 rpm for 35 seconds. Ten seconds before the end of the second spin coating step, 110 μL of anisole was added uniformly to the center of the substrate, followed by thermal annealing at 110°C for 20 minutes. After the perovskite film annealing was complete and cooled to room temperature, a passivation layer was prepared by dropping 110 μL of PDADI2 solution (1,3-propanediamine hydroiodate dissolved in isopropanol (IPA), concentration 0.5 mg / mL) onto the center of the substrate. The layer was then spin-coated at 5000 rpm for 30 seconds and annealed at 100°C for 5 minutes. After annealing, the battery is transferred to a vapor deposition system, where a 21 nm thick C60 layer is deposited on the perovskite layer using vacuum thermal evaporation. Subsequently, a 25 nm thick SnO2 layer is deposited at 90°C using atomic layer deposition (ALD). Finally, after scraping off excess film at the common end, a 100 nm thick Ag electrode is deposited by vacuum evaporation under masked conditions.

[0210] Based on A1 obtained in Example 1, the performance of perovskite solar cell devices was fabricated and characterized according to the above procedure. The current-voltage (J-V) characteristic curves of the cell device performance are shown below. Figure 14 As shown, the open-circuit voltage Voc is 1.177V, and the short-circuit current density Jsc is 25.42mA / cm². 2 The fill factor FF is 0.863 and the photoelectric conversion efficiency is 25.82%.

[0211] Example 7

[0212] Perovskite solar cells were fabricated using the self-assembled monolayer material A2 obtained in Example 2, such as... Figure 19 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0213] The specific device fabrication process is as follows: First, the FTO conductive glass substrate is pretreated. The FTO glass is ultrasonically cleaned sequentially in detergent, deionized water, ethanol, and acetone for 15 minutes each, and then dried in a 75°C oven. Before use, the glass is treated with ultraviolet ozone for 10 minutes, and then a NiOx layer is prepared in air by spin coating. A 5 mg / mL NiOx aqueous solution is filtered through a 0.22 μm PTFE membrane and dropped onto the surface of the FTO substrate. It is then spin-coated at 5000 rpm for 30 s on a spin coater, followed by thermal annealing at 120°C for 15 minutes. The substrate after NiOx preparation is transferred to a nitrogen glove box to continue preparing a self-assembled monolayer (SAM). 110 μL of a 0.35 mg / mL A2 ethanol solution is dropped onto the center of the substrate, spin-coated at 5000 rpm for 30 s, and then thermally annealed at 100°C for 10 minutes. The perovskite layer was deposited using a two-step spin-coating method, applying 110 μL of perovskite precursor solution (FA). 0.9 MA 0.05 Cs. 0.05 A 1.5M PbI3 (DMF:DMSO = 4:1) solution was dropped onto the center of the substrate. The first spin coating was performed at 2000 rpm for 20 seconds, followed by a second spin coating at 4500 rpm for 35 seconds. Ten seconds before the end of the second spin coating, 110 μL of anisole was added uniformly to the center of the substrate, followed by thermal annealing at 110°C for 20 minutes. After the perovskite film annealing was complete and the temperature cooled to room temperature, a passivation layer was prepared. 110 μL of PDADI2 (dissolved in IPA, 0.5 mg / mL) solution was dropped onto the center of the substrate, and the layer was spin-coated at 5000 rpm for 30 seconds, followed by annealing at 100°C for 5 minutes. After annealing, the cell was transferred to an evaporation system, where a 21 nm layer of C60 was deposited on the perovskite layer using vacuum thermal evaporation. Subsequently, a 25 nm layer of SnO2 was deposited at 90°C using 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 was deposited by vacuum evaporation under masked conditions.

[0214] Based on A2 obtained in Example 2, perovskite solar cell devices were fabricated and characterized according to the above procedure. The current-voltage (J-V) characteristic curves of the cell device performance are shown below. Figure 15 The open-circuit voltage Voc is 1.072V, and the short-circuit current density Jsc is 25.05mA / cm². 2 The fill factor FF is 0.8535 and the photoelectric conversion efficiency is 22.92%.

[0215] Example 8

[0216] Perovskite solar cells were fabricated using the self-assembled monolayer material A3 obtained in Example 3 as the hole transport layer, such as... Figure 19 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0217] The specific device fabrication process is as follows: First, the FTO conductive glass substrate is pretreated. The FTO glass is ultrasonically cleaned sequentially in detergent, deionized water, ethanol, and acetone for 15 minutes each, and then dried in a 75°C oven. Before use, the glass is treated with ultraviolet ozone for 10 minutes, and then a NiOx layer is prepared in air by spin coating. A 5 mg / mL NiOx aqueous solution is filtered through a 0.22 μm PTFE membrane and dropped onto the surface of the FTO substrate. It is then spin-coated at 5000 rpm for 30 s on a spin coater, followed by thermal annealing at 120°C for 15 minutes. The substrate after NiOx preparation is transferred to a nitrogen glove box to continue preparing a self-assembled monolayer (SAM). 110 μL of an 0.35 mg / mL A3 ethanol solution is dropped onto the center of the substrate, spin-coated at 5000 rpm for 30 s, and then thermally annealed at 100°C for 10 minutes. The perovskite layer was deposited using a two-step spin-coating method, applying 110 μL of perovskite precursor solution (FA). 0.9 MA 0.05 Cs. 0.05 A 1.5M PbI3 (DMF:DMSO = 4:1) solution was dropped onto the center of the substrate. The first spin coating was performed at 2000 rpm for 20 seconds, followed by a second spin coating at 4500 rpm for 35 seconds. Ten seconds before the end of the second spin coating, 110 μL of anisole was added uniformly to the center of the substrate, followed by thermal annealing at 110°C for 20 minutes. After the perovskite film annealing was complete and the temperature cooled to room temperature, a passivation layer was prepared. 110 μL of PDADI2 (dissolved in IPA, 0.5 mg / mL) solution was dropped onto the center of the substrate, and the layer was spin-coated at 5000 rpm for 30 seconds, followed by annealing at 100°C for 5 minutes. After annealing, the cell was transferred to an evaporation system, where a 21 nm layer of C60 was deposited on the perovskite layer using vacuum thermal evaporation. Subsequently, a 25 nm layer of SnO2 was deposited at 90°C using 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 was deposited by vacuum evaporation under masked conditions.

[0218] Based on A3 obtained in Example 3, perovskite solar cell devices were fabricated and characterized according to the above procedure. The current-voltage (J-V) characteristic curves of the cell device performance are shown below. Figure 16 The open-circuit voltage Voc is 1.113V, and the short-circuit current density Jsc is 25.31mA / cm². 2 The fill factor FF is 0.8507 and the photoelectric conversion efficiency is 23.96%.

[0219] Example 9

[0220] Perovskite solar cells were fabricated using the self-assembled monolayer material A20 obtained in Example 4 as the hole transport layer, such as... Figure 19 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0221] The specific device fabrication process is as follows: First, the FTO conductive glass substrate is pretreated. The FTO glass is ultrasonically cleaned sequentially in detergent, deionized water, ethanol, and acetone for 15 minutes each, and then dried in a 75°C oven. Before use, the glass is treated with ultraviolet ozone for 10 minutes, and then a NiOx layer is prepared in air by spin coating. A 5 mg / mL NiOx aqueous solution is filtered through a 0.22 μm PTFE membrane and dropped onto the surface of the FTO substrate. It is then spin-coated at 5000 rpm for 30 s on a spin coater, followed by thermal annealing at 120°C for 15 minutes. The substrate after NiOx preparation is transferred to a nitrogen glove box to continue preparing a self-assembled monolayer (SAM). 110 μL of an ethanol solution with a concentration of 0.35 mg / mL A2O is dropped onto the center of the substrate, spin-coated at 5000 rpm for 30 s, and then thermally annealed at 100°C for 10 minutes. The perovskite layer was deposited using a two-step spin-coating method, applying 110 μL of perovskite precursor solution (FA). 0.9 MA 0.05 Cs. 0.05 A 1.5M PbI3 (DMF:DMSO = 4:1) solution was dropped onto the center of the substrate. The first spin coating was performed at 2000 rpm for 20 seconds, followed by a second spin coating at 4500 rpm for 35 seconds. Ten seconds before the end of the second spin coating, 110 μL of anisole was added uniformly to the center of the substrate, followed by thermal annealing at 110°C for 20 minutes. After the perovskite film annealing was complete and the temperature cooled to room temperature, a passivation layer was prepared. 110 μL of PDADI2 (dissolved in IPA, 0.5 mg / mL) solution was dropped onto the center of the substrate, and the layer was spin-coated at 5000 rpm for 30 seconds, followed by annealing at 100°C for 5 minutes. After annealing, the cell was transferred to an evaporation system, where a 21 nm layer of C60 was deposited on the perovskite layer using vacuum thermal evaporation. Subsequently, a 25 nm layer of SnO2 was deposited at 90°C using 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 was deposited by vacuum evaporation under masked conditions.

[0222] Based on the A20 obtained in Example 4, perovskite solar cell devices were fabricated and characterized according to the above procedure. The current-voltage (J-V) characteristic curves of the cell device performance are shown below. Figure 17The open-circuit voltage Voc is 1.191V, and the short-circuit current density Jsc is 25.21mA / cm². 2 The fill factor FF is 0.8579 and the photoelectric conversion efficiency is 25.76%.

[0223] Example 10

[0224] Perovskite solar cells were fabricated using the self-assembled monolayer material A21 obtained in Example 5 as the hole transport layer, such as... Figure 19 As shown, its structure is: Glass / FTO / NiOx / SAM / PVSK / C60 / SnO2 / Ag.

[0225] The specific device fabrication process is as follows: First, the FTO conductive glass substrate is pretreated. The FTO glass is ultrasonically cleaned sequentially in detergent, deionized water, ethanol, and acetone for 15 minutes each, and then dried in a 75°C oven. Before use, the glass is treated with ultraviolet ozone for 10 minutes, and then a NiOx layer is prepared in air by spin coating. A 5 mg / mL NiOx aqueous solution is filtered through a 0.22 μm PTFE membrane and dropped onto the surface of the FTO substrate. It is then spin-coated at 5000 rpm for 30 s on a spin coater, followed by thermal annealing at 120°C for 15 minutes. The substrate after NiOx preparation is transferred to a nitrogen glove box to continue preparing a self-assembled monolayer (SAM). 110 μL of an ethanol solution of 0.35 mg / mL A21 is dropped onto the center of the substrate, spin-coated at 5000 rpm for 30 s, and then thermally annealed at 100°C for 10 minutes. The perovskite layer was deposited using a two-step spin-coating method, applying 110 μL of perovskite precursor solution (FA). 0.9 MA 0.05 Cs. 0.05 A 1.5M PbI3 (DMF:DMSO = 4:1) solution was dropped onto the center of the substrate. The first spin coating was performed at 2000 rpm for 20 seconds, followed by a second spin coating at 4500 rpm for 35 seconds. Ten seconds before the end of the second spin coating, 110 μL of anisole was added uniformly to the center of the substrate, followed by thermal annealing at 110°C for 20 minutes. After the perovskite film annealing was complete and the temperature cooled to room temperature, a passivation layer was prepared. 110 μL of PDADI2 (dissolved in IPA, 0.5 mg / mL) solution was dropped onto the center of the substrate, and the layer was spin-coated at 5000 rpm for 30 seconds, followed by annealing at 100°C for 5 minutes. After annealing, the cell was transferred to an evaporation system, where a 21 nm layer of C60 was deposited on the perovskite layer using vacuum thermal evaporation. Subsequently, a 25 nm layer of SnO2 was deposited at 90°C using 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 was deposited by vacuum evaporation under masked conditions.

[0226] Based on the A21 obtained in Example 5, perovskite solar cell devices were fabricated and characterized according to the above procedure. The current-voltage (J-V) characteristic curves of the cell device performance are shown below. Figure 18 The open-circuit voltage Voc is 1.192V, and the short-circuit current density Jsc is 25.25mA / cm². 2 The fill factor FF is 0.8459 and the photoelectric conversion efficiency is 25.45%.

[0227] Comparative Example 1

[0228] The self-assembled monolayer material A1 in Example 5 was replaced with the following comparative compound 1:

[0229] .

[0230] The battery fabricated therein has an open-circuit voltage (Voc) of 1.143V and a short-circuit current density (Jsc) of 23.335 mA / cm². 2 The fill factor FF is 0.81 and the photoelectric conversion efficiency is 21.6%.

[0231] Furthermore, this invention performed energy level calculations and heterointerface transport model density of states calculations on the compound of Comparative Example 1 and the compounds of Comparative Examples 2-6 as follows:

[0232] Comparative Example 2

[0233]

[0234] Comparative Example 3

[0235]

[0236] Comparative Example 4

[0237]

[0238] Comparative Example 5

[0239]

[0240] Comparative Example 6

[0241] .

[0242] (1) Energy levels of self-assembled single-molecule hole transport materials

[0243] The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the SAM molecule were determined by density functional theory (DFT) calculations and aligned with the vacuum level. The HOMO levels range from -5.0 eV to -6.0 eV, aligned with the valence band top of typical perovskite absorbers (e.g., the valence band top of FAPbI3 is approximately -5.4 to -6.0 eV), thus enabling good hole transport. The LUMO levels lie between -1.0 eV and -3.0 eV, providing a sufficient barrier for electron injection and reducing charge recombination at the interface. Specific values ​​are as follows:

[0244] Table 1. HOMO and LUMO energy levels of self-assembled monomolecular hole transport materials

[0245]

[0246]

[0247] As shown in Table 1, the compound of the present invention has a suitable HOMO energy level that matches the valence band top of the perovskite, thereby achieving good hole transport; and the LUMO energy level is greater than the conduction band bottom of the perovskite, preventing electron injection into the perovskite, thus improving the photoelectric conversion efficiency of the perovskite photovoltaic device containing the compound of the present invention.

[0248] (2) Heterogeneous interface transport model

[0249] The heterointerface transport model is used to more accurately describe the carrier (electron and hole) transfer behavior at the SAM molecule-perovskite heterointerface. When the highest occupied molecular orbital (HOMO) energy level of the SAM molecule is higher than the perovskite valence band top (VBM), the electrons of the SAM molecule will transfer to the lower energy perovskite valence band. Equivalently, holes from the perovskite will transfer to the SAM, thus realizing hole transport.

[0250] First-principles DFT simulations were used to calculate the density of states (DOS) of each SAM molecule adsorbed on the perovskite interface to elucidate the electronic structure and interfacial interactions. The calculations were performed using Vienna Ab initio simulation software package version 6.4.2, employing a hybrid functional approach to balance computational efficiency with accuracy in describing the band gap and localized states. The simulation workflow is as follows:

[0251] Model Construction: A perovskite surface model was constructed using a FAPbI3 unit cell (3x3x1) with {001} crystal planes capped by PbI2. SAM molecules are adsorbed through their functional groups. Van der Waals interactions were introduced using DFT-D3 correction to account for non-covalent bonding. Periodic boundary conditions were applied, and a vacuum layer of at least 20 Å was created perpendicular to the interface to mitigate spurious interactions.

[0252] Geometric optimization: Initial structural relaxation was performed using the Generalized Gradient Approximation (GGA) and the Perdew-Burke-Ernzerhof (PBE) function. A plane-wave basis set with an energy cutoff of 400 eV was used, and the Brillouin zone was sampled using a 3×3×1 gamma-centered k-point grid. The core electron was treated with a Projected Enhanced Wave (PAW) pseudopotential, whose valence configuration includes the 5d Pb. 10 6s 2 6p 2 ,I's 5s 2 5p 5 And the corresponding settings for organic elements. The electronic self-consistent convergence criterion is set to 10. -5 eV, with the ionic force convergence criterion set at 0.02 eV / Å.

[0253] Electronic structure calculations: After optimization, single-point energies were calculated using the hybrid Heyd-Scuseria-Ernzerhof (HSE06) functional, which incorporates 25% accurate Hartree-Fock exchange with a screening parameter of 0.2 Å. -1 This hybrid approach corrects the inherent bandgap underestimation problem of pure GGA functionals, thus providing a more reliable DO spectrum.

[0254] Density of states calculation: The total density of states and projected density of states (PDOS) were calculated using the tetrahedral method, and Bloch correction was performed to eliminate dispersion effects, thus ensuring a high-resolution description of states near the Fermi level. The DOS was calculated from -10 eV to +5 eV relative to the Fermi level, with a grid spacing of 0.01 eV. The contributions of SAM molecules, perovskite lattice, and interface atoms to the PDOS were analyzed to identify hybridization effects, such as orbital overlap between the SAM π-conjugated system and the perovskite valence band states.

[0255] This calculation scheme reveals key interfacial electronic properties, including the bandgap mid-states generated by the SAM-perovskite interaction and the shift in the effective work function, which are crucial for improving the open-circuit voltage and fill factor of solar cells.

[0256] As can be seen from the density of states (DOS) diagram of the SAM-perovskite composite structure, compounds A1~A21 of the present invention and Comparative Example 1 have suitable HOMO energy levels, which form an energy level difference with the valence band top of the perovskite, which is conducive to the transport of holes from the perovskite to the SAM material, thereby improving the photoelectric conversion efficiency of the perovskite photovoltaic device containing the compounds of the present invention.

[0257] Comparative Examples 2, 4, and 5 were adsorbed on the surface of perovskite crystals, and the density of states (DOS) was continuously distributed, failing to form an effective heterostructure, suggesting that Comparative Examples 2, 4, and 5 cannot be used as hole transport materials.

[0258] Comparative Examples 3 and 6 are adsorbed on the surface of perovskite crystals. Their HOMO energy levels are comparable to the valence band top of perovskite, and no energy level difference is formed, which is not conducive to the transport of holes from perovskite to SAM materials.

[0259] The applicant declares that this invention illustrates the self-assembled monolayer hole transport material based on polycarbazole derivatives, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A self-assembled monolayer hole transport material based on polycarbazole derivatives, characterized in that, It has the structure shown in Equation I: ； Ar1 and Ar2 are extended conjugated groups, where Ar1 is selected from G2 and Ar2 is selected from any one of the following groups: ； The asterisk represents the bonding site of the functional group; Where L is a linking group, selected from any one of L2 to L3: ； in The linking site of the representative group.

2. The self-assembled monolayer hole transport material based on polycarbazole derivatives according to claim 1, characterized in that, The self-assembled monolayer hole transport material based on polycarbazole derivatives is any one of the following compounds: 。 3. A self-assembled monolayer hole transport material based on a polycarbazole derivative, characterized in that, The self-assembled monolayer hole transport material based on polycarbazole derivatives is the following compound: 。 4. The method for preparing a self-assembled monolayer hole transport material based on a polycarbazole derivative according to claim 1 or 2, characterized in that, The preparation method includes the following steps: (2) Synthesis of self-assembled monolayer hole transport materials with L = L2: S2-1. The compound shown in formula B reacts with the compound shown in formula C to give the compound shown in formula D. The reaction formula is as follows: ； S2-2. The compound shown in formula D reacts with the compound shown in formula E to give the compound shown in formula F. The reaction formula is as follows: ； S2-3. The compound shown in formula E undergoes a hydrogenation reduction reaction to obtain the compound shown in formula E, as shown in the following reaction formula: ； S2-4 and the compound shown in formula H undergo hydrolysis to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in formula I. The reaction formula is as follows: ； (3) Synthesis of self-assembled monolayer hole transport materials with L=L3: S3-1. Compound B reacts with compound c to give compound d, as shown in the following reaction equation: ； S3-2. The compound shown in formula d reacts with the compound shown in formula e to give the compound shown in formula f. The reaction formula is as follows: ； S3-3. The compound shown in formula f undergoes a hydrolysis reaction to obtain the self-assembled monolayer hole transport material based on the polycarbazole derivative shown in formula I. The reaction formula is as follows: ； R1 and R2 are independently selected from C1-C5 alkyl groups, and X is selected from halogens.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the compound shown in formula B to the compound shown in formula C in step S2-1 is 1:5 to 1:

7. The reaction described in step S2-1 is carried out in the presence of an alkaline substance, which is selected from potassium phosphate or sodium phosphate; The reaction described in step S2-1 is carried out in an organic solvent, wherein the organic solvent is selected from N-methylpyrrolidone; The reaction temperature in step S2-1 is 160~180℃, and the reaction time is 40~48 h; The reaction described in step S2-1 is carried out under the protection of an inert gas; The molar ratio of the compound shown in formula D to the compound shown in formula E in step S2-2 is 1:3 to 1:

4. The reaction described in step S2-2 is carried out in the presence of an alkaline substance, namely triethylamine; The reaction described in step S2-2 is carried out in the presence of a ligand selected from tris(o-tolyl)phosphine; The reaction described in step S2-2 is carried out in the presence of a catalyst, namely palladium acetate. The reaction temperature in step S2-2 is 100~120℃, and the reaction time is 12~20h; The reducing agent in the hydrogenation reduction reaction described in step S2-3 is sodium borohydride; The hydrogenation reduction reaction described in steps S2-3 is carried out in the presence of a catalyst, namely cobalt chloride. The hydrogenation reduction reaction described in steps S2-3 is carried out in an organic solvent, namely methanol. The hydrogenation reduction reaction described in steps S2-3 is carried out under nitrogen protection; The hydrogenation reduction reaction described in steps S2-3 is carried out at room temperature for 1-2 hours. The hydrolysis reaction described in steps S2-4 is carried out in the presence of trimethylbromosilane; The molar ratio of the trimethylbromosilane to the compound represented by formula H is 2:1 to 4:1; The hydrolysis reaction described in steps S2-4 is carried out in an organic solvent, wherein the organic solvent is selected from 1,4-dioxane; The hydrolysis reaction described in steps S2-4 is carried out at room temperature for 12-18 hours.

6. The preparation method according to claim 4, characterized in that, The molar ratio of the compound shown in formula B to the compound shown in formula c in step S3-1 is 1:3.5 to 1:5; The reaction described in step S3-1 is carried out in the presence of an alkaline substance, which is selected from potassium carbonate or sodium carbonate. The reaction described in step S3-1 is carried out in the presence of a catalyst selected from cuprous iodide; The reaction described in step S3-1 is carried out in an organic solvent, wherein the organic solvent is selected from N,N-dimethylacetamide; The reaction temperature in step S3-1 is 160~200℃, and the reaction time is 20~30 h; The molar ratio of the compound shown in formula d to the compound shown in formula e in step S3-2 is 1:1.5 to 1:3; The reaction described in step S3-2 is carried out in the presence of a catalyst, namely palladium acetate; The reaction described in step S3-2 is carried out in the presence of a ligand selected from 1,1'-bis(diphenylphosphine)ferrocene; The reaction described in step S3-2 is carried out in the presence of an alkaline substance, namely potassium acetate; The reaction temperature in step S3-2 is 100~120℃, and the reaction time is 20~30 hours; The reaction described in step S3-2 is carried out under nitrogen protection; The hydrolysis reaction described in step S3-3 is carried out in the presence of trimethylbromosilane; The molar ratio of the trimethylbromosilane to the compound shown in formula f is 2:1 to 4:

1.

7. A perovskite solar cell, characterized in that, The perovskite solar cell includes a self-assembled monolayer, which includes the hole transport material based on a polycarbazole derivative as described in any one of claims 1-3.

8. The perovskite solar cell according to claim 7, characterized in that, The perovskite solar cell is an inverted perovskite solar cell. The perovskite solar cell comprises, from top to bottom, a cathode layer, an electron transport layer, a passivation layer, a perovskite light-absorbing layer, a self-assembled monolayer, a hole transport layer, and an anode layer arranged sequentially. And / or, the self-assembled monolayer is obtained by coating a solution of the self-assembled monolayer hole transport material based on the polycarbazole derivative as described in any one of claims 1-3 onto the surface of the hole transport layer and then performing thermal annealing. The heat annealing temperature is 80~120℃, and the heat annealing time is 5~20 minutes.

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