Triphenylamine-carbazole-phosphonic acid derivatives, methods of preparation and uses thereof

Abstract

This invention relates to a triphenylamine-carbazole-phosphonic acid derivative, its preparation method, and its applications, belonging to the field of optoelectronic materials and devices technology. The preparation method of the triphenylamine-carbazole-phosphonic acid derivative includes: mixing compound 1a, compound 2a, a catalyst, and a mixed solvent under an inert gas atmosphere, followed by heating to obtain intermediate M0; dissolving intermediate M0 in dibromide, then adding a phase transfer catalyst and a base, and heating to obtain intermediate M1; dissolving intermediate M1 in triethyl phosphite, and heating to obtain intermediate M2; and hydrolyzing intermediate M2 to obtain the final product. Perovskite-based solar cells using the triphenylamine-carbazole-phosphonic acid derivative prepared according to this invention as the hole-selective contact layer can achieve a photoelectric conversion efficiency of >24.8%, which is superior to cells using traditional 2PACZ as the hole-selective contact layer.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic materials and devices technology, specifically relating to a triphenylamine-carbazole-phosphonic acid derivative, its preparation method, and its application. Background Technology

[0002] Thin-film optoelectronic devices, encompassing perovskite solar cells (PSCs), organic solar cells (OSCs), and perovskite light-emitting diodes (PeLEDs), have achieved groundbreaking research progress over the past few decades. With their excellent intrinsic properties such as solution processability, mechanical flexibility, and low-cost large-area fabrication, thin-film optoelectronic devices have shown enormous application potential in next-generation photovoltaic conversion, display imaging, and solid-state lighting technologies, becoming a research hotspot in both scientific research and industry. At the device fabrication level, most planar heterojunction thin-film optoelectronic devices are fabricated using a layer-by-layer solution deposition process, in which the charge transport layer (CTL) and photoactive layer are deposited sequentially and stepwise. The core performance characteristics of the device, such as photoelectric conversion efficiency and stability, can be significantly improved through the compositional control of the photosensitive material and the structural optimization of the interlayer interfaces.

[0003] Currently, reducing defects and regulating energy level matching to minimize interfacial recombination losses are crucial for improving device performance. Interface engineering has become a research hotspot. Inserting interface layers such as hole transport layers (HTLs) and electron transport layers (ETLs) between the photoactive layer and the electrode can effectively alleviate energy level mismatch and promote charge carrier transport, injection, and extraction. In addition to traditional HTL materials, self-assembled monolayers (SAMs), with their unique advantages such as regular structure, excellent interfacial contact, and low charge transport impedance, are also high-performance HTL materials, providing diverse and efficient options for performance optimization and structural innovation of perovskite devices.

[0004] SAMs (Solid Atomically Transparent Oxide Electrodes) consist of two-dimensional organic molecular arrays, with a thickness of only one or a few molecules. Due to their highly ordered and ultrathin structure, SAMs offer significant advantages over traditional HTLs (High-Temperature Transparent Oxide Electrodes). These advantages include minimal parasitic absorption and negligible electrical losses, leading to considerable interest in PSCs, OSCs, and PeLEDs in recent years. Introducing SAMs into these devices is considered the most effective strategy for reducing surface defects and improving hole injection or extraction at the device interface. From a molecular structure perspective, SAMs can be divided into three parts: anchoring groups, spacers, and functional groups, each with a distinct function. Anchoring groups (such as phosphonic acids or carboxylic acids) have a strong affinity for transparent conductive oxide (TCO) electrodes through their functional groups, such as hydrogen bonds, covalent bonds, or coordination bonds, facilitating chemical bonding with the substrate. Spacers, primarily composed of non-conjugated alkyl chains, act as connectors between the anchoring groups and functional groups, contributing to the overall functionality of the SAM. Functional groups are the most important components endowing SAMs with specific properties or functions. These properties include, but are not limited to, hole transport capability, electron transport capability, photoresponsiveness, and chemical reactivity. For example, when using p-type semiconductor carbazole as the functional group, SAM exhibits efficient hole transport, making it suitable for PSC, OSC, and PeLED.

[0005] Carbazole and its derivatives have become commonly used building blocks in the molecular design of perovskite photovoltaic SAMs due to their rigid planar structure and tunable electronic properties. The electron-donating properties of the carbazole core, coupled with the delocalized electron system, lead to a high charge density distribution and facilitate efficient hole transport. As high-level tractors (HTLs) in perovskite photovoltaics (PSCs), carbazole-based SAMs exhibit excellent performance: (i) excellent hole extraction through favorable energy level alignment with the perovskite layer, (ii) negligible parasitic absorption in the visible spectrum, (iii) cost-effective and simple solution processability, and (iv) structural adaptability through system molecular engineering.

[0006] Carbazole-based self-assembled monolayers possess unique helical π-extension properties, which enhance molecular dipole moments and π-π interactions, resulting in highly ordered monolayers and improved hole extraction. Furthermore, aromatic amine-based SAMs exhibit superior performance in thermodynamic stability and electrical performance tuning. The strong electron-donating properties of the triphenylamine (TPA) group can effectively tune interfacial energy levels, thereby optimizing energy level alignment with the perovskite layer. This energy level alignment is crucial for efficient hole extraction and transport, significantly reducing non-radiative recombination at the interface. The introduction of aromatic amine groups can also improve the stability and solubility of SAMs by enhancing the conjugation length of the molecules, thereby improving the film quality of SAMs on the substrate, reducing interfacial defects, and enhancing the overall device performance. Currently, carbazole derivatives modified with triphenylamine substituents have been applied in perovskite solar cells, but the poor performance of perovskite solar cells still exists. Summary of the Invention

[0007] The first objective of this invention is to provide a triphenylamine-carbazole-phosphonic acid derivative to solve the technical problem that existing triphenylamine-substituted carbazole derivatives still have poor performance in perovskite solar cells.

[0008] A second objective of this invention is to provide a method for preparing a triphenylamine-carbazole-phosphonic acid derivative.

[0009] A third objective of this invention is to provide an application of a triphenylamine-carbazole-phosphonic acid derivative as a hole-selective contact layer in perovskite-based solar cells.

[0010] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0011] The structural formula of the triphenylamine-carbazole-phosphonic acid derivative is shown in Formula I:

[0012] Formula I;

[0013] In Formula I, n is an integer from 1 to 10, and R is one of hydrogen atom, halogen atom, alkyl, alkoxy, substituent-substituted alkoxy, aryl, or substituent-substituted aryl.

[0014] Furthermore, the halogen atom is one of fluorine, chlorine, bromine, and iodine atoms; the alkyl group is C1-C. 20 Alkyl; the alkoxy group is C1-C 20 Alkoxy group; the alkoxy group in the substituent-substituted alkoxy group is C1-C. 20 Alkoxy group; the substituent in the alkoxy group substituted by the substituent and the aryl group substituted by the substituent is one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, hydroxy, carboxyl, and mercapto.

[0015] The preparation method of the triphenylamine-carbazole-phosphonic acid derivative includes the following steps:

[0016] S1: Under an inert gas atmosphere, compound 1a, compound 2a, catalyst, and mixed solvent are mixed and heated to react and obtain intermediate M0;

[0017] S2: Under an inert gas atmosphere, the intermediate M0 is dissolved in dibromide, and then a phase transfer catalyst and a base are added, and the reaction is heated to obtain intermediate M1;

[0018] S3: Under an inert gas atmosphere, intermediate M1 is dissolved in triethyl phosphite and heated to obtain intermediate M2. Intermediate M2 is hydrolyzed to obtain triphenylamine-carbazole-phosphonic acid derivative.

[0019] The structural formula of compound 1a is shown in Formula II; the structural formula of compound 2a is shown in Formula III; the structural formula of intermediate M0 is shown in Formula IV; the structural formula of the dibromide is shown in Formula V; the structural formula of intermediate M1 is shown in Formula VI; and the structural formula of intermediate M2 is shown in Formula VII.

[0020] Formula II; Formula III; Formula IV; Formula V; Formula VI; Formula VII.

[0021] Furthermore, in S1, the molar ratio of compound 1a to compound 2a is 1:2 to 1:2.2; the molar ratio of compound 1a to the catalyst is 5:0.125 to 5:0.2; and 30 to 36 mL of mixed solvent is added for every 5 mmol of compound 1a.

[0022] Furthermore, the catalyst in S1 is tetra(triphenylphosphine)palladium; the mixed solvent is a mixture of sodium carbonate aqueous solution with a concentration of 1-2 M and 1,4-dioxane; the volume ratio of sodium carbonate aqueous solution to 1,4-dioxane in the mixed solvent is 1:5 to 1:6.

[0023] Furthermore, in S2, 8-10 mL of dibromide is added for every 5 mmol of the intermediate Mo; the molar ratio of the intermediate Mo to the phase transfer catalyst is 5:1; 1-3 mL of base is added for every 5 mmol of the intermediate Mo; the base is a 40-50% potassium hydroxide aqueous solution; and the phase transfer catalyst is tetrabutylammonium bromide.

[0024] Furthermore, in S3, 8-10 mL of triethyl phosphite is added for every 2 mmol of intermediate M1; the hydrolysis is performed by dissolving intermediate M2 in 1,4-dioxane, cooling to 0 °C and adding trimethylbromosilane, then heating to 25 °C and reacting for 12-24 h to obtain intermediate a, which is dissolved in methanol, then hydrolyzed with water and filtered.

[0025] Furthermore, the heating reaction in S1 is carried out at a temperature of 90–100 °C for 12–24 h; the heating reaction in S2 is carried out at a temperature of 100–120 °C for 12–24 h; and the heating reaction in S3 is carried out at a temperature of 160–165 °C for 12–24 h.

[0026] Application of triphenylamine-carbazole-phosphonic acid derivatives as hole-selective contact layers in optoelectronic devices.

[0027] Furthermore, the optoelectronic device is one or more of the following: perovskite solar cell, organic single-junction solar cell, tandem solar cell, perovskite light-emitting diode, organic light-emitting diode, perovskite photodetector, and organic photodetector; the tandem solar cell is one or more of the following: perovskite-crystalline silicon tandem cell, all-perovskite tandem cell, perovskite-Cu(InGa)Se2 tandem cell, and perovskite-organic tandem cell.

[0028] An optoelectronic device, comprising, in sequence, a conductive substrate layer, a hole-selective contact layer, a photoactive layer, an electron transport layer, a modification layer, and a top electrode layer, wherein the hole-selective contact layer is prepared from the aforementioned triphenylamine-carbazole-phosphonic acid derivative.

[0029] Furthermore, the conductive substrate includes, but is not limited to, ITO, FTO, AZO, IZO, Si, and CIGS; the hole-selective contact layer is prepared from a triphenylamine-carbazole-phosphonic acid derivative by immersion, blade coating, spin coating, or vapor deposition; the photoactive layer is prepared from tin-based perovskite, lead-based perovskite, tin-lead perovskite, or organic materials by spin coating, blade coating, slot coating, screen printing, spraying, ink printing, roll-to-roll process, or vapor deposition; the electron transport layer is made from C 60 C 70 PC 61 BM, PC 71 BM, TiO2, ZnO or SnO2 are prepared by spin coating, blade coating, vapor deposition, atomic deposition or magnetron sputtering; the top electrode is prepared by Ag, Cu, Au, Al, Cr, ITO, IZO, FTO, AZO or C electrode by blade coating, slot coating, screen printing, thermal vapor deposition, atomic deposition or magnetron sputtering.

[0030] The beneficial effects of this invention are:

[0031] The triphenylamine-carbazole-phosphonic acid derivative of this invention uses triphenylamine as a substituent to enhance the interaction between the molecule and perovskite, with a carbazole group having a rigid planar structure and tunable electronic properties as the parent core, and alkylphosphonic acid as the anchoring group. The triphenylamine-carbazole-phosphonic acid derivative of this invention has advantages such as simple synthesis steps, mild synthesis conditions, and good physical and chemical stability, making it suitable as a highly efficient and stable hole-selective contact layer for applications in perovskite, organic single-junction solar cells, perovskite-crystalline silicon tandem cells, all-perovskite tandem cells, perovskite-Cu(InGa)Se2 tandem cells, perovskite-organic tandem cells, perovskite / organic light-emitting diodes, and perovskite / organic photodetectors.

[0032] The triphenylamine-carbazole-phosphonic acid derivative of this invention has a more efficient interface charge extraction efficiency and exhibits superior photovoltaic performance compared with traditional 2PACz-based devices.

[0033] The perovskite-based solar cell prepared using the triphenylamine-carbazole-phosphonic acid derivative of this invention as the hole-selective contact layer can achieve a photoelectric conversion efficiency of >24.8%, which is superior to the performance of the perovskite-based solar cell using the traditional 2PACZ as the hole-selective contact layer. Attached Figure Description

[0034] Figure 1 This is a structural diagram of the perovskite-based solar cell in Application Example 1;

[0035] Figure 2 The current-voltage (JV) characteristic curve of the perovskite-based solar cell in Application Example 1 is shown.

[0036] Figure 3 The current-voltage characteristic curve of the perovskite-based solar cell in Application Example 2 is shown.

[0037] Figure 4 The current-voltage characteristic curve of the perovskite-based solar cell in Application Example 3 is shown.

[0038] Figure 5 The current-voltage characteristic curves of the perovskite-based solar cell in Comparative Example 1 are shown.

[0039] Figure 6 The 1H NMR spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 1;

[0040] Figure 7 The carbon spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 1;

[0041] Figure 8 The phosphorus spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 1;

[0042] Figure 9 The 1H NMR spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 2;

[0043] Figure 10 The carbon spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 2;

[0044] Figure 11 The phosphorus spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 2;

[0045] Figure 12 The 1H NMR spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 3;

[0046] Figure 13 The carbon spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 3;

[0047] Figure 14 The phosphorus spectrum of the triphenylamine-carbazole-phosphonic acid derivative in Example 3 is shown. Detailed Implementation

[0048] The present invention will be further described below with reference to the embodiments and accompanying drawings.

[0049] Flowcharts of the preparation of triphenylamine-carbazole-phosphonic acid derivatives in Examples 1-3 of this invention:

[0050]

[0051] Example 1

[0052] The preparation method of the triphenylamine-carbazole-phosphonic acid derivative in Example 1 includes the following steps:

[0053] (1) Synthesis of intermediate M0

[0054] 5.0 mmol of compound 1a, 10.0 mmol of compound 2a, and 0.2 mmol of tetra(triphenylphosphine)palladium were added sequentially to a dry reaction vessel. The reaction system was then purged under a nitrogen atmosphere, followed by the sequential addition of 6 mL of 2 M sodium carbonate aqueous solution and 30 mL of 1,4-dioxane under stirring to obtain a reaction mixture. The reaction mixture was heated to 100 °C and stirred for 24 h. After the reaction was complete, dichloromethane was added for extraction. The organic phases were combined and dried over anhydrous sodium sulfate, followed by vacuum distillation to remove the solvent, yielding crude intermediate M0. Crude intermediate M0 was purified by silica gel column chromatography to obtain 3.25 mmol of a white powder, with a yield of 65%. The eluent for silica gel column chromatography was petroleum ether and dichloromethane in a volume ratio of 2:1.

[0055] The 1H NMR spectrum data of intermediate M0 are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.29 (s,1H), 7.65 (dd, J = 8.4, 1.7 Hz, 1H), 7.58 (d, J = 8.1 Hz, 2H), 7.50 – 7.38(m, 1H), 7.27 (t, J = 7.8 Hz, 4H), 7.16 (dd, J = 13.9, 8.1 Hz, 6H), 7.02 (t,J = 7.3 Hz, 2H).

[0056] The carbon spectral data of intermediate M0 are as follows: 13 C NMR (151 MHz, Chloroform-d) δ 147.17 (d, J =203.1 Hz), 139.19, 136.34, 135.87, 132.66, 129.26, 127.93, 125.26, 125.01,124.47, 124.21, 124.06, 123.38, 122.72, 121.81, 118.42, 110.94.

[0057] The high-resolution mass spectrometry results for intermediate M0 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 48 H 36 N3): 654.2909, found 654.2888.

[0058] (2) Synthesis of intermediate M1-C3

[0059] Under a nitrogen atmosphere, 5.0 mmol of M0 was dissolved in 10 mL of 1,3-dibromopropane, followed by the sequential addition of 1.0 mmol of tetrabutylammonium bromide and 2 mL of a 50% potassium hydroxide aqueous solution to obtain a mixture. The mixture was stirred at 120 °C for 24 h. After the reaction was complete, the combined organic layers were extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure to obtain crude M1-C3. The crude M1-C3 was purified by column chromatography to obtain 2.83 g of white powder M1-C3, with a yield of 73%.

[0060] The 1H NMR spectrum of intermediate M1-C3 is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.31 (s, 2H),7.71 (d, J = 8.5 Hz, 2H), 7.59 (d, J = 8.1 Hz, 4H), 7.52 (d, J = 8.5 Hz, 2H),7.28 – 7.25 (m, 8H), 7.19 – 7.15 (m, 12H), 7.02 (t, J = 7.3 Hz, 4H), 4.53 (s,2H), 3.42 (t, J = 6.1 Hz, 2H), 2.48 (t, J = 6.3 Hz, 2H).

[0061] The carbon spectrum results of intermediate M1-C3 are as follows: 13C NMR (151 MHz, CDCl3) δ 147.83, 146.51,140.08, 136.21, 132.38, 129.25, 127.89, 125.20, 124.43, 124.22, 122.72,118.53, 108.99, 41.16, 32.05, 30.83.

[0062] The high-resolution mass spectrometry results for intermediate M1-C3 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 51 H 41 BrN3): 775.2516, found 775.2397.

[0063] (3) Synthesis of intermediate M2-C3

[0064] Under a nitrogen atmosphere, 2.0 mmol of M1-C3 was dissolved in 8 mL of triethyl phosphite to obtain a mixture. The mixture was heated at 160 °C for 24 h, then cooled to 25 °C, and the organic solvent was removed by rotary evaporation to obtain crude M2-C3. The crude M2-C3 was purified by column chromatography to give 1.50 g of white solid M2-C3, with a yield of 90%.

[0065] The 1H NMR spectrum of intermediate M2-C3 is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.32 (s, 2H),7.70 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.2 Hz, 4H), 7.50 (s, 6H), 7.29 – 7.25(m, 4H), 7.19 – 7.14 (m, 12H), 7.02 (t, J = 7.3 Hz, 4H), 4.46 (t, J = 7.1 Hz,2H), 4.09 – 4.05 (m, 4H), 2.27 – 2.22 (m, 2H), 1.83 – 1.76 (m, 2H), 1.29 (t,J = 7.1 Hz, 6H).

[0066] The carbon spectrum results of intermediate M2-C3 are as follows: 13C NMR (151 MHz, CDCl3) δ 171.12, 147.83,146.47, 140.06, 136.29, 132.24, 129.25, 127.89, 125.15, 124.45, 124.20,123.61, 122.72, 118.50, 109.04, 63.66, 60.38, 53.47, 21.04, 14.21.

[0067] The phosphorus spectrum results of intermediate M2-C3 are as follows: 31 P NMR (202 MHz, CDCl3) δ 30.99.

[0068] The high-resolution mass spectrometry results for intermediate M2-C3 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 55 H 51 N3O3P):832.3668, found 832.3622.

[0069] (4) Synthesis of triphenylamine-carbazole-phosphonic acid derivative WU-2

[0070] Under a nitrogen atmosphere, 2.0 mmol of M2-C3 was dissolved in 10 mL of dry 1,4-dioxane and placed in a Schlenk flask. Then, 1.5 g of trimethylbromosilane (TMSBr) was added dropwise at 0 °C to obtain a mixture. The mixture was heated to 25 °C and stirred for 12 h to allow the reaction to proceed. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure to obtain intermediate a. Intermediate a was dissolved in 10 mL of methanol (MeOH), followed by the addition of 20 mL of distilled water until the solution became cloudy. The reaction was continued with stirring for 12 h. After the reaction was complete, the solid was collected by filtration and washed with water to obtain 1.40 g of milky white powder WU-2, with a yield of 90%.

[0071] The results of the 1H NMR spectrum of WU-2 are as follows: Figure 6 As shown: 1 H NMR (500 MHz, DMSO-d6) δ 8.55 (s,2H), 7.76 – 7.69 (m, 8H), 7.31 (t, J = 7.7 Hz, 8H), 7.10 – 7.03 (m, 16H), 4.51 (t, J = 6.8 Hz, 2H), 2.05 – 1.97 (m, 2H), 1.60 – 1.53 (m, 2H).

[0072] The carbon spectrum results of WU-2 are as follows Figure 7 As shown: 13 C NMR (151 MHz, DMSO-d6) δ 147.13, 145.70,139.70, 135.52, 130.70, 129.43, 127.54, 123.64, 122.80, 118.24, 109.72,25.52, 24.61, 22.78.

[0073] The phosphorus spectrum results of WU-2 are as follows: Figure 8 As shown: 31 P NMR (202 MHz, DMSO-d6) δ 25.77.

[0074] The high-resolution mass spectrometry results for WU-2 are: HRMS-ESI (m / z): [M+H] + Calcd. for (C 51 H 43 N3O3P):776.3042, found 776.2996.

[0075] Example 2

[0076] The preparation method of the triphenylamine-carbazole-phosphonic acid derivative in Example 2 includes the following steps:

[0077] (1) Synthesis of intermediate M0

[0078] The synthesis method of intermediate M0 is the same as that of Example 1.

[0079] (2) Synthesis of intermediate M1-C4

[0080] Under a nitrogen atmosphere, 5.0 mmol of M0 was dissolved in 10 mL of 1,4-dibromobutane, followed by the sequential addition of 1.0 mmol of tetrabutylammonium bromide and 2 mL of a 50% potassium hydroxide aqueous solution to obtain a mixture. The mixture was stirred at 120 °C for 24 h. After the reaction was complete, the combined organic layers were extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure to obtain crude M1-C4. The crude M1-C4 was purified by column chromatography to obtain 2.76 g of white powder M1-C4, with a yield of 70%.

[0081] The 1H NMR spectrum of intermediate M1-C4 is as follows: 1H NMR (500 MHz, CDCl3) δ 8.32 (s, 2H),7.71 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.1 Hz, 4H), 7.45 (d, J = 8.3 Hz, 2H),7.29 – 7.26 (m, 10H), 7.20 – 7.15 (m, 10H), 7.03 (t, J = 7.5 Hz, 4H), 4.40 (s, 2H), 3.41 (t, J = 6.4 Hz, 2H), 2.15 – 2.09 (m, 2H), 1.99 – 1.94 (m, 2H).

[0082] The carbon spectrum results for intermediate M1-C4 are as follows: 13 C NMR (151 MHz, CDCl3) δ 132.20, 129.25,127.90, 125.12, 124.46, 124.22, 123.60, 122.72, 108.92, 33.13, 30.26.

[0083] The high-resolution mass spectrometry results for intermediate M1-C4 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 52 H 43 BrN3): 788.2640, found 788.2595.

[0084] (3) Synthesis of intermediate M2-C4

[0085] Under a nitrogen atmosphere, 2.0 mmol of M1-C4 was dissolved in 8 mL of triethyl phosphite to obtain a mixture. The mixture was heated at 160 °C for 24 h, then cooled to 25 °C, and the organic solvent was removed by rotary evaporation to obtain crude M2-C4. The crude M2-C4 was purified by column chromatography to give 1.52 g of white solid M2-C4, with a yield of 90%.

[0086] The 1H NMR data for intermediate M2-C4 are as follows: 1H NMR (500 MHz, CDCl3) δ 8.31 (s, 2H), 7.69 (d, J = 10.3 Hz, 2H), 7.59 (d, J = 8.4 Hz, 4H), 7.43 (d, J = 8.5 Hz, 2H), 7.30 – 7.25 (m, 8H), 7.19 – 7.14 (m, 12H), 7.03 – 7.00 (m, 4H), 4.35 (s,2H), 4.06 – 3.99 (m, 4H), 2.07 – 2.02 (m, 2H), 1.79 – 1.69 (m, 4H), 1.25 (t,J = 7.1 Hz, 6H).

[0087] The carbon spectral data of intermediate M2-C4 are as follows: 13 C NMR (151 MHz, CDCl3) δ 147.83, 146.44,140.05, 136.32, 132.11, 129.24, 127.87, 125.06, 124.44, 124.19, 123.56,122.69, 118.50, 108.95, 61.60, 42.81, 25.93, 24.99, 20.46, 16.44.

[0088] The phosphorus spectrum data of intermediate M2-C4 are as follows: 31 P NMR (202 MHz, CDCl3) δ 32.07.

[0089] The high-resolution mass spectrometry data for intermediate M2-C4 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 52 H 53 N3O3P): 846.3824, found 846.3779.

[0090] (4) Synthesis of triphenylamine-carbazole-phosphonic acid derivative WU-1

[0091] Under a nitrogen atmosphere, 2.0 mmol of M2-C4 was dissolved in 10 mL of dry 1,4-dioxane and placed in a Schlenk flask. Then, 1.5 g of trimethylbromosilane was added dropwise at 0 °C to obtain a mixture. The mixture was heated to 25 °C and stirred for 24 h. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure to obtain intermediate a. Intermediate a was dissolved in 10 mL of methanol, followed by the addition of 20 mL of distilled water until the solution became cloudy. The reaction was continued with stirring for 24 h. After the reaction was complete, the solid was collected by filtration and washed with water to obtain 1.50 g of milky white powder WU-1, with a yield of 95%.

[0092] The 1H NMR data of WU-1 are as follows Figure 9 As shown: 1 H NMR (500 MHz, CDCl3) δ 8.54 (s, 2H),7.77 – 7.69 (m, 6H), 7.67 (d, J = 8.6 Hz, 2H), 7.35 – 7.28 (m, 8H), 7.09 –7.03 (m, 16H), 4.42 (t, J = 7.0 Hz, 2H), 1.91 – 1.86 (m, 2H), 1.55 (d, J =8.8 Hz, 4H).

[0093] The carbon spectral data of WU-1 are as follows Figure 10 As shown: 13 C NMR (151 MHz, CDCl3) δ 147.18, 145.73,139.73, 135.59, 130.66, 129.48, 127.58, 124.43, 124.03, 123.68, 122.85,118.25, 109.77, 29.59, 27.79, 26.88, 20.45.

[0094] Phosphorus spectrum data of WU-1 as follows Figure 11 As shown: 31 P NMR (202 MHz, CDCl3) δ 26.08.

[0095] The high-resolution mass spectrometry data for WU-1 are: HRMS-ESI (m / z): [M+H] + Calcd. for (C 52 H 45 N3O3P):790.3198, found 790.3153.

[0096] Example 3

[0097] The preparation method of the triphenylamine-carbazole-phosphonic acid derivative in Example 3 includes the following steps:

[0098] (1) Synthesis of intermediate M0

[0099] The synthesis method of intermediate M0 is the same as that of Example 1.

[0100] (2) Synthesis of intermediate M1-C8

[0101] Under a nitrogen atmosphere, 5.0 mmol of M0 was dissolved in 10 mL of 1,8-dibromooctane, followed by the sequential addition of 1.0 mmol of tetrabutylammonium bromide and 2 mL of a 50% potassium hydroxide aqueous solution to obtain a mixture. The mixture was stirred at 120 °C for 24 h. After the reaction was complete, the combined organic layers were extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure to obtain crude M1-C8. The crude M1-C8 was purified by column chromatography to obtain 2.79 g of white powder M1-C8, with a yield of 66%.

[0102] The 1H NMR data for intermediate M1-C8 are as follows: 1 H NMR (500 MHz, CDCl3) δ 8.31 (s, 2H),7.69 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.0 Hz, 4H), 7.44 (s, 2H), 7.29 – 7.26(m, 8H), 7.16 – 7.14 (m, 12H), 7.02 (s, 4H), 4.38 (s, 2H), 3.37 (t, J = 7.0Hz, 2H), 1.93 – 1.80 (m, 4H), 1.49 – 1.30 (m, 8H).

[0103] The carbon spectral data of intermediate M1-C8 are as follows: 13 C NMR (151 MHz, CDCl3) δ 131.94, 129.18,127.81, 124.96, 124.55, 124.29, 123.48, 122.75, 118.53, 109.04, 33.93, 32.68,29.22, 28.59, 28.03, 27.21.

[0104] (3) Synthesis of intermediate M2-C8

[0105] Under a nitrogen atmosphere, 2.0 mmol of M1-C8 was dissolved in 10 mL of triethyl phosphite to obtain a mixture. The mixture was heated at 160 °C for 24 h, then cooled to 25 °C, and the organic solvent was removed by rotary evaporation to obtain crude M2-C8. The crude M2-C8 was purified by column chromatography to give 1.53 g of white solid M2-C8, with a yield of 85%.

[0106] The 1H NMR spectrum data of intermediate M2-C8 are as follows: 1 H NMR (500 MHz, CDCl3) δ 8.32 (s, 2H),7.70 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 6.8 Hz, 4H), 7.51 (s, 1H), 7.44 (d, J= 8.5 Hz, 2H), 7.29 – 7.26 (m, 7H), 7.20 – 7.13 (m, 12H), 7.02 (t, J = 7.3Hz, 4H), 4.33 (s, 2H), 4.12 – 4.07 (m, 4H), 2.04 (s, 8H), 1.91 (t, J = 7.4Hz, 2H), 1.60 – 1.55 (m, 4H), 1.18 (t, J = 7.7 Hz, 6H).

[0107] The carbon spectral data of intermediate M2-C8 are as follows: 13 C NMR (151 MHz, CDCl3) δ 131.93, 129.23,127.88, 124.97, 124.49, 124.19, 123.49, 122.68, 118.47, 109.01, 63.66, 61.82,53.43, 29.18, 27.28, 19.31, 18.37, 16.12, 6.59.

[0108] The phosphorus spectrum data of intermediate M2-C8 are as follows: 31 P NMR (202 MHz, CDCl3) δ 32.51.

[0109] The high-resolution mass spectrometry data for intermediate M2-C8 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for(C 60 H 61 N3O3P):902.4451, found 902.4449.

[0110] (4) Synthesis of triphenylamine-carbazole-phosphonic acid derivative WU-3

[0111] Under a nitrogen atmosphere, 2.0 mmol of M2-C8 was dissolved in 10 mL of dry 1,4-dioxane and placed in a Schlenk flask. Then, 1.5 g of trimethylbromosilane was added dropwise at 0 °C to obtain a mixture. The mixture was heated to 25 °C and stirred for 24 h. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure to obtain intermediate a. Intermediate a was dissolved in 10 mL of methanol, followed by the addition of 20 mL of distilled water until the solution became cloudy. The reaction was continued with stirring for 24 h. After the reaction was complete, the solid was collected by filtration and washed with water to obtain 1.44 g of milky white powder WU-3, with a yield of 85%.

[0112] The 1H NMR data of WU-3 are as follows Figure 12 As shown: 1 H NMR (500 MHz, CDCl3) δ 8.55 (s, 2H),7.76 – 7.72 (m, 6H), 7.64 (d, J = 8.5 Hz, 2H), 7.32 (t, J = 7.7 Hz, 8H), 7.11– 7.04 (m, 16H), 4.40 (t, J = 7.1 Hz, 2H), 1.81 – 1.78 (m, 2H), 1.49 – 1.44(m, 4H), 1.36 – 1.23 (m, 8H).

[0113] The carbon spectral data of WU-3 are as follows Figure 13 As shown: 13 C NMR (151 MHz, CDCl3) δ 147.13, 145.68,135.54, 130.59, 129.44, 127.52, 124.39, 123.99, 123.64, 122.83, 118.22,109.64, 29.95, 29.84, 28.51, 27.89, 26.99, 26.38, 22.56.

[0114] Phosphorus spectrum data of WU-3 as follows Figure 14 As shown: 31 P NMR (202 MHz, CDCl3) δ 26.56.

[0115] The high-resolution mass spectrometry data for WU-3 are as follows: HRMS-ESI (m / z): [M+H] + Calcd. for (C 56 H 53O3P):846.3824, found 846.3818.

[0116] Application Example 1

[0117] Perovskite-based solar cells were fabricated using the triphenylamine-carbazole-phosphonic acid derivative WU-1 prepared in Example 2 as a hole-selective contact layer. Figure 1 As shown, the structure of the perovskite-based solar cell is ITO / WU-1 / perovskite / C 60 / BCP / Ag.

[0118] The fabrication method of perovskite-based solar cells includes the following steps: ITO conductive glass is sequentially ultrasonically cleaned with glass cleaner, purified water, and isopropanol for 15 min. After cleaning the ITO glass with an air gun, it is treated with a plasma cleaner for 5 min. Using WU-1 synthesized in Example 2 as the hole-selective contact layer, WU-1 is dissolved at a concentration of 0.5 mg / mL in a mixed solution of chlorobenzene and N,N-dimethylformamide. 60 µL of the WU-1 solution is pipetted and uniformly dropped onto the ITO glass. The glass is rotated at 3000 rpm for 20 s, heat-annealed at 120 °C for 10 min, and then cooled to room temperature before adding 1.7 M FA... 0.9 MA 0.05 Cs 0.05 PbI 2.75 Br 0.15 The perovskite precursor solution was spin-coated onto the WU-1 surface at 5000 rpm and then heat-annealed at 120 °C for 20 min. After cooling to room temperature, 30 nm C films were deposited on the perovskite film surface. 60 And 6 nm of 2,9-dimethyl-4,7-diphenyl-1,10-o-phenanthroline (BCP). Finally, 100 nm of Ag was vacuum thermally deposited as the top electrode to obtain the perovskite-based solar cell device with an effective area of ​​0.1 cm². 2 The volume ratio of chlorobenzene to N,N-dimethylformamide is 3:1.

[0119] Application Example 2

[0120] The fabrication method of the perovskite-based solar cell in Application Example 2 is the same as that in Application Example 1. The difference between the fabrication method of the perovskite-based solar cell in Application Example 2 and Application Example 1 is that WU-2 is used instead of WU-1 as the hole-selective contact layer in Application Example 2.

[0121] Application Example 3

[0122] The fabrication method of the perovskite-based solar cell in Application Example 3 is the same as that in Application Example 1. The difference between the fabrication method of the perovskite-based solar cell in Application Example 3 and Application Example 1 is that WU-3 is used instead of WU-1 as the hole-selective contact layer in Application Example 3.

[0123] Comparative Example 1

[0124] The fabrication method of the perovskite-based solar cell in Comparative Example 1 is the same as that in Application Example 1. The difference between the fabrication method of the perovskite-based solar cell in Comparative Example 1 and Application Example 1 is that 2-(9H-carbazole-9-yl)ethylphosphonic acid (2PACZ) is used instead of WU-1 as the hole-selective contact layer in Comparative Example 1.

[0125] A xenon lamp solar simulator was used to test the light source intensity at AM 1.5G (100 mW cm⁻¹). -2 The current-voltage (JV) characteristic curves of the inverted perovskite solar cell device were tested, and the test results are as follows: Figure 2-5 As shown.

[0126] from Figure 2 It can be seen that the open-circuit voltage (V) of the perovskite-based solar cell device based on WU-1 oc The voltage is 1.16 V, and the short-circuit current density is J. sc 25.4 mA cm -2 The fill factor FF is 84.7%, and the photoelectric conversion efficiency can reach 25.0%.

[0127] from Figure 3 It can be seen that the perovskite-based solar cell device based on WU-2 V oc It is 1.16 V, J sc 25.4 mA cm -2 The FF is 84.3% and the photoelectric conversion efficiency is 24.8%.

[0128] from Figure 4 It can be seen that the perovskite-based solar cell device based on WU-3 V oc It is 1.17 V, J sc 25.2 mA cm -2 The FF is 85.0% and the photoelectric conversion efficiency is 25.0%.

[0129] from Figure 5 It is known that the photoelectric conversion efficiency of perovskite-based solar cell devices based on 2PACZ is very low, only 23.5%. oc It is 1.14 V, J sc 24.7 mA cm -2 FF was 83.8%.

[0130] from Figure 2-5 As can be seen, the triphenylamine-carbazole-phosphonic acid derivative prepared in this invention, when used as a self-assembled hole-selective material to prepare perovskite-based solar cells, can achieve a photoelectric conversion efficiency of >24.8%. Compared with the traditional material 2PACZ, WU-1, WU-2, and WU-3 of this invention, as molecular hole transport layers in perovskite-based solar cells, significantly improve the charge extraction rate, thereby greatly enhancing the photoelectric conversion efficiency and stability of perovskite-based solar cells.

[0131] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the claims.

[0132] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. The scope of patent protection of the present invention shall be determined by the claims. Similarly, any equivalent structural changes made based on the content of the present invention's specification shall also be included within the scope of protection of the present invention.

Claims

1. A triphenylamine-carbazole-phosphonic acid derivative, characterized in that, The structural formula of the triphenylamine-carbazole-phosphonic acid derivative is shown in Formula I: Formula I; In Formula I, n is an integer from 1 to 10, and R is one of hydrogen atom, halogen atom, alkyl, alkoxy, substituent-substituted alkoxy, aryl, or substituent-substituted aryl.

2. The triphenylamine-carbazole-phosphonic acid derivative according to claim 1, characterized in that, The halogen atom is one of fluorine, chlorine, bromine, or iodine atoms; the alkyl group is C1-C6. 20 Alkyl; the alkoxy group is C1-C 20 Alkoxy group; the alkoxy group in the substituent-substituted alkoxy group is C1-C. 20 Alkoxy group; the substituent in the alkoxy group substituted by the substituent and the aryl group substituted by the substituent is one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, hydroxy, carboxyl, and mercapto.

3. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to any one of claims 1 to 2, characterized in that, Includes the following steps: S1: Under an inert gas atmosphere, compound 1a, compound 2a, catalyst, and mixed solvent are mixed and heated to react and obtain intermediate M0; S2: Under an inert gas atmosphere, the intermediate M0 is dissolved in dibromide, and then a phase transfer catalyst and a base are added, and the reaction is heated to obtain intermediate M1; S3: Under an inert gas atmosphere, intermediate M1 is dissolved in triethyl phosphite and heated to obtain intermediate M2. Intermediate M2 is hydrolyzed to obtain triphenylamine-carbazole-phosphonic acid derivative. The structural formula of compound 1a is shown in Formula II; the structural formula of compound 2a is shown in Formula III; Formula II; Formula III.

4. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to claim 3, characterized in that, The molar ratio of compound 1a to compound 2a in S1 is 1:2 to 1:2.2; the molar ratio of compound 1a to the catalyst is 5:0.125 to 5:0.2; and 30 to 36 mL of mixed solvent is added for every 5 mmol of compound 1a.

5. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to claim 3, characterized in that, The catalyst in S1 is tetra(triphenylphosphine)palladium; the mixed solvent is a mixture of sodium carbonate aqueous solution with a concentration of 1-2 M and 1,4-dioxane; the volume ratio of sodium carbonate aqueous solution to 1,4-dioxane in the mixed solvent is 1:5 to 1:

6.

6. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to claim 3, characterized in that, In S2, 8–10 mL of dibromide is added for every 5 mmol of the intermediate MO; the molar ratio of the intermediate MO to the phase transfer catalyst is 5:1; 1–3 mL of base is added for every 5 mmol of the intermediate MO; the base is a 40–50% (w / w) aqueous solution of potassium hydroxide; the phase transfer catalyst is tetrabutylammonium bromide; the structural formula of the dibromide is shown in Formula V. Formula V.

7. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to claim 3, characterized in that, In S3, 8-10 mL of triethyl phosphite is added for every 2 mmol of intermediate M1; the hydrolysis is performed by dissolving intermediate M2 in 1,4-dioxane, cooling to 0 °C and adding trimethylbromosilane, then heating to 25 °C and reacting for 12-24 h to obtain intermediate a, which is dissolved in methanol, then hydrolyzed with water and filtered.

8. The method for preparing the triphenylamine-carbazole-phosphonic acid derivative according to claim 3, characterized in that, The heating reaction in S1 is carried out at a temperature of 90–100 °C for 12–24 h; the heating reaction in S2 is carried out at a temperature of 100–120 °C for 12–24 h; and the heating reaction in S3 is carried out at a temperature of 160–165 °C for 12–24 h.

9. The application of the triphenylamine-carbazole-phosphonic acid derivative as described in claim 1 as a hole-selective contact layer in optoelectronic devices.

10. An optoelectronic device, characterized in that, The hole-selective contact layer of the optoelectronic device is prepared from the triphenylamine-carbazole-phosphonic acid derivative as described in claim 1.

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