Hole transport material and its application

Abstract

The present invention belongs to the technical field of solar energy industry, and specifically relates to a hole transport material containing halogen and its application as an organic hole transport material. The present invention designs a cyanoacetic acid or cyanophosphoric acid as an anchoring group, and introduces halogen into the molecular structure through a self-assembled monolayer strategy, thereby obtaining a new type of hole transport material containing halogen, the purpose of which is to solve the technical problems such as poor stability and poor device performance faced by existing organic small molecule hole transport materials with anchoring groups. In addition, the present invention also relates to a perovskite battery and a flexible perovskite battery prepared using the aforementioned organic hole transport material. The beneficial effect of the present invention is that the introduction of halogen atoms in the material can improve the stability of the battery and extend its service life.

Description

Technical Field

[0001] The present invention belongs to the field of organic optoelectronic materials, and more specifically, relates to a hole transport material and its application in electron transport devices. The hole transport material of the present invention can be used in the preparation of devices such as perovskite light-emitting diodes and perovskite batteries. Background Art

[0002] Perovskite light-emitting diodes (PeLEDs) are an emerging technology with significant potential in display, lighting, communications, and other fields. Besides their cost advantages, such as ease of fabrication, PeLEDs also offer advantages such as flexible fabrication, thinness and light weight, continuously tunable emission wavelength, and high color purity, making them a strong contender for next-generation light source technology. In recent years, significant breakthroughs have been made in the development of PeLEDs, with their maximum external quantum efficiency (EQE) rapidly increasing from 1% to ~28%.

[0003] The classic PeLED structure is similar to that of an organic light-emitting diode (OLED), both of which are sandwich structures, including a cathode, a light-emitting layer, and an anode. In order to improve the luminous efficiency of the device, a hole transport material (HTM) is often added between the anode and the light-emitting layer. Currently, the most widely used hole transport materials are poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS) and poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). PEDOT:PSS has average device efficiency due to energy level mismatch and low hole transport rate. Although PTAA has relatively high device efficiency, its high price makes it unsuitable for large-scale production. Therefore, the development of low-cost, high-performance HTM materials is the key to promoting the development of the PeLED industry.

[0004] As third-generation solar cells, perovskite solar cells, with their high photoelectric conversion efficiency, low cost, and pollution-free properties, show strong commercial application prospects in the fields of clean green energy development and environmental protection. The hole-transporting layer (HTL) in perovskite devices plays an important role in carrier transport and suppressing non-radiative hole recombination. Currently, the most commonly used hole-transporting and hole-injection layer materials are mainly organic materials, such as sprio-OMeTAD, PEDOT:PSS, and PTAA. However, these organic hole-transporting layer materials are often complex to manufacture and expensive. They also have poor thermal stability, poor interfacial bonding with perovskites, are prone to leakage, and have a short service life.

[0005] Furthermore, the molecular design of existing HTM materials, whether for perovskite light-emitting devices or perovskite solar cells, focuses on improving hole transport and interface passivation to enhance luminescence efficiency. Despite significant progress in HTM material development, the material costs remain high, and the materials are not suitable for large-scale manufacturing, hindering their industrialization. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a hole transport material with good hole transport properties, strong interface passivation ability and suitable for large-scale applications.

[0007] To achieve the above objectives, the present invention adopts a self-assembled monolayer synthesis strategy to synthesize a hole transport material. The hole transport material is based on a carbazole derivative as a parent core and cyanoacetic acid or cyanophosphoric acid as an anchoring group, and has the following structural formula:

[0008]

[0009] Wherein, R represents a carboxyl group, a phosphoric acid group, a sulfonic acid group, or an aldehyde group;

[0010] L represents a C6-C30 substituted or unsubstituted arylene group, or a C3-C30 substituted or unsubstituted heteroarylene group;

[0011] R1-R9 independently represent hydrogen, deuterium, halogen, aldehyde, carboxyl, cyano, nitro, amino, sulfonic acid, boric acid, silicon, sulfone, sulfoxide, amide; C1-C30 substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy; C1-C30 substituted or unsubstituted haloalkyl, C1-C30 substituted or unsubstituted alkylsilyl, C6-C30 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl;

[0012] A represents O, S, SO, SO2, Se, NR 10 , CR 11 R 12 ; R 10 -R 12 R is independently represented by hydrogen, deuterium, C1-C30 substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy; C1-C30 substituted or unsubstituted haloalkyl, C1-C30 substituted or unsubstituted alkylsilyl, C6-C30 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl; and R 11 and R 12 Can be connected to each other to form a ring;

[0013] Preferably, L is phenylene or biphenylene;

[0014] R1-R9 independently represent hydrogen, deuterium, fluorine, chlorine, bromine, iodine, methyl, ethyl, phenyl, cyano, nitro, amino, methoxy, methylthio;

[0015] Further preferably, the structure of the hole transport material includes but is not limited to any one of the following compound formulas (1) to (67):

[0016]

[0017]

[0018]

[0019]

[0020] The synthesis route of the hole transport material of the present invention is as follows:

[0021]

[0022]

[0023] The strong base used in step a) is one of potassium tert-butoxide, sodium tert-butoxide, and sodium hydride, the reaction solvent is N'N-dimethylformamide, and the heating temperature is 100-140°C; the strong base used in step b) is piperidine, the reaction solvent is acetonitrile, and the heating temperature is 60-80°C; and in step c), the hydrolysis reagent used is trimethylsilyl bromide, the reaction solvent is dichloromethane, the reaction temperature is 15-25°C, and the quenching reagent used in the reaction is methanol.

[0024] Compared with existing hole transport materials (HTM) as hole transport layer (HTL) materials, the present invention adopts a self-assembled monolayer (SAM) strategy to develop HTM materials. Its unique technical advantages are: (1) SAM molecules are simple to synthesize and require low dosage; (2) SAM films can be manufactured with high throughput and low cost by methods such as immersion; (3) SAM molecules can be chemically bonded to the substrate, with good solution processability and stability; (4) SAM can minimize the thickness of the HTM film to reduce series resistance and promote battery efficiency. The synthesis method of the present invention can greatly improve the performance of HTM material products by enhancing the hole transport and interface passivation properties of the material through molecular design. At the same time, the present invention adopts simplified synthesis steps, reducing the synthesis cost of HTM materials, making it suitable for large-scale promotion and application, and helping to promote the industrialization of perovskite solar cells.

[0025] The structure of a perovskite light-emitting diode prepared by using the hole transport material of the present invention is: ITO / hole transport layer / perovskite / C60 / BCP / Cu, wherein the structural formula of the BCP material is

[0026]

[0027] The structure of a quantum dot perovskite light-emitting diode prepared using the hole transport material of the present invention is: ITO / hole injection layer / hole transport layer / quantum dot / electron transport layer / electron injection layer / cathode; wherein the electron transport layer uses TPBi material, and its structural formula is as follows:

[0028]

[0029] The preparation method of the above-mentioned quantum dot perovskite light-emitting diode is as follows:

[0030] S1: Prepare a mixed liquid of PEDOT and DSS in a certain molar ratio and filter it through a 0.22 μm filter to obtain a filtrate;

[0031] S2: In an air environment, a thin film is spin-coated on a clean ITO glass substrate using the filtrate obtained in step S1 at a certain rotation speed, and annealed at 140° C. for 15 minutes to obtain an intermediate A having a hole injection layer of PEDOT:DSS, and then the intermediate A is transferred to an inert atmosphere;

[0032] S3: Prepare an ethanol solution of a certain concentration of a hole transport material, then spin-coat a thin film on the surface of the PEDOT:DSS layer of intermediate A at a certain rotation speed, anneal at 150°C for 15 minutes, and then spin-coat a perovskite quantum dot solution dissolved in n-octane on the hole transport layer at a certain rotation speed, and anneal at 60°C for 10 minutes to obtain intermediate B;

[0033] S4: Intermediate B was transferred to a thermal evaporation system and heated to 2 × 10 -4 An electron transport layer of a certain thickness is deposited under a high vacuum environment of Pa, an electron injection layer is evaporated on the electron transport layer, and a cathode is evaporated on the surface of the electron injection layer, and the layer is packaged to obtain a quantum dot perovskite light-emitting diode.

[0034] The above description merely illustrates the application of the present invention by using the hole transport material of the present invention to prepare perovskite light-emitting diodes and quantum dot perovskite light-emitting diodes. Furthermore, those skilled in the art, based on common knowledge and technical expertise in the field of optoelectronic materials, can also apply the hole transport material of the present invention to fields such as perovskite cells, organic electroluminescent devices, organic solar cells, organic thin-film transistors, organic photodetectors, organic field-effect transistors, organic integrated circuits, and organic photoreceptors.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The self-assembled monolayer hole transport material based on carbazole derivatives of the present invention uses indenocarbazole / benzofurancarbazole / benzothiophenecarbazole with a rigid conjugated large plane as a parent core to ensure the excellent hole transport performance of the material. Different parent cores can regulate the molecular stacking pattern and interface passivation properties, thereby improving the photovoltaic performance of the material. Cyanoacetic acid or cyanophosphoric acid is used as an anchoring group to achieve the firm self-assembly of the hole transport molecules on the substrate surface. The parent core and the anchoring group are bridged by a double bond, which, unlike previous SAM molecules, can further enhance the degree of conjugation of the molecule, thereby increasing the charge transport capacity of the material.

[0037] In addition, thanks to the characteristics of the self-assembled monolayer, the self-assembled monolayer hole transport material provided by the present invention has maximized atom economy, and large-area thin films can be continuously prepared by the immersion method. The driving voltage of the perovskite light-emitting diode prepared as a hole transport material is lower than 4.6V, and the efficiency is greater than 6.1%. When the synthesized material is used as the hole transport layer of an inverted perovskite solar cell, a high open circuit voltage of >11 V and a photoelectric conversion efficiency of >23% can be obtained without doping, while greatly improving the life and stability of the perovskite solar cell, which is expected to help the perovskite solar cell achieve industrialization, and is used as a hole transport material in quantum dot light-emitting devices to prepare high-efficiency quantum dot light-emitting devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The H-NMR spectrum and C-NMR spectrum of Formula 19 prepared by the present invention;

[0039] Figure 2 H NMR spectrum and C NMR spectrum of formula 34 prepared by the present invention;

[0040] Figure 3 The H-NMR spectrum and C-NMR spectrum of Formula 35 prepared by the present invention;

[0041] Figure 4 H NMR spectrum and C NMR spectrum of Formula 48 prepared by the present invention;

[0042] Figure 5 The H-NMR spectrum and C-NMR spectrum of Formula 64 prepared by the present invention;

[0043] Figure 6 H NMR spectrum and C NMR spectrum of Formula 65 prepared by the present invention;

[0044] Figure 7 The J / V curve of Formula 19 prepared by the present invention as a hole transport material for a perovskite light-emitting diode;

[0045] Figure 8 The J / V curve of Formula 34 prepared by the present invention as a hole transport material for a perovskite light-emitting diode;

[0046] Figure 9 The J / V curve of Formula 35 prepared by the present invention as a hole transport material for a perovskite light-emitting diode;

[0047] Figure 10 The J / V curve of Formula 48 prepared by the present invention as a hole transport material for a perovskite light-emitting diode;

[0048] Figure 11 The J / V curve of Formula 64 prepared by the present invention as a hole transport material for a perovskite light-emitting diode;

[0049] Figure 12 The J / V curve of Formula 65 prepared by the present invention as a hole transport material for perovskite light-emitting diodes. DETAILED DESCRIPTION

[0050] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below with reference to the accompanying drawings and preferred embodiments.

[0051] The self-assembled monolayer hole transport material of the present invention uses a carbazole derivative as a mother core and cyanoacetic acid or cyanophosphoric acid as an anchoring group, and is synthesized and developed using a self-assembled monolayer (SAM) strategy.

[0052] When the anchoring group is cyanoacetic acid, taking Formula 19, Formula 34 and Formula 35 as examples, the detailed synthesis routes are as follows:

[0053] Step 1: 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (raw material 1) / 5H-benzofuran[3,2-c]carbazole (raw material 3) / 5H-benzo[4,5]thieno[3,2-c]carbazole (raw material 4) and p-fluorobenzaldehyde (raw material 2) react to obtain 4-(7,7-dimethylindeno[2,1-b]carbazole-5(7H)-yl)benzaldehyde (intermediate 1) / 4-(5H-benzofuran[3,2-c]carbazole-5-yl)benzaldehyde (intermediate 2) / 4-(5H-benzo[4,5]thieno[3,2-c]carbazole-5-yl)benzaldehyde (intermediate 3):

[0054]

[0055] Step 2: Intermediate 1 / Intermediate 2 / Intermediate 3 react with 2-cyanoacetic acid (raw material 5) to obtain 2-cyano-3-(4-(7,7-dimethylindeno[2,1-b]carbazole-5(7H)-yl)phenyl)acrylic acid (Formula 19) / 3-(4-(5H-benzofurano[3,2-c]carbazole-5-yl)phenyl)-2-cyanoacrylic acid (Formula 34) / 3-(4-(5H-benzo[4,5]thieno[3,2-c]carbazole-5-yl)phenyl)-2-cyanoacrylic acid (Formula 35):

[0056]

[0057] Furthermore, in step 1, the strong base used in the reaction is one of potassium tert-butoxide, sodium tert-butoxide, and sodium hydride, the reaction solvent is N'N-dimethylformamide (DMF), and the reaction temperature is 100-140°C.

[0058] Furthermore, in step 2, the strong base used in the reaction is piperidine, the reaction solvent is acetonitrile (MeCN), and the reaction temperature is 60-80°C.

[0059] When the anchoring group is cyanophosphate, taking Formula 48, Formula 64 and Formula 65 as examples, the detailed synthesis routes are as follows:

[0060] Step 1: 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (raw material 1) / 5H-benzofuran[3,2-c]carbazole (raw material 3) / 5H-benzo[4,5]thieno[3,2-c]carbazole (raw material 4) and p-fluorobenzaldehyde (raw material 2) react to obtain 4-(7,7-dimethylindeno[2,1-b]carbazole-5(7H)-yl)benzaldehyde (intermediate 1) / 4-(5H-benzofuran[3,2-c]carbazole-5-yl)benzaldehyde (intermediate 2) / 4-(5H-benzo[4,5]thieno[3,2-c]carbazole-5-yl)benzaldehyde (intermediate 3):

[0061]

[0062] Step 2: Intermediate 1 / Intermediate 2 / Intermediate 3 react with diethyl (cyanomethyl)phosphonate (raw material 6) to obtain diethyl (1-cyano-2-(4-(7,7-dimethylindeno[2,1-b]carbazole-5(7H)-yl)phenyl)vinyl)phosphonate (Intermediate 4) / diethyl (2-(4-(5H-benzofurano[3,2-c]carbazole-5-yl)phenyl)-1-cyanovinyl)phosphonate (Intermediate 5) / diethyl (2-(4-(5H-benzo[4,5]thieno[3,2-c]carbazole-5-yl)phenyl)-1-cyanovinyl)phosphonate (Intermediate 6):

[0063]

[0064] Step 3: Intermediate 1 / Intermediate 2 / Intermediate 3 are hydrolyzed to obtain (1-cyano-2-(4-(7,7-dimethylindeno[2,1-b]carbazole-5(7H)-yl)phenyl)vinyl)phosphonic acid (Formula 48) / (2-(4-(5H-benzofurano[3,2-c]carbazole-5-yl)phenyl)-1-cyanovinyl)phosphonic acid (Formula 64) / (2-(4-(5H-benzo[4,5]thieno[3,2-c]carbazole-5-yl)phenyl)-1-cyanovinyl)phosphonic acid (Formula 65):

[0065]

[0066] Furthermore, in step 1, the strong base used in the reaction is one of potassium tert-butoxide, sodium tert-butoxide, and sodium hydride, the reaction solvent is N'N-dimethylformamide (DMF), and the reaction temperature is 100-140°C.

[0067] Furthermore, in step 2, the strong base used in the reaction is piperidine, the reaction solvent is acetonitrile (MeCN), and the reaction temperature is 60-80°C.

[0068] Furthermore, in step three, the hydrolysis reagent used in the reaction is trimethylsilyl bromide (Me3SiBr), the reaction solvent is dichloromethane (DCM), the reaction temperature is 15-25°C, and the quenching reagent used in the reaction is methanol.

[0069] The preferred embodiments of the present invention are further described below through preferred examples.

[0070] Example 1

[0071] The synthetic route of formula 19:

[0072]

[0073] Specific synthesis steps:

[0074] 1) Synthesis of Intermediate 1: Drain raw materials 1 (5 g, 17.7 mmol) and t-BuOK (5.9 g, 53.0 mmol), add 300 mL of DMF, and stir at 50°C for 30 min. Raise the temperature to 130°C, and gradually add raw material 2 (3.3 g, 26.5 mmol) in three portions. Initially, the reaction solution turns dark, but as the temperature rises and the reaction proceeds, the solution gradually becomes clear. Reflux at 130°C for 3 h with a PE / DCM (1 / 1) filter plate, and the reaction is complete. Remove the reaction mixture, spin-dry the DMF, and rinse with a 2-3 cm silica gel filter using a PE / DCM (1 / 1) filter plate. Concentrate the eluate, add EtOH, and the product precipitates. Filter and dry to obtain 4.1 g of a white solid, yield 59.9%. HRMS (ESI, m / z): [M]+ calculated for C 28 H 21 NO,387.1623,found 387.1626. 1 HNMR (400MHz, Chloroform-d) δ10.06 (s, 1H), 8.35 (d, J = 0.8Hz, 1H), 8.10 (td, J = 8.1, 1.4Hz, 3H), 7.81–7.71 (m, 3H), 7.42–7.19 (m, 7H), 1.44 (s, 6H). 13 C NMR (101MHz, CDCl3) δ191.06,153.47,153.38,143.57,140.58,140.42,139.43,134.75,133.22,131.54,127.17, 127.06,126.61,125.99,124.24,123.58,122.63,120.88,120.38,119.51,111.53,109.81,103.95,46.87,27.95.

[0075] 2) Synthesis of Formula 19: Intermediate 1 (0.6 g, 1.55 mmol) and raw material 3 (0.39 g, 4.65 mmol) were purged three times, 60 mL of MeCN was added, and then piperidine (1.05 g, 12.40 mmol) was added. The temperature was raised to 120°C and refluxed for 4.5 h. PE / DCM = 1 / 1 was used to fill the plate. No raw material remained, and the reaction was complete. Remove the reaction mixture, spin-dry the MeCN, and pass it through a short silica gel. First, rinse with pure DCM to remove impurities. Then, rinse with DCM / MeOH = 5 / 1 to obtain the product. The product was concentrated and precipitated in MeOH. Filter and dry to obtain 350 mg of a white solid with a yield of 49.7%. HRMS (ESI, m / z): [M-COOH+H] + calculated for C 30 H 22N2,410.1783,found410.1786. 1 H NMR(600MHz,DMSO-d6)δ8.70(d,J=0.7Hz,1H),8.30(dt,J=7.8,1.0Hz,1H),8.26-8.21(m,2H) ,8.10(s,1H),7.93(dt,J=7.6,0.9Hz,1H),7.86-7.80(m,2H),7.61(d,J=0.7Hz,1H),7.54(dt, J=7.4,0.9Hz,1H),7.47(dt,J=8.2,1.0Hz,1H),7.44(ddd,J=8.2,6.8,1.2Hz,1H),7.38(td,J =7.4, 1.1Hz, 1H), 7.33 (ddd, J = 7.9, 6.8, 1.2Hz, 1H), 7.29 (td, J = 7.4, 1.2Hz, 1H), 1.49 (s, 6H). 13 C NMR (151MHz, DMSO) δ163.60,153.68,153.53,146.89,140.75,140.55,139.40,139.33,132.76,132.61,131.82,127.59,127. 45,127.00,126.61,123.73,123.20,123.17,121.00,120.86,119.95,119.65,114.10,112.35,110.42,104.70,46.98,28.03.

[0076] Example 2

[0077] The synthetic route of formula 34 is as follows:

[0078]

[0079] Specific synthesis steps:

[0080] 1) Synthesis of Intermediate 2: The synthesis steps of Intermediate 2 were similar to those of Intermediate 1, except that starting material 4 (5 g, 19.45 mmol) was used instead of starting material 1. The resulting product was a pale yellow solid (4.0 g) with a yield of 57.0%. HRMS (ESI, m / z): [M] + calculated for C 25 H 15 NO2,361.1103, found 361.1105. 1H NMR(400MHz,Chloroform-d)δ10.18(s,1H),8.65–8.58(m,1H),8.24–8.17(m,2H),8.05–7.97 (m,2H),7.92–7.86(m,2H),7.81–7.75(m,1H),7.60–7.46(m,5H),7.43(td,J=7.4,1.1Hz,1H). 13 CNMR (101MHz, CDCl3) δ191.01,156.41,151.18,143.35,140.52,139.85,135.03,131.48,127.26,126. 15,125.65,124.89,123.03,121.63,121.49,119.89,118.29,117.34,111.79,109.80,109.38,105.40.

[0081] 2) Synthesis of Formula 34: The synthesis steps of Formula 34 are similar to those of Formula 19, except that Intermediate 2 (0.7 g, 1.94 mmol) was used in place of Intermediate 1. The resulting product was a yellow solid (0.3 g) with a yield of 36.1%. HRMS (ESI, m / z): [M-COOH+H]+ calculated for C 27 H 16 N2O,384.1263, found 384.1266. 1 H NMR(600MHz,DMSO-d6)δ8.45(d,J=7.7Hz,1H),8.23(d,J=8.0Hz,2H),8.19(d ,J=8.1Hz,2H),8.08(s,1H),7.87(dd,J=11.4,8.1Hz,3H),7.60–7.43(m,6H). 13 C NMR (151MHz, DMSO) δ162.73,156.07,150.66,146.04,140.88,140.14,138.75,133.45,131.60,127.71,126.97,126.4 1,124.85,123.92,122.51,121.77,120.83,120.67,119.91,119.48,116.76,115.64,112.21,110.78,108.35,106.55.

[0082] Example 3

[0083] The synthetic route of formula 35 is as follows:

[0084]

[0085] Specific synthesis steps:

[0086] 1) Synthesis of Intermediate 3: The synthesis steps of Intermediate 3 were similar to those of Intermediate 1, except that starting material 5 (5 g, 18.32 mmol) was used instead of starting material 1. The resulting product was a pale yellow solid (4.3 g) with a yield of 62.0%. HRMS (ESI, m / z): [M] + calculated for C 25 H 15 NOS,377.0874,found 377.0877. 1 H NMR (400MHz, Chloroform-d) δ10.17(s,1H),8.41–8.30(m,1H),8.25–8.14(m,4H),8.02(dd,J=7.6,1.4Hz,1H),7.89–7.83(m,2H),7.63–7.47(m,6H). 13 C NMR (101MHz, CDCl3) δ191.00,143.20,140.03,139.16,138.84,135.81,135.03,132.99,131.49,129.74,127.22,126.12,125.68,125.61,125.2 1,124.75,124.58,123.11,123.06,123.00,121.94,121.66,121.46,12 1.08,120.85,119.57,119.33,117.78,110.76,109.94,108.37,107.47.

[0087] 2) Synthesis of Formula 35: The synthesis steps of Formula 35 were similar to those of Formula 19, except that Intermediate 3 (0.7 g, 1.86 mmol) was used in place of Intermediate 1. The resulting product was a yellow solid (0.29 g) with a yield of 35.0%. HRMS (ESI, m / z): [M-COOH+H]+ calculated for C 27 H 16 N2S,400.1034,found 400.1033. 1H NMR(600MHz,DMSO-d6)δ8.41(dd,J=12.8,8.2Hz,2H),8.26–8.20(m,3H),8.19–8.13(m,2H),7.90– 7.86(m,2H),7.62(dd,J=19.9,8.4Hz,2H),7.56(ddd,J=14.6,6.9,1.4Hz,2H),7.53–7.48(m,2H). 13 C NMR (101MHz, DMSO) δ162.43,145.77,140.29,139.53,138.56,138.16,135.92,133.53,132.07,131.55,129.36,127.6 7,126.92,126.33,125.64,123.77,122.19,121.97,121.77,121.46,120.74,120.00,116.76,116.00,110.89,108.59.

[0088] Example 4

[0089] The synthetic route of formula 48 is as follows:

[0090]

[0091] Specific synthesis steps:

[0092] 1) Synthesis of Intermediate 4: Intermediate 1 (0.8 g, 2.07 mmol) was purged three times, 80 mL of MeCN was added, and then starting material 6 (1.1 g, 6.50 mmol) and piperidine (1.04 g, 16.27 mmol) were added. The temperature was raised to 80°C and refluxed for 3.5 h. PE / DCM = 1 / 1 was used to point the plate. When no starting material remained, the reaction was completed. The reaction mixture was removed and cooled to room temperature. The reaction solvent was spin-dried. Silica gel was passed through a short column and pure DCM was used as the eluent. The filtrate was spin-dried. Samples were prepared and separated by column chromatography, with the eluent PE / DCM = 4 / 1 → 2 / 1. 0.57 g of the product was obtained as a yellow solid with a yield of 50.4%. HRMS (ESI, m / z): [M] + calculated for C 34 H 31 N2O3P,546.2072,found546.2068. 1H NMR(600MHz,DMSO-d6)δ8.71(d,J=0.7Hz,1H),8.42–8.37(m,2H),8.31(dt,J=7.7,1. 0Hz,1H),8.23(d,J=21.1Hz,1H),7.98–7.91(m,3H),7.64(d,J=0.8Hz,1H),7.53(ddt, J=20.1,8.2,0.9Hz,2H),7.46(ddd,J=8.2,7.0,1.3Hz,1H),7.40–7.34(m,2H),7.29(t d,J=7.4,1.2Hz,1H),4.22(dq,J=8.9,7.0Hz,4H),1.49(s,6H),1.35(t,J=7.0Hz,6H). 13 C NMR (101MHz, CDCl3) δ157.49,153.51,153.41,142.23,140.49,140.30,139.40,133.29,132.39,130.75,127.14,127.01,126.6 1,126.01,124.28,123.62,122.62,120.94,120.37,119.50,111.52,109.85,103.98,63.81,63.76,46.89,27.94,16.37,16.32.

[0093] 2) Synthesis of Formula 48: Intermediate 4 (0.4 g, 0.73 mmol) was ventilated. 20 mL of DCM and 2 mL of Me3SiBr were added. Stirring was continued overnight at room temperature. The reaction was complete by tapping. Methanol was added to quench the remaining Me3SiBr. The reaction solution was spin-dried to dryness. The solution was washed with water and extracted with DCM several times until the aqueous phase was free of product. The organic phase was dried over anhydrous sodium sulfate, concentrated, and a large amount of PE was added. The product was filtered to obtain 0.3 g of product, with a yield of 67%. HRMS (ESI, m / z): [M-H2PO3+H]+ calculated for C 30 H 22 N2,410.1783,found410.1781. 1H NMR (600MHz, DMSO-d6) δ8.70(s,1H),8.33–8.28(m,3H),8.03(d,J=19.8Hz,1H),7.96–7.87(m,3H),7.63(s,1H),7.54(d,J=7.4 Hz,1H),7.49(d,J=8.2Hz,1H),7.45(ddd,J=8.2,6.9,1.3Hz,1H),7.41–7.32(m,2H),7.29(td,J=7.3,1.1Hz,1H),1.49(s,6H). 13 C NMR (151MHz, DMSO) δ153.65,153.54,140.59,140.42,140.27,139.37,132.89,131.97,127.61,127.47,1 27.04,126.61,123.84,123.28,123.20,121.13,120.90,119.98,112.39,110.38,104.69,46.96,28.00.

[0094] Example 5

[0095] The synthetic route of formula 64 is as follows:

[0096]

[0097] Specific synthesis steps:

[0098] 1) Synthesis of Intermediate 5: The synthesis steps of Intermediate 5 were similar to those of Intermediate 4, except that Intermediate 2 (0.8 g, 2.22 mmol) was used in place of Intermediate 1. The product was obtained as a yellow solid (0.53 g) with a yield of 46.1%. HRMS (ESI, m / z): [M] + calculated for C 31 H 25 N2O4P,520.1552, found 546.2068. 1 H NMR(400MHz, DMSO-d6)δ8.46(dd,J=7.6,1.3Hz,1H),8.43–8.36(m,2H),8.31–8.17(m,3H),8.03–7.96 (m,2H),7.88(d,J=8.1Hz,1H),7.64–7.43(m,6H),4.22(dq,J=8.8,7.0Hz,4H),1.36(t,J=7.0Hz,6H). 13CNMR(101MHz,DMSO)δ158.09,156.09,150.61,141.11,140.57,139.87,132.82,132.02,131.84,127.81,127.08,126.55,124 .75,123.96,122.59,122.09,120.89,119.60,117.07,112.24,110.81,108.60,106.56,101.66,63.86,63.81,16.65,16.60.

[0099] 2) Synthesis of Formula 64: The synthesis steps of Formula 64 are similar to those of Formula 48, except that Intermediate 5 (0.4 g, 0.77 mmol) was used in place of Intermediate 4 to obtain 0.25 g of product with a yield of 70%. HRMS (ESI, m / z): [M-H2PO3+H]+ calculated for C 27 H 16 N2O,384.1263,found 384.1265. 1 H NMR (400MHz, DMSO-d6) δ8.43(d,J=7.7Hz,1H),8.30(d,J=8.5Hz,2H),8.16(td,J=6.2,4.9,2.9Hz, 2H),8.06(d,J=19.7Hz,1H),7.94(dd,J=8.6,2.2Hz,2H),7.87(d,J=8.1Hz,1H),7.62–7.41(m,6H). 13 CNMR(151MHz,DMSO)δ156.07,153.28,153.24,150.60,140.62,140.38,140.16,139.92,132.66,132.55,132.23,132.01,127.77,126.97,126.4 6,124.76,123.90,122.54,121.96,121.93,120.82,119.46,117.39,11 7.32,116.95,116.92,112.21,110.73,108.49,107.81,106.60,106.47.

[0100] Example 6

[0101] The synthetic route of formula 65 is as follows:

[0102]

[0103] Specific synthesis steps:

[0104] 1) Synthesis of Intermediate 6: The synthesis steps of Intermediate 6 were similar to those of Intermediate 4, except that Intermediate 3 (1.2 g, 3.18 mmol) was used in place of Intermediate 1. The product was obtained as a yellow solid (0.51 g) with a yield of 29.9%. HRMS (ESI, m / z): [M] + calculated for C 31 H 25 N2O3PS,530.1233, found 530.1230. 1 H NMR(400MHz,DMSO-d6)δ8.50–8.37(m,4H),8.31–8.21(m,2H),8.19–8.14(m,1H),8.0 4–7.96(m,2H),7.70–7.51(m,6H),4.23(dq,J=8.8,7.0Hz,4H),1.36(t,J=7.1Hz,6H). 13 C NMR (101MHz, DMSO) δ158.10,158.02,141.01,140.01,139.23,138.21,135.83,132.83,132.10,131.99,131.81,129.65,127.76,127.05,126.44 ,125.67,123.79,122.43,122.11,122.02,121.55,120.84,117.04,116. 19,116.08,110.90,108.57,101.64,99.71,63.86,63.81,16.66,16.60.

[0105] 2) Synthesis of Formula 65: The synthesis steps of Formula 65 are similar to those of Formula 48, except that Intermediate 6 (0.4 g, 0.65 mmol) was used in place of Intermediate 4 to obtain 0.19 g of product with a yield of 53%. HRMS (ESI, m / z): [M-H2PO3+H]+ calculated for C 27 H 16 N2S,400.1034,found 400.1037. 1 H NMR (400MHz, DMSO-d6) δ8.38 (dd, J=8.0, 5.1Hz, 2H), 8.29 (d, J=8.1Hz, 2H), 8.23 –8.12(m,2H),8.04(d,J=19.7Hz,1H),7.92(d,J=8.2Hz,2H),7.67–7.45(m,6H). 13C NMR (151MHz, DMSO) δ153.19,153.15,140.04,139.25,138.19,135.83,132.64,132.53,132.15,132.08,132.00,129.50,127.7 0,126.92,126.36,125.60,123.76,122.33,121.94,121.49,120.69,117.42,117.36,116.91,110.83,108.49,107.90,106.69.

[0106] In the following Examples 7 to 12, compounds 19, 34, 35, 48, 64, and 65 prepared by the present invention are used as hole transport materials to prepare perovskite light-emitting diode devices, and the prepared devices are subjected to corresponding performance tests to further illustrate the performance of the hole transport materials provided by the present invention in perovskite light-emitting diodes. It should be noted that in the following Examples 7 to 12, the electron transport layer material used is TPBi, whose chemical structure is as follows:

[0107]

[0108] Example 7

[0109] A perovskite light-emitting diode was prepared using the compound Formula 19 of the present invention as a hole transport material. The device structure was: ITO / hole injection layer / hole transport layer / quantum dots / electron transport layer / electron injection layer / cathode.

[0110] Device preparation: A PEDOT:PSS (PEDOT is a polymer of 3,4-ethylenedioxythiophene monomers; PSS is polystyrene sulfonate) solution (Baytron PVPAl 4083, filtered through a 0.22 μm filter) was spin-coated onto clean ITO glass in air (3000 rpm, 60 s). After annealing at 140°C for 15 min, the film served as the hole injection layer and was then transferred to a nitrogen glove box. A hole transport material, compound 19 (concentration 15 mg / mL) dissolved in ethanol was spin-coated onto the PEDOT:DSS layer and annealed at 150°C for 15 min. Perovskite quantum dots dissolved in n-octane were then spin-coated onto the hole transport layer at 3000 rpm, 60 s. The quantum dot layer was annealed at 60°C for 10 min. The sample was transferred to a thermal evaporation system and heated to ~2×10 -4 Under a high vacuum environment at Pa, 40nm of TPBi was deposited as an electron transport layer, followed by 1nm of LiF as an electron injection layer, and then 100nm of Al as a cathode. The device's light-emitting area is 9 square millimeters, determined by the overlap between the ITO anode and the Al cathode.

[0111] The EL spectrum, current density-voltage curve (JV curve), and external quantum efficiency of the device were obtained using an integrated LED test system, including an integrating sphere, a Keithley 2400 light source, and a PMA-12 spectrometer (the measurement equipment was designed by Hamamatsu Photonics Co., Ltd.). The data were obtained by testing the unpackaged device in a nitrogen atmosphere glove box at room temperature. The test results are shown in Tables 1 and 2, respectively. Figure 7 .

[0112] Examples 8-12

[0113] Quantum dot electroluminescent devices were prepared using compounds 34, 35, 48, 64, and 65 as hole transport materials in sequence in Examples 8 to 12. The device structure was: ITO / hole injection layer / hole transport layer (compound of the present invention) / quantum dot / electron transport layer / electron injection layer / cathode.

[0114] The device preparation method and testing method are the same as in Example 7. The test results of the device performance are shown in Table 1 and Figures 8 to 12 .

[0115] Comparative Example 1

[0116] A quantum dot light-emitting device was prepared using compound SAM1 (structural formula shown below) as a hole transport material. The device preparation method and testing method were the same as those in Example 7.

[0117] Comparative Example 2

[0118] A quantum dot light-emitting device was prepared using compound SAM2 (structural formula shown below) as a hole transport material. The device preparation method and testing method were the same as those in Example 7.

[0119]

[0120] Table 1 Performance parameters of quantum dot light-emitting devices

[0121]

[0122]

[0123] like Figure 7-12As shown in Table 1, quantum dot light-emitting devices prepared under the same conditions, the compounds of the present invention are used as hole transport materials in quantum dot devices, with indenocarbazole / benzofurancarbazole / benzothiophenecarbazole having a rigid conjugated large plane as the mother core to ensure the excellent hole transport performance of the material; compared with SAM1 and SAM2, the light-emitting diode prepared using the compounds of the present invention has a high hole transport performance at 20 mA / cm 2 The operating voltage under the current density is reduced from 5.5V and 5.2V to 4.0-4.6V, and the maximum luminous brightness is reduced from 8463cd / m 2 Increased to 15113-20099cd / m 2 , and the maximum quantum efficiency is also increased from 3.6% to 6.1%-11.2%. It can be seen that the compound of the present invention can effectively reduce the operating voltage of the device as a hole transport material and show higher luminescence brightness and luminous efficiency.

[0124] In the following Examples 13 to 18, compounds 19, 34, 35, 48, 64, and 65 prepared by the present invention are used as hole transport materials to prepare perovskite solar cell devices, and the prepared devices are subjected to corresponding performance tests to further illustrate the performance of the hole transport materials provided by the present invention in perovskite solar cells. It should be noted that in the following Examples 7 to 12, the electron transport layer material used is BCP, whose chemical structure is as follows:

[0125]

[0126] Example 13

[0127] The compound 19 prepared in the present invention is used as a hole transport material to prepare a perovskite solar cell device, comprising the following steps:

[0128] S1. Cleaning of ITO conductive glass substrate

[0129] ITO (Indium tin oxide) transparent conductive glass was ultrasonically cleaned for 30 minutes using a surfactant solution, deionized water, ethanol, and acetone, sequentially. After drying the solvent, the glass was treated with UV-ozone for 20 minutes and then transferred to a glove box for later use.

[0130] S2. Preparation of hole transport layer

[0131] Compound 9 was dissolved in ethanol solvent at a concentration of 2 mg mL-1, and then spin-coated on ITO, and annealed at 120 °C for 20 min to remove adsorbed water molecules.

[0132] S3. Preparation of perovskite film

[0133] The solubility of the perovskite precursor solution is 1.2M, and the perovskite film is prepared by the anti-solvent one-step method. The spin coating is divided into two stages. The speed of the first stage is 1000 rpm s -1 , spin coating for 10 s, acceleration of 200 rpm s -2 , the second stage is 5000rpm s -1 , spin coating for 30s, acceleration of 2000rpm s -1 20 seconds before the end of the second stage, 600 μL of toluene was added as an antisolvent in the center of the perovskite film, and finally heated at 100 °C for 10 min to obtain the final perovskite film;

[0134] S4. Preparation of electron transport layer and hole blocking layer

[0135] A PCBM solution was prepared using chlorobenzene at a concentration of 20 mg mL -1 , two-step spin coating (800rmp s -1 , 10s; 4000rmp s -1 , 30s), and annealed at 80°C for 10min. Finally, 120μL of BCP isopropanol solution was drop-coated to prepare the hole-blocking layer;

[0136] S5, back electrode preparation: using a vacuum evaporation apparatus (<5×10 -4 Pa) was evaporated to form the negative electrode.

[0137] Performance testing of perovskite solar cells: The perovskite solar cells prepared using the above method were exposed to simulated AM1.5 sunlight. Their open-circuit voltage, fill factor, and short-circuit current density were measured using a Keithley 2400 SourceMeter instrument (Keithley, USA). Their efficiency was also calculated. The test results are shown in Table 2.

[0138] Examples 14-18

[0139] Perovskite solar cell devices were prepared using compounds 34, 35, 48, 64, and 65 as hole transport materials, respectively, in Examples 14 to 18. The device preparation method was the same as that of Example 13, differing only in the hole transport layer materials used. The performance parameter test results of the prepared devices are shown in Table 2.

[0140] Comparative Example 3

[0141] The preparation and testing methods of the device are the same as those of Example 17, except that SAM1 is used as the hole transport layer material. The performance test results of the device are shown in Table 2.

[0142] Comparative Example 4

[0143] The preparation and testing methods of the device are the same as those of Example 17, except that SAM2 is used as the hole transport layer material. The performance test results of the device are shown in Table 2.

[0144] Table 2 Perovskite solar performance parameters

[0145]

[0146]

[0147] As shown in Table 2, perovskite cells prepared under the same conditions use the compound of the present invention as a hole transport material in the cell, with a rigid conjugated large-planar indenocarbazole / benzofurancarbazole / benzothiophenecarbazole as the parent core, which increases the hole transport capacity. The open circuit voltage of the cell increases from 1.076 V to 1.191-1.17 V, the fill factor increases from 0.74 to 0.78-0.80, the photoelectric conversion efficiency also increases from 20.9% to 24.0-24.4%, and the short-circuit current increases from 21.85 to 24 mA cm -2 The large conjugated system can improve the energy level of the compound, increase the hole injection ability, and improve the photoelectric conversion performance.

[0148] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A hole transport material having a carbazole derivative as a core and cyanoacetic acid or cyanophosphoric acid as an anchoring group, and having the following structural formula (I): in, R represents a carboxyl group or a phosphate group; L represents a phenyl group; R1-R9 independently represent hydrogen; and A represents O, S, or CMe2.

2. A hole transport material, characterized in that Including any one of the compounds shown in the following formula (1) to formula (67):

3. A method for preparing a hole transport material according to claim 1 or 2, characterized in that: The synthetic route is: Synthesis Route 1: Or, Synthesis Route 2: Wherein, the definition of A is the same as the corresponding position of the compound in claim 1 or 2; the strong base used in step a) of Synthesis Route 1 and Synthesis Route 2 is any one of potassium tert-butoxide, sodium tert-butoxide, and sodium hydride; the strong base used in step b) of Synthesis Route 1 and Synthesis Route 2 is piperidine.

4. The method for preparing a hole transport material according to claim 3, wherein: In synthetic route 1, the reaction solvent in step a) is N'N-dimethylformamide, and the heating temperature is 100-140°C; the reaction solvent in step b) is acetonitrile, and the heating temperature is 60-80°C.

5. The method for preparing a hole transport material according to claim 3, wherein: In synthetic route 2, the reaction solvent in step a) is N'N-dimethylformamide, and the heating temperature is 100-140°C; the reaction solvent in step b) is acetonitrile, and the heating temperature is 60-80°C; the hydrolysis reagent used in step c) is trimethylsilyl bromide, the reaction solvent is dichloromethane, the reaction temperature is 15-25°C, and the quenching reagent used in the reaction is methanol.

6. A hole transport material according to any one of claims 1 or 2, applied to perovskite light-emitting diodes, perovskite cells, organic electroluminescent devices, organic solar cells, organic thin-film transistors, organic photodetectors, organic field-effect transistors, organic integrated circuits and organic photoreceptors.

7. A perovskite light-emitting diode having the structure: ITO / hole transport layer / perovskite / C60 / BCP / Cu, wherein the structural formula of the BCP material is It is characterized by: The hole transport layer contains the hole transport material according to any one of claims 1 or 2.

8. A quantum dot perovskite light-emitting diode, having the structure of: ITO / hole injection layer / hole transport layer / quantum dot / electron transport layer / electron injection layer / cathode; wherein: The electron transport layer uses TPBi material, whose structural formula is The feature of the present invention is that the hole transport layer contains the hole transport material according to any one of claims 1 or 2.

9. A method for preparing the quantum dot perovskite light-emitting diode according to claim 8, comprising the following steps: S1: Prepare a mixed liquid of PEDOT and DSS in a certain molar ratio and filter it through a 0.22 μm filter to obtain a filtrate; S2: In an air environment, a thin film is spin-coated on a clean ITO glass substrate using the filtrate obtained in step S1 at a certain rotation speed, and annealed at 140° C. for 15 minutes to obtain an intermediate A having a hole injection layer of PEDOT:DSS, and then the intermediate A is transferred to an inert atmosphere; S3: preparing an ethanol solution of the hole transport material according to claim 8 at a certain concentration, and then spin-coating a thin film on the surface of the PEDOT:DSS layer of intermediate A at a certain rotation speed by spin coating, and annealing at 150° C. for 15 minutes. Then, spin-coating a perovskite quantum dot solution dissolved in n-octane on the hole transport layer at a certain rotation speed, and annealing at 60° C. for 10 minutes to obtain intermediate B; S4: Intermediate B was transferred to a thermal evaporation system and heated to 2 × 10 -4 An electron transport layer of a certain thickness is deposited under a high vacuum environment of Pa, an electron injection layer is evaporated on the electron transport layer, and a cathode is evaporated on the surface of the electron injection layer, and the layer is packaged to obtain a quantum dot perovskite light-emitting diode.

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