Self-assembly hole transport material containing triphenylamine dicarboxyl, synthesis method and application of self-assembly hole transport material as photoelectric device

Abstract

The invention belongs to the technical field of organic semiconductor photoelectricity, and discloses a triphenylamine dicarboxyl-containing self-assembly hole transport material, a synthesis method and application of the triphenylamine dicarboxyl-containing self-assembly hole transport material as a photoelectric device. The triphenylamine dicarboxyl group is used as an anchoring group, and a bridging unit and a hole transport unit are introduced into a molecular structure through a self-assembly monomolecular layer strategy, so that the hole transport material containing the triphenylamine dicarboxyl group is obtained; the technical problems of poor stability, poor device performance and the like of small organic molecules with anchoring groups in the prior art can be solved. The triphenylamine dicarboxyl group is introduced into the hole transport material, so that the efficiency of a photoelectric device can be improved, the service life of the photoelectric device can be prolonged, and the hole transport material comprises a perovskite solar cell, a perovskite light-emitting diode, a quantum dot light-emitting diode and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic semiconductors, and in particular relates to a triphenylamine dicarboxyl-containing self-assembled hole transport material, a synthesis method and an application thereof. Background Art

[0002] Organic semiconductor materials have been widely used in solution-processed thin-film electronic devices, including organic field-effect transistors (OFETs), organic solar cells (OSCs), organic light-emitting diodes (OLEDs), and perovskite solar cells (PSCs), due to their diverse molecular designs, light weight, ease of processing, and wide range of integrated applications. The performance of these devices depends critically on the intrinsic properties of the active materials and the processing conditions at the interfaces of different functional layers. In addition to the optimization of the active layers, ensuring the quality of the heterojunction interfaces through which charge carriers pass is also critical to improving device performance. These interfaces not only determine the coverage, uniformity, and crystallinity of the post-deposited materials, but also significantly affect charge extraction, injection, transport, and recombination by regulating the defect density and electric field in the device.

[0003] As charge selective layers, single-molecule self-assembled (SAMs) hole transport materials can effectively extract charge carriers and realize high-efficiency photovoltaic devices by adjusting energy level arrangement, passivating substrate defects and regulating active layer morphology, thus becoming ideal candidates for solving the problems associated with traditional charge transport layers. In particular, SAMs containing substituents such as heteroatoms (such as sulfur and oxygen), amines, ammonium salts and halogens can effectively passivate defects, fill vacancies on the perovskite / SAM surface, and improve device performance. However, commonly used SAMs, such as [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), are unevenly distributed on the substrate and have poor surface wettability to the perovskite precursor (Nature, 2024, 632, 536-542). These characteristics pose challenges to the direct deposition of high-quality perovskite films on the Me-4PACz surface, which may lead to low manufacturing yields and undesirable interface losses at the buried interface. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a self-assembled monolayer hole transport material with good hole transport properties and strong interface passivation ability and suitable for large-scale applications.

[0005] In order to achieve the above object, the present invention provides a hole transport material containing triphenylamine dicarboxyl group, having the chemical formula shown in the following formula (I):

[0006]

[0007] In the formula, R1-R2 are independently selected from any one or two of hydrogen, halogen, alkoxy, thioalkoxy, trifluoromethyl, and Cl-C6 alkyl, and R l -R2 can be different substitution positions or different substitution numbers; L represents a single bond, phenyl, thiophene, furan, biphenyl; X represents space, a single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl dimethyl, nitrogen methyl, silicon dimethyl.

[0008] Further, formula (I) is any one of the following compounds i to ix:

[0009]

[0010] Wherein, R1 and R2 are independently selected from any one of -H, -F, -Cl, -Br, -I, -OCH3, -SCH3, -CH3, -CH2CH3, and -CF3, and R l and R2 may be different substitution positions or different substitution numbers; L represents a single bond, phenyl, thiophene, furan or biphenyl.

[0011] Furthermore, R1 and R2 are independently -H, -F or -OCH3, and R l and R2 are at the same para-substituted position; L is a single bond or a phenyl group; only when L is a single bond in formula (i) and (ii), R1 and R2 are not -H.

[0012] In a second aspect, the present invention provides a method for synthesizing the triphenylamine dicarboxyl self-assembled hole transport material according to the first aspect, comprising:

[0013] S1, a step of preparing intermediate 1 by subjecting methyl p-bromobenzoate and aniline to a Buchwald-Hartwig coupling reaction in toluene in the presence of sodium tert-butyl phosphine (t-BuONa), tri-tert-butyl phosphine (P(t-Bu)3) and trisdibenzylideneacetone dipalladium (Pd2(dba)3),

[0014]

[0015] S2, the step of preparing intermediate 2 by subjecting intermediate 1 to a substitution reaction with N-bromosuccinimide (NBS) in an N,N-dimethylformamide (DMF) solution,

[0016]

[0017] S3, the intermediate 2 and the aromatic amine compound are subjected to a Buchwald-Hartwig coupling reaction in toluene in the presence of sodium tert-butyl phosphine and tridibenzylideneacetone dipalladium, followed by a hydrolysis reaction in a sodium hydroxide solution to prepare a target product, a hole transport material containing triphenylamine dicarboxyl group,

[0018]

[0019] Among them, R1, R2 = -H, -F, -OCH3, X = space, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl, nitrogen, dimethyl, silicon.

[0020] Furthermore, in step S1, the molar ratio of aniline, methyl p-bromobenzoate, sodium tert-butyl phosphine, and tridibenzylideneacetone dipalladium is 1:2-2.5:1.5-3:0.1-0.2:0.01-0.05; the coupling reaction temperature is 80-100° C., and the coupling reaction time is 8-12 h.

[0021] Furthermore, in step S2, the molar ratio of intermediate 1 to N-bromosuccinimide is 1.0-1.01:1-1.5; the substitution reaction temperature is -5-0°C, and the substitution reaction time is 4-8h.

[0022] Advantageously, in step S3, the molar ratio of intermediate 2, aromatic amine compound, sodium tert-butoxide, tri-tert-butylphosphine, and tridibenzylideneacetone dipalladium is 1:1.1-1.2:1.5-2:0.1-0.2:0.01-0.05; the coupling reaction temperature is 80-100°C, and the coupling reaction time is 4-12h.

[0023] In a third aspect, the present invention provides a method for synthesizing the triphenylamine dicarboxyl self-assembled hole transport material according to the first aspect, comprising:

[0024] (a) intermediate 2 and diboronic acid pinacol ester are reacted in a mixed solution of potassium acetate and toluene by bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2Cl2) catalyzed coupling reaction to prepare intermediate 3,

[0025]

[0026] (b) subjecting the intermediate 3 and bromoaryl hydrocarbon to a Buchwald-Hartwig coupling reaction with potassium carbonate and bis(triphenylphosphine)palladium dichloride in a mixed solution of toluene / ethanol / water, and subjecting the mixture to a hydrolysis reaction in a hydrochloric acid system to prepare a target product, a hole transport material containing triphenylamine dicarboxyl group.

[0027]

[0028] Among them, R1, R2 = -H, -F, -OCH3, X = space, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl, nitrogen, dimethyl, silicon.

[0029] Furthermore, in step (a), the molar ratio of intermediate 2, bipyraclostrobin, potassium acetate and bis(triphenylphosphine)palladium dichloride is 1:1.2-2:2-3:0.01-0.05; the coupling reaction temperature is 80-120°C, and the coupling reaction time is 6-12h.

[0030] Furthermore, in step (b), the molar ratio of intermediate 3, bromoaryl hydrocarbon, potassium carbonate and bis(triphenylphosphine)palladium dichloride is 1:1.1-1.2:1.5-3:0.1-0.05; the coupling reaction temperature is 80-100°C, and the coupling reaction time is 4-12h.

[0031] In a fourth aspect, the present invention provides a photoelectric device comprising a hole transport layer prepared from the triphenylamine dicarboxyl group-containing self-assembled hole transport material described in the first aspect.

[0032] Furthermore, the photoelectric device is a perovskite cell, which at least includes a transparent conductive oxide substrate, a hole transport layer, a light absorption layer, an electron transport layer and an electrode layer arranged in sequence.

[0033] Furthermore, the optoelectronic device is a perovskite light-emitting diode, which at least includes a transparent conductive oxide substrate, a hole transport layer, a light-emitting layer, an electron transport layer and an electrode layer arranged in sequence.

[0034] Furthermore, the hole transport layer is obtained by dissolving the triphenylamine dicarboxyl self-assembled hole transport material in an alcohol solvent to prepare a solution with a concentration of 1 to 10 mg / mL, and then coating the solution on a transparent conductive oxide substrate.

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

[0036] (1) The introduction of triphenylamine carboxyl groups can passivate the structural defects of the interface, prolong the carrier lifetime in the active layer, and improve the open circuit voltage and fill factor of the optoelectronic device.

[0037] (2) The introduction of triphenylamine carboxyl groups can adjust the frontier orbital energy level of the material to make it more compatible with the energy level of the active layer material, thereby improving the efficiency of interfacial carrier injection and extraction and enhancing the power conversion efficiency and stability of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of the structure of the optoelectronic device of the present invention;

[0039] Figure 2 The J / V curve of the perovskite battery prepared by using the compounds 1 to 4 provided by the present invention as hole transport materials;

[0040] Figure 3The J / V curve of the perovskite battery prepared by using the compounds 5 to 8 provided by the present invention as hole transport materials;

[0041] Figure 4 The J / V curve of the perovskite battery prepared by using the compounds 9 to 11 provided by the present invention as hole transport materials;

[0042] Figure 5 The J / V curve of the perovskite battery prepared by using the compounds 12 to 15 provided by the present invention as hole transport materials;

[0043] Figure 6 The J / V curve of the perovskite cell prepared by using the compounds 16 to 19 provided by the present invention as hole transport materials;

[0044] Figure 7 The J / V curve of the perovskite cell prepared by using the compounds 20 to 22 provided by the present invention as hole transport materials;

[0045] Figure 8 The graph of the external quantum efficiency of the perovskite light-emitting diode prepared by using the compounds 1 to 4 provided by the present invention as hole transport materials and the change of the current density;

[0046] Fig. 9 The graph of the external quantum efficiency of the perovskite light-emitting diode prepared by using the compounds 5 to 8 provided by the present invention as hole transport materials and the change of the current density;

[0047] Fig.10 The graph of the external quantum efficiency of the perovskite light-emitting diode prepared by using the compounds 9 to 11 provided by the present invention as hole transport materials and the change of the current density;

[0048] Fig.11 The graph of the external quantum efficiency of the perovskite light-emitting diode prepared by using the compounds 12 to 15 provided by the present invention as hole transport materials and the change of current density;

[0049] Fig.12 The graph of the external quantum efficiency of the perovskite light-emitting diode prepared by using the compounds 16 to 19 provided by the present invention as hole transport materials and the change of current density;

[0050] Fig.13 The figure is a graph showing the change of external quantum efficiency of a perovskite light-emitting diode prepared by using compounds 20 to 22 provided by the present invention as hole transport materials as a function of current density. DETAILED DESCRIPTION

[0051] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation mode, structure, characteristics and effects of the present invention are described in detail below in conjunction with the accompanying drawings and preferred embodiments.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0053] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0054] The present invention uses triphenylamine dicarboxyl as an anchoring group, introduces a bridging unit and a hole transport unit into the molecular structure through a self-assembled monolayer strategy, thereby obtaining a hole transport material containing triphenylamine dicarboxyl, which can solve the technical problems of poor stability and poor device performance faced by organic small molecules with anchoring groups in the prior art. The introduction of triphenylamine dicarboxyl in the hole transport material of the present invention can improve the efficiency of optoelectronic devices and extend their service life, including perovskite solar cells, perovskite light-emitting diodes, and quantum dot light-emitting diodes, etc.

[0055] Specifically, the example compounds are selected from the following structures:

[0056]

[0057]

[0058]

[0059] Example 1

[0060] Synthesis of compound 1

[0061]

[0062] (1) Synthesis of intermediate 1:

[0063]

[0064] Sodium tert-butoxide (7.74 g, 80.53 mmol) and 80 mL of toluene were added to a 250 mL three-necked flask, heated under reflux to remove water for 1 hour, and then cooled to room temperature. Aniline (5.0 g, 53.69 mmol), methyl p-bromobenzoate (24.25 g, 112.75 mmol), Pd2(dba)3 (0.1 g, 0.109 mmol) and P(t-Bu)3 (2.0 g, 9.88 mmol) were then added in sequence. The reaction was stopped after the temperature was raised to 80°C and stirred for 10 hours. The reaction solution was cooled to room temperature, diluted hydrochloric acid was added to adjust the pH to neutral, the organic phase was separated and dried over anhydrous sodium sulfate, and 16.2 g of a white solid product was obtained by column chromatography, with a yield of 83.5%. 1 H NMR (400MHz, Chloroform-d) δ7.71-7.65(m,4H),7.38-7.33(m,4H),7.32-7.25(m,2H),7.13-7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),3.89(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 22 H 20 NO4,362.4050, found 362.4053.

[0065] (2) Synthesis of intermediate 2:

[0066]

[0067] Under ice bath (0°C), intermediate 1 (10.0 g, 27.67 mmol) was dissolved in 90 mL of DMF solution, and then 10 mL of N-bromosuccinimide (5.91 g, 33.20 mmol) DMF mixed solution was added dropwise, and the reaction was stopped after stirring for 4 hours. 300 mL of deionized water was added, and the solid crude product was filtered and recrystallized from 100 mL of toluene to obtain 9.85 g of white solid product with a yield of 80.0%. 1 H NMR (400MHz, Chloroform-d) δ 7.71-7.65 (m, 4H), 7.52-7.46 (m, 2H), 7.38-7.33 (m, 4H), 7.15 (dd, J = 8.6, 1.4Hz, 2H), 3.89 (s, 6H). HRMS(ESI,m / z):[M+H] + calculated for C 22 H 19 BrNO4,441.3010,found441.3015.

[0068] (3) Synthesis of Compound 1:

[0069]

[0070] Sodium tert-butoxide (0.65 g, 6.81 mmol) and 20 mL of toluene were added to a 100 mL three-necked flask, heated under reflux to remove water for 1 hour, and then cooled to room temperature. Then, intermediate 2 (2.0 g, 4.54 mmol), aromatic amine compound (1.03 g, 5.00 mmol), Pd2(dba)3 (0.04 g, 0.043 mmol) and P(t-Bu)3 (0.8 g, 3.95 mmol) were added in sequence, and the temperature was raised to 80°C and stirred for 15 hours before stopping the reaction. After concentrating the reaction solution, a solid crude product was obtained, which was purified by column chromatography to obtain an ester product, and then hydrolyzed under alkaline conditions and stirred for about 12 hours. A large amount of solid product precipitated in the reaction solution, and 1.30 mg of yellow solid was obtained by suction filtration, with a yield of 53.3%. 1 H NMR (400MHz, Chloroform-d) δ12.71(s,2H),8.00-7.95(m,4H),7.33-7.28(m,4H),7.27-7.17(m,8H),7.11-7.03(m,4H). HRMS(ESI,m / z):[M+H] + calculated for C 32 H 23 F2N2O4,537.5428, found 537.5425.

[0071] Example 2

[0072] Synthesis of compound 2

[0073]

[0074] (1) Synthesis of Intermediate 1: The synthesis of Intermediate 1 was the same as that in Example 1, with a yield of 81%. 1 H NMR (400MHz, Chloroform-d) δ7.71-7.65(m,4H),7.38-7.33(m,4H),7.32-7.25(m,2H),7.13-7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),3.89(s,6H).

[0075] (2) Synthesis of Intermediate 2: The synthesis of Intermediate 2 was the same as that of Example 1, with a yield of 80.6%. 1H NMR (400MHz, Chloroform-d) δ 7.71-7.65 (m, 4H), 7.52-7.46 (m, 2H), 7.38-7.33 (m, 4H), 7.15 (dd, J = 8.6, 1.4Hz, 2H), 3.89 (s, 6H).

[0076] (3) Synthesis of Compound 2:

[0077]

[0078] Sodium tert-butoxide (0.65 g, 6.81 mmol) and 20 mL of toluene were added to a 100 mL three-necked flask, heated under reflux to remove water for 1 hour, and then cooled to room temperature. Then, intermediate 2 (2.0 g, 4.54 mmol), aromatic amine compound (1.15 g, 5.00 mmol), Pd2(dba)3 (0.04 g, 0.043 mmol) and P(t-Bu)3 (0.8 g, 3.95 mmol) were added in sequence, and the temperature was raised to 80°C and stirred for 15 hours before stopping the reaction. After concentrating the reaction solution, a solid crude product was obtained, which was purified by column chromatography to obtain an ester product, and then hydrolyzed under alkaline conditions and stirred for about 12 hours. A large amount of solid product precipitated in the reaction solution, and 1.15 mg of a yellow solid was obtained by suction filtration with a yield of 45.1%. 1 H NMR (400MHz, Chloroform-d) δ12.71(s,2H),8.01-7.95(m,4H),7.33-7.28(m,4H),7.19(s,4H),7.14-7.09(m,4H),6.95-6.89(m,4H),3.79(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 34 H 29 N2O6,561.6140, found 561.6146.

[0079] Example 3

[0080] Synthesis of compound 3:

[0081]

[0082] The synthesis steps of compound 3 are similar to those of compound 2, and 1.63 g of product is obtained with a yield of 67.1%. 1HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.93(m,5H),7.82(dd,J=8.1,2.8Hz,1H),7.69(dd,J=7.8,4.9Hz,1H ),7.60(dd,J=7.9,5.0Hz,1H),7.31(d,J=6.4Hz,4H),7.25-7.20(m,2H),7.20-7.11(m,3H),7.07(td,J=8.0,2.7Hz,1H). HRMS(ESI,m / z):[M+H] + calculated for C 32 H 21 F2N2O4,535.5268, found 535.5264.

[0083] Example 4

[0084] Synthesis of compound 4:

[0085]

[0086] The synthesis steps of compound 4 are similar to those of compound 2, and 1.51 g of product is obtained with a yield of 59.5%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.89(d,J=2.8Hz,1H),7.65(d,J=2.9Hz,1H),7.36(t, J=7.9Hz,2H),7.33-7.28(m,4H),7.25-7.20(m,2H),7.17-7.11(m,2H),6.92(ddd,J=9.2,8.1,2.7Hz,2H),3.83(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 34 H 27 N2O6,559.5980,found 409.559.5983.

[0087] Example 5

[0088] Synthesis of compound 5:

[0089]

[0090] The synthesis steps of compound 5 are similar to those of compound 2, and 1.26 g of product is obtained with a yield of 53.9%. 1HNMR (400MHz, Chloroform-d) δ 12.71 (s, 2H), 8.01-7.89 (m, 4H), 7.33-7.28 (m, 4H), 7.25-7.11 (m, 10H), 6.86 (dd, J = 8.1, 1.3Hz, 2H). HRMS(ESI,m / z):[M+H] + calculated for C 32 H 23 N2O5,515.5450,found 515.5457.

[0091] Example 6

[0092] Synthesis of compound 6:

[0093]

[0094] The synthesis steps of compound 6 are similar to those of compound 2, and 1.80 g of product is obtained with a yield of 74.6%. 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.40-7.34(m ,3H),7.33(s,1H),7.33-7.29(m,6H),7.22-7.14(m,4H),7.14-7.08(m,2H). HRMS(ESI,m / z):[M+H] + calculated for C 32 H 23 N2O4S,531.6060, found 531.6065.

[0095] Example 7

[0096] Synthesis of compound 7:

[0097]

[0098] The synthesis of compound 7 was similar to that of compound 2, and 1.47 g of product was obtained with a yield of 61.4%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.05(dd,J=7.7,1.5Hz,2H),8.01-7.95(m,4H) ,7.52(ddd,J=8.1,7.3,1.7Hz,2H),7.35-7.26(m,8H),7.22-7.16(m,2H),7.14-7.08(m,2H). HRMS(ESI,m / z):[M+H] +calculated for C 33 H 23 N2O5,527.5560, found 527.5561.

[0099] Example 8

[0100] Synthesis of compound 8:

[0101]

[0102] The synthesis of compound 8 was similar to that of compound 2, and 1.36 g of product was obtained with a yield of 53.2%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.92(dd,J=8.7,1.4Hz,2H),7 .57-7.49(m,4H),7.46-7.40(m,2H),7.33-7.28(m,4H),7.22-7.17(m,2H),7.17-7.12(m,2H). HRMS(ESI,m / z):[M+H] + calculated for C 32 H 23 N2O6S,563.6040, found 563.6043.

[0103] Example 9

[0104] Synthesis of compound 9:

[0105]

[0106] The synthesis of compound 9 was similar to that of compound 2, and 1.66 g of product was obtained with a yield of 67.6%. 1 HNMR (400MHz, Chloroform-d) δ12.71 (s, 2H), 8.01-7.95 (m, 4H), 7.33-7.24 (m, 6H), 7.22-7.05 (m, 8H), 6.96 (dd, J = 6.3, 1.4Hz, 2H), 1.62 (s, 6H). HRMS(ESI,m / z):[M+H] + calculated for C 35 H 29 N2O4,541.6270, found 541.6273.

[0107] Example 10

[0108] Synthesis of compound 10:

[0109]

[0110] The synthesis of compound 10 was similar to that of compound 2, and 1.23 g of product was obtained with a yield of 51.3%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.32-7.23( m,6H),7.22-7.16(m,2H),7.16-7.12(m,5H),7.12-7.03(m,3H),3.57(s,3H). HRMS(ESI,m / z):[M+H] + calculated for C 33 H 26 N3O4,528.5880,found 528.5885.

[0111] Embodiment 11

[0112] Synthesis of compound 11:

[0113]

[0114] The synthesis steps of compound 11 are similar to those of compound 2, and 1.47 g of product is obtained with a yield of 58.1%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.43(dd,J=8.8,1.5Hz,2H),7.35( ddd,J=7.9,6.6,1.5Hz,2H),7.32-7.25(m,6H),7.22-7.16(m,2H),7.09-7.00(m,4H),0.47(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 34 H 29 N2O4Si,557.7010,found557.7013.

[0115] Example 12

[0116] Synthesis of compound 12:

[0117]

[0118] (1) Synthesis of Intermediate 1: The synthesis of Intermediate 1 was the same as that in Example 1, with a yield of 81%. 1H NMR(400MHz,Chloroform-d)δ12.71(s,2H),7.71-7.65(m,4H),7.38-7.33(m,4H) ,7.32-7.25(m,2H),7.13-7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),3.89(s,6H).

[0119] (2) Synthesis of Intermediate 2: The synthesis of Intermediate 2 was the same as that of Example 1, with a yield of 80.6%. 1 H NMR (400MHz, Chloroform-d) δ 7.71-7.65 (m, 4H), 7.52-7.46 (m, 2H), 7.38-7.33 (m, 4H), 7.15 (dd, J = 8.6, 1.4Hz, 2H), 3.89 (s, 6H).

[0120] (3) Synthesis of intermediate 3:

[0121]

[0122] Potassium acetate (1.34 g, 13.63 mmol) and 60 mL of toluene were added to a 100 mL three-necked flask, heated under reflux to remove water for 1 hour, and then cooled to room temperature. Intermediate 2 (2.0 g, 4.54 mmol), biboric acid pinacol ester (1.38 g, 5.45 mmol) and Pd(PPh3)2Cl2 (0.04 g, 0.057 mmol) were then added in sequence. The temperature was raised to 100°C and stirred for 12 hours before stopping the reaction. The reaction solution was concentrated to obtain a solid crude product, which was purified by column chromatography to obtain 1.70 g of an ester product with a yield of 76.7%. 1 H NMR (400MHz, Chloroform-d) δ7.71-7.65(m,4H),7.61-7.55(m,2H),7.38-7.33(m,4H),7.13-7.07(m,2H),3.89(s,6H),1.24(s,12H). HRMS(ESI,m / z):[M+H] + calculated for C 28 H 31 BNO6,488.3670, found 488.3671.

[0123] (4) Synthesis of compound 12:

[0124]

[0125] Add intermediate 2 (3.31 g, 6.79 mmol) and bromoaryl hydrocarbon (2.0 g, 6.17 mmol) to a 100 mL three-necked flask, then add potassium carbonate (2.56 g, 18.51 mmol) and a mixed solution of 40 mL toluene / ethanol / deionized water (2 / 1 / 1, v / v), heat to 40 ° C and add Pd (PPh) 3 Cl 2 (0.04 g, 0.057 mmol). Continue to heat to reflux, stir for 12 hours, and then stop the reaction. After concentrating the reaction solution, a solid crude product is obtained, which is purified by column chromatography to obtain an ester product, and then hydrolyzed under alkaline conditions, stirred for about 12 hours, and a large amount of solid product is precipitated in the reaction solution. Suction filtration gives 2.10 g of a yellow solid with a yield of 59.0%. 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.60-7.55(m,4H),7 .33-7.25(m,8H),7.23-7.17(m,4H),7.14-7.08(m,4H),7.04(tt,J=7.8,1.5Hz,2H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 29 N2O4,577.6600,found 577.6605.

[0126] Embodiment 13

[0127] Synthesis of compound 13:

[0128]

[0129] The synthesis of compound 13 was similar to that of compound 12, and 1.92 g of product was obtained with a yield of 53.8%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.17-8.10(m,2H),8.01-7.95(m,4H),7.70- 7.62(m,4H),7.61-7.54(m,4H),7.39-7.33(m,1H),7.33-7.27(m,7H),7.23-7.17(m,2H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 27 N2O4,575.6440,found 575.6445.

[0130] Embodiment 14

[0131] Synthesis of compound 14:

[0132]

[0133] The synthesis steps of compound 14 are similar to those of compound 12, and 2.11 g of product is obtained with a yield of 61.8%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.93(m,5H),7.82(dd,J=8.1,2.8Hz,1H),7.72- 7.65(m,3H),7.63-7.54(m,5H),7.33-7.28(m,4H),7.23-7.12(m,3H),7.07(td,J=8.0,2.7Hz,1H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 25 F2N2O4,611.6248,found611.6247.

[0134] Embodiment 15

[0135] Synthesis of compound 15:

[0136]

[0137] The synthesis steps of compound 15 are similar to those of compound 12, and 1.86 g of product is obtained with a yield of 56.0%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.89(d,J=2.8Hz,1H),7.70-7.63(m,3H) ,7.62-7.54(m,4H),7.39-7.28(m,6H),7.23-7.17(m,2H),6.92(ddd,J=9.2,8.1,2.7Hz,2H),3.83(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 40 H 31 N2O6,635.6960, found 635.6963.

[0138] Example 16

[0139] Synthesis of compound 16:

[0140]

[0141] The synthesis of compound 16 was similar to that of compound 12, and 1.96 g of product was obtained with a yield of 56.1%. 1 HNMR (400MHz, Chloroform-d) δ12.71 (s, 2H), 8.01-7.95 (m, 4H), 7.63-7.54 (m, 4H), 7.33-7.28 (m, 4H), 7.25-7.11 (m, 10H), 6.86 (dd, J = 8.2, 1.3Hz, 2H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 27 N2O5,591.6430, found 591.6433.

[0142] Embodiment 17

[0143] Synthesis of compound 17:

[0144]

[0145] The synthesis of compound 17 was similar to that of compound 12, and 2.01 g of product was obtained with a yield of 58.7%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.63-7.54(m,4H),7.40- 7.35(m,3H),7.35-7.30(m,5H),7.29(d,J=5.8Hz,2H),7.19(ddd,J=7.5,4.6,1.4Hz,6H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 27 N2O4S,607.7040, found 607.7042.

[0146] Embodiment 18

[0147] Synthesis of compound 18:

[0148]

[0149] The synthesis of compound 18 was similar to that of compound 12, and 1.76 g of product was obtained with a yield of 51.2%. 1HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.63-7.54(m,4H),7.33-7 .28(m,4H),7.26(dd,J=7.6,1.6Hz,2H),7.25-7.17(m,4H),7.17-7.03(m,6H),3.57(s,3H). HRMS(ESI,m / z):[M+H] + calculated for C 39 H 30 N3O4,604.6860,found 604.6861.

[0150] Embodiment 19

[0151] Synthesis of compound 19:

[0152]

[0153] The synthesis of compound 19 was similar to that of compound 12, and 2.12 g of product was obtained with a yield of 64.0%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.92(dd,J=8.7,1.4Hz,2H),7 .63-7.49(m,8H),7.46-7.40(m,2H),7.33-7.28(m,4H),7.26-7.21(m,2H),7.21-7.17(m,2H). HRMS(ESI,m / z):[M+H] + calculated for C 38 H 27 N2O6S,639.7020, found 639.7025.

[0154] Embodiment 20

[0155] Synthesis of compound 20:

[0156]

[0157] The synthesis of compound 20 was similar to that of compound 12, and 1.85 g of product was obtained with a yield of 55.6%. 1HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.63-7.54(m,4H),7.43(ddd,J=8.9,1.5,0.7Hz,2H),7 .35(ddd,J=7.9,6.7,1.5Hz,2H),7.32-7.25(m,6H),7.23-7.15(m,4H),7.04(ddd,J=9.6,6.7,1.6Hz,2H),0.47(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 40 H 33 N2O4Si,633.7990, found 633.7992.

[0158] Embodiment 21

[0159] Synthesis of compound 21:

[0160]

[0161] The synthesis steps of compound 21 are similar to those of compound 12, and 1.48 g of product is obtained with a yield of 43.7%. 1 HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.01-7.95(m,4H),7.63-7.54(m,4H),7.33-7.28(m,4H),7.28-7 .24(m,2H),7.23-7.17(m,4H),7.17-7.12(m,1H),7.12-7.05(m,3H),6.96(dd,J=6.3,1.4Hz,2H),1.62(s,6H). HRMS(ESI,m / z):[M+H] + calculated for C 41 H 33 N2O4,617.7250,found 617.7256.

[0162] Embodiment 22

[0163] Synthesis of compound 22:

[0164]

[0165] The synthesis of compound 22 was similar to that of compound 12, and 1.99 g of product was obtained with a yield of 57.8%. 1HNMR(400MHz,Chloroform-d)δ12.71(s,2H),8.05(dd,J=7.7,1.5Hz,2H),8.01-7.95(m,4H),7.6 3-7.55(m,4H),7.52(ddd,J=8.1,7.3,1.7Hz,2H),7.35-7.26(m,8H),7.19(dq,J=7.8,1.8Hz,4H). HRMS(ESI,m / z):[M+H] + calculated for C 39 H 27 N2O5,603.6540,found603.6544.

[0166] The following is a further detailed description of the use and effect of the compounds of the present invention by analyzing the preparation process and performance test results of the perovskite solar cell devices A1 to A22 and perovskite light-emitting diode devices B1 to B22 prepared by the compounds 1 to 22 synthesized in the present invention, wherein the schematic diagram of the structure of the optoelectronic device of the present invention is shown in FIG. Figure 1 shown.

[0167] Application Example 1

[0168] The preparation of device A1, i.e., the perovskite cell, is as follows:

[0169] 1) Cleaning of ITO conductive glass substrate;

[0170] 2) Preparation of hole transport layer (HTL): Compound 1 was dissolved in ethanol solvent, spin-coated on ITO, and annealed at 120° C. for 20 min to remove adsorbed water molecules for use;

[0171] 3) Preparation of perovskite film (perovskite layer): 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 first stage speed is 1000rpms -1 , spin coating for 10 s, acceleration of 200 rpm s -2 ; The second stage is 5000rpm s -1 Apply for 30 seconds, acceleration is 2000 rpm s -2 , 20s before the end of the second stage, 600 μL of toluene was added as an anti-solvent in the center of the perovskite film, and finally heated at 100 °C for 30 min to obtain the final perovskite film;

[0172] 3) Preparation of electron transport layer (ETL) and hole blocking layer: Use chlorobenzene to prepare a PCBM solution with a concentration of 20 mg / mL -1, two-step spin coating (800rmp s -1 , 10s; 4000rmp s -1 , 30s), annealed at 80℃ for 10min.

[0173] 4) Preparation of hole blocking layer: Finally, 120uL BCP isopropanol solution is drop-coated to prepare the hole blocking layer (ITO);

[0174] 5) Back electrode preparation: Use vacuum evaporation apparatus (<5×10 -4 The negative electrode was formed by evaporating 100 nm of silver.

[0175] The preparation method of device A2 is the same as that of device A1, except that compound 2 is used to prepare the hole transport layer on ITO.

[0176] The preparation method of device A3 is the same as that of device A1, except that compound 3 is used to prepare the hole transport layer on ITO.

[0177] The preparation method of device A4 is the same as that of device A1, except that compound 4 is used to prepare the hole transport layer on ITO.

[0178] The preparation method of device A5 is the same as that of device A1, except that compound 5 is used to prepare the hole transport layer on ITO.

[0179] The preparation method of device A6 is the same as that of device A1, except that compound 6 is used to prepare the hole transport layer on ITO.

[0180] The preparation method of device A7 is the same as that of device A1, except that compound 7 is used to prepare the hole transport layer on ITO.

[0181] The preparation method of device A8 is the same as that of device A1, except that compound 8 is used to prepare the hole transport layer on ITO.

[0182] The preparation method of device A9 is the same as that of device A1, except that compound 9 is used to prepare the hole transport layer on ITO.

[0183] The preparation method of device A10 is the same as that of device A1, except that compound 10 is used to prepare the hole transport layer on ITO.

[0184] The preparation method of device A11 is the same as that of device A1, except that compound 11 is used to prepare the hole transport layer on ITO.

[0185] The preparation method of device A12 is the same as that of device A1, except that compound 12 is used to prepare the hole transport layer on ITO.

[0186] The preparation method of device A13 is the same as that of device A1, except that compound 13 is used to prepare the hole transport layer on ITO.

[0187] The preparation method of device A14 is the same as that of device A1, except that compound 14 is used to prepare the hole transport layer on ITO.

[0188] The preparation method of device A15 is the same as that of device A1, except that compound 15 is used to prepare the hole transport layer on ITO.

[0189] The preparation method of device A16 is the same as that of device A1, except that compound 16 is used to prepare the hole transport layer on ITO.

[0190] The preparation method of device A17 is the same as that of device A1, except that compound 17 is used to prepare the hole transport layer on ITO.

[0191] The preparation method of device A18 is the same as that of device A1, except that compound 18 is used to prepare the hole transport layer on ITO.

[0192] The preparation method of device A19 is the same as that of device A1, except that compound 19 is used to prepare the hole transport layer on ITO.

[0193] The preparation method of device A20 is the same as that of device A1, except that compound 20 is used to prepare the hole transport layer on ITO.

[0194] The preparation method of device A21 is the same as that of device A1, except that compound 21 is used to prepare the hole transport layer on ITO.

[0195] The preparation method of device A22 is the same as that of device A1, except that compound 22 is used to prepare the hole transport layer on ITO.

[0196] Application Comparative Example 1

[0197] The preparation method of the reference device A0 is the same as that of the device A1, except that the hole transport layer is prepared by using the hole transport material Ref on the ITO. The structural formula of Ref is as follows:

[0198]

[0199] Perovskite cell performance test: The volt-ampere characteristic curve (IV) of the solar cell was recorded by a Keithley 2400 digital source meter. The light source was a xenon lamp (Osram XBO 450) simulating AM 1.5 sunlight with an intensity of 1000W / m 2, calibrated by silicon cells, the test temperature is 25℃. The incident photon conversion efficiency (IPCE), also known as the external quantum efficiency (EQE) test system is oriel-74125, the light source is a 300W xenon lamp (ILC Technology, USA), and the modulation frequency is 2Hz. The JV data of the test battery are shown in Table 1 and Figure 2-Figure 7 shown.

[0200] Stability test of perovskite solar cells: After the prepared perovskite solar cell device was placed under a relative humidity (RH) of 85% and a temperature of 50°C for 240 hours, the relative value of its photoelectric conversion efficiency compared to the original efficiency is shown in Table 1.

[0201] Table 1

[0202]

[0203]

[0204] From Table 1 and Figure 2-Figure 7 It can be seen that: (1) the triphenylamine carboxyl compound of the present invention is used as a hole transport material in a perovskite battery, and the short-circuit density of the battery is greater than 20 mA / cm -2 , the open circuit voltage is greater than 1.05V, and the filling factor is greater than 74%. The photoelectric conversion efficiency under the simulated solar light intensity of 1.5AM is greater than 17%, and the highest reaches 21.29%. Compared with the reference device A0, it shows a higher photoelectric conversion efficiency. This is mainly due to the introduction of the transmission unit and the triphenylamine carboxyl group, which adjusts the frontier orbital energy level of the material to make it more matched with the energy level of the active layer material, improves the interface carrier injection and extraction efficiency, and improves the device efficiency. In addition, it can passivate the structural defects of the interface, extend the carrier life in the perovskite active layer, and improve the open circuit voltage and filling factor of the perovskite battery. (2) Due to the introduction of the transmission unit and the triphenylamine carboxyl group, the light stability and redox stability of the hole transport material can be improved. It can be seen from Table 1 that after being placed under high temperature and high humidity for 240 hours, the perovskite battery using the compound of the present invention as the hole transport material still has a good photoelectric conversion efficiency. Compared with the original value, it is higher than 70%, while the reference device A0 is only 55%, showing the good stability of the battery of the present invention. In addition to increasing the stability of the material, the transmission unit can also increase the hydrophobicity of the material, reduce the erosion of the perovskite layer by moisture in the air when the perovskite battery is working, and increase the service life of the battery.

[0205] Application Example 2

[0206] The preparation of device B1, i.e., a perovskite light-emitting diode device, is carried out in the following steps:

[0207] 1) ITO anode: The ITO (indium tin oxide) glass substrate with a coating thickness of 150 nm was scrubbed with ethanol, then cleaned twice with acetone, and ultrasonically washed for 20 min. After washing, it was transferred to an isothermal stage for drying, cooled after baking, and transferred to UV-O3 for 15 min;

[0208] 2) Preparation of hole transport layer (HTL): Compound 1 was dissolved in ethanol solvent, spin-coated on ITO, and annealed at 120° C. for 20 min to remove adsorbed water molecules for use;

[0209] 3) The perovskite quantum dots were spun onto the transport layer at a spin coating parameter of 2000 rpm / 45 s and an acceleration of 1000, and a vacuum evaporator was used to evaporate 45 nm of TPBi as the electron transport layer, and 100 nm of Al was vacuum evaporated on the electron injection layer as the back electrode.

[0210] The preparation method of device B2 is the same as that of device B1, except that compound 2 is used to prepare the hole transport layer on ITO.

[0211] The preparation method of device B3 is the same as that of device B1, except that compound 3 is used to prepare the hole transport layer on ITO.

[0212] The preparation method of device B4 is the same as that of device B1, except that compound 4 is used to prepare the hole transport layer on ITO.

[0213] The preparation method of device B5 is the same as that of device B1, except that compound 5 is used to prepare the hole transport layer on ITO.

[0214] The preparation method of device B6 is the same as that of device B1, except that compound 6 is used to prepare the hole transport layer on ITO.

[0215] The preparation method of device B7 is the same as that of device B1, except that compound 7 is used to prepare the hole transport layer on ITO.

[0216] The preparation method of device B8 is the same as that of device B1, except that compound 8 is used to prepare the hole transport layer on ITO.

[0217] The preparation method of device B9 is the same as that of device B1, except that compound 9 is used to prepare the hole transport layer on ITO.

[0218] The preparation method of device B10 is the same as that of device B1, except that compound 10 is used to prepare the hole transport layer on ITO.

[0219] The preparation method of device B11 is the same as that of device B1, except that compound 11 is used to prepare the hole transport layer on ITO.

[0220] The preparation method of device B12 is the same as that of device B1, except that compound 12 is used to prepare the hole transport layer on ITO.

[0221] The preparation method of device B13 is the same as that of device B1, except that compound 13 is used to prepare the hole transport layer on ITO.

[0222] The preparation method of device B14 is the same as that of device B1, except that compound 14 is used to prepare the hole transport layer on ITO.

[0223] The preparation method of device B15 is the same as that of device B1, except that compound 15 is used to prepare the hole transport layer on ITO.

[0224] The preparation method of device B16 is the same as that of device B1, except that compound 16 is used to prepare the hole transport layer on ITO.

[0225] The preparation method of device B17 is the same as that of device B1, except that compound 17 is used to prepare the hole transport layer on ITO.

[0226] The preparation method of device B18 is the same as that of device B1, except that compound 18 is used to prepare the hole transport layer on ITO.

[0227] The preparation method of device B19 is the same as that of device B1, except that compound 19 is used to prepare the hole transport layer on ITO.

[0228] The preparation method of device B20 is the same as that of device B1, except that compound 20 is used to prepare the hole transport layer on ITO.

[0229] The preparation method of device B21 is the same as that of device B1, except that compound 21 is used to prepare the hole transport layer on ITO.

[0230] The preparation method of device B22 is the same as that of device B1, except that compound 22 is used to prepare the hole transport layer on ITO.

[0231] Application Comparative Example 2

[0232] The preparation method of the reference device B0 is the same as that of the device B1, except that the hole transport layer is prepared by using the hole transport material Ref on the ITO. The structural formula of Ref is as follows:

[0233]

[0234] The perovskite light-emitting device obtained above was subjected to IVL test, and its relevant performance parameters were obtained as shown in Table 2.

[0235] Table 2

[0236]

[0237]

[0238] From Table 2 and Figure 8-Figure 13 It can be seen that: (1) the triphenylamine carboxyl compound of the present invention is used as a hole transport material in a perovskite light-emitting diode, the turn-on voltage is 2.6V, and the luminous brightness is greater than 10000cd / m 2 , the external quantum efficiency is greater than 11%, even up to 17%. Due to the introduction of the transport unit and triphenylamine carboxyl group, the frontier orbital energy level of the material is adjusted to make it more compatible with the energy level of the active layer material, showing good interface carrier injection and extraction efficiency.

[0239] The above-mentioned implementation cases are only preferred implementation cases in the present invention, but the implementation methods of the present invention are not limited to the above-mentioned implementation cases. For example, various forms of combinations of the schemes in the embodiments, any other changes, modifications, substitutions, and combinations made without departing from the spirit and principles of the present invention should be equivalent replacement methods and are within the protection scope of the present invention.

Claims

1. A hole transport material containing triphenylamine dicarboxyl group, characterized in that: It has the chemical formula shown in the following formula (I): In the formula, R1-R2 are independently selected from any one or two of hydrogen, halogen, alkoxy, thioalkoxy, trifluoromethyl, and Cl-C6 alkyl, and R l -R2 represents different substitution positions or different substitution numbers; L represents a single bond, phenyl, thiophene, furan, or biphenyl; X represents space, a single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl dimethyl, nitrogen methyl, or silicon dimethyl.

2. A hole transport material containing triphenylamine dicarboxyl group, characterized in that: Its structure is any one of formulas i to ix: Wherein, R1 and R2 are independently selected from any one of -H, -F, -Cl, -Br, -I, -OCH3, -SCH3, -CH3, -CH2CH3, and -CF3, and R l and R2 represent different substitution positions or different substitution numbers; L represents a single bond, phenyl, thiophene, furan or biphenyl.

3. The hole transport material containing triphenylamine dicarboxyl group according to claim 1, characterized in that: R1, R2 are independently -H, -F or -OCH3, and R l and R2 are at the same para-substituted position; L is a single bond or a phenyl group; and when L in formulas (i) and (ii) is a single bond, R1 and R2 are not -H.

4. A method for synthesizing a triphenylamine dicarboxyl-containing self-assembled hole transport material, characterized in that: include: S1, a step of preparing intermediate 1 by subjecting methyl p-bromobenzoate and aniline to a Buchwald-Hartwig coupling reaction in toluene in the presence of sodium tert-butyl phosphine (t-BuONa), tri-tert-butyl phosphine (P(t-Bu)3) and trisdibenzylideneacetone dipalladium (Pd2(dba)3), S2, a step of preparing intermediate 2 by subjecting intermediate 1 to a substitution reaction with N-bromosuccinimide (NBS) in an N,N-dimethylformamide (DMF) solution, S3, the intermediate 2 and the aromatic amine compound are subjected to a Buchwald-Hartwig coupling reaction in toluene in the presence of sodium tert-butyl phosphine and tridibenzylideneacetone dipalladium, followed by a hydrolysis reaction in a sodium hydroxide solution to prepare a target product, a hole transport material containing triphenylamine dicarboxyl group, Among them, R1, R2 = -H, -F, -OCH3, X = space, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl, nitrogen, dimethyl, silicon.

5. The method according to claim 4, characterized in that In step S1, the molar ratio of aniline, methyl p-bromobenzoate, sodium tert-butyl phosphine, tri-tert-butyl phosphine, tridibenzylideneacetone dipalladium is 1:2-2.5:1.5-3:0.1-0.2:0.01-0.05; the coupling reaction temperature is 80-100°C, and the coupling reaction time is 8-12h; in step S2, the molar ratio of intermediate 1 to N-bromosuccinimide is 1.0-1.01 :1~1.5; the substitution reaction temperature is -5~0℃, and the substitution reaction time is 4~8h; in step S3, the molar ratio of intermediate 2, aromatic amine compound, sodium tert-butoxide, tri-tert-butylphosphine, and tridibenzylideneacetone dipalladium is 1:1.1~1.2:1.5~2:0.1~0.2:0.01~0.05; the coupling reaction temperature is 80~100℃, and the coupling reaction time is 4~12h.

6. A method for synthesizing a triphenylamine dicarboxyl-containing self-assembled hole transport material, characterized in that: include: (a) intermediate 2 and diboronic acid pinacol ester are reacted in a mixed solution of potassium acetate and toluene by bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2Cl2) catalyzed coupling reaction to prepare intermediate 3, (b) subjecting the intermediate 3 and bromoaryl hydrocarbon to a Buchwald-Hartwig coupling reaction with potassium carbonate and bis(triphenylphosphine)palladium dichloride in a mixed solution of toluene / ethanol / water, and subjecting the mixture to a hydrolysis reaction in a hydrochloric acid system to prepare a target product, a hole transport material containing triphenylamine dicarboxyl group. Among them, R1, R2 = -H, -F, -OCH3, X = space, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbonyl, nitrogen, dimethyl, silicon.

7. The method according to claim 6, characterized in that In step (a), the molar ratio of intermediate 2, bipyraclostrobin, potassium acetate and bis(triphenylphosphine)palladium dichloride is 1:1.2-2:2-3:0.01-0.05; the coupling reaction temperature is 80-120°C, and the coupling reaction time is 6-12h; in step (b), the molar ratio of intermediate 3, bromoaryl, potassium carbonate and bis(triphenylphosphine)palladium dichloride is 1:1.1-1.2:1.5-3:0.1-0.05; the coupling reaction temperature is 80-100°C, and the coupling reaction time is 4-12h.

8. Use of the triphenylamine dicarboxyl group-containing self-assembled hole transport material according to any one of claims 1 to 3 in preparing a hole transport layer.

9. A photoelectric device, characterized in that: It comprises a hole transport layer prepared from the triphenylamine dicarboxyl self-assembled hole transport material according to any one of claims 1 to 3.

10. The optoelectronic device according to claim 9, characterized in that The hole transport layer is obtained by dissolving the triphenylamine dicarboxyl self-assembled hole transport material in an alcohol solvent to prepare a solution with a concentration of 1-10 mg / mL, and then coating the solution on a substrate.

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