Triphenylamine dicarboxylic self-assembled hole transport material, synthesis method and application as optoelectronic device

Abstract

The application belongs to the technical field of organic semiconductor optoelectronics, and discloses a triphenylamine dicarboxy self-assembled hole transport material, a synthesis method and application as an optoelectronic device. The triphenylamine dicarboxy is used as an anchor group, a bridging unit and a hole transport unit are introduced into the molecular structure through a self-assembled monolayer strategy, thereby obtaining a hole transport material containing triphenylamine dicarboxy, which can solve the technical problems that the organic small molecules with anchor groups in the prior art have poor stability and poor device performance. The introduction of triphenylamine dicarboxy in the hole transport material can improve the efficiency of the optoelectronic device, prolong the service life of the optoelectronic device, including a perovskite solar cell, a perovskite light-emitting diode, a quantum dot light-emitting diode and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor technology, specifically relating to a self-assembled hole transport material containing triphenylamine dicarboxylic acid, its synthesis method, and its application. Background Technology

[0002] Organic semiconductor materials, due to their diverse molecular designs, light weight, ease of fabrication, and wide range of integrated application characteristics, 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). The performance of these devices heavily depends on the inherent properties of the active material and the fabrication conditions at the interfaces of different functional layers. Besides optimizing the active layer, ensuring the quality of the heterojunction interfaces through which charge carriers pass is also crucial for improving device performance. These interfaces not only determine the coverage, uniformity, and crystallinity of the post-deposited material but also significantly influence charge extraction, injection, transport, and recombination by adjusting the defect density and electric field within the device.

[0003] Single-molecule self-assembled (SAMs) hole transport materials, as charge-selective layers, can effectively extract charge carriers and achieve high-efficiency photovoltaic devices by adjusting energy level alignment, passivating substrate defects, and regulating the morphology of the active layer, thus becoming ideal candidates for solving problems related to traditional charge transport layers. In particular, SAMs containing substituents such as heteroatoms (e.g., 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), exhibit uneven distribution on the substrate and poor surface wettability to perovskite precursors (Nature, 2024, 632, 536-542). These characteristics pose challenges to the direct deposition of high-quality perovskite films on the Me-4PACz surface, potentially leading to lower manufacturing yields and undesirable interface losses at the buried interface. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a self-assembled monolayer hole transport material with good hole transport performance, strong interface passivation capability, and suitable for large-scale applications.

[0005] To achieve the above objectives, the present invention provides a hole transport material containing triphenylamine dicarboxyl groups, having the following general chemical formula (I):

[0006]

[0007] In the formula, R1-R2 are independently selected from any one or two of hydrogen, halogen, alkoxy, thioalkoxy, trifluoromethyl, and C1-C6 alkyl, and R l -R2 can represent different substitution positions or different numbers of substitutions; L represents single bond, phenyl, thiophene, furan, biphenyl; X represents empty, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbodimethyl, nitromethyl, silyldimethyl.

[0008] Furthermore, formula (I) can be 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 R2 can be different substitution positions or different numbers of substitutions; L represents a single bond, phenyl, thiophene, furan or biphenyl.

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

[0012] In a second aspect, the present invention provides a method for synthesizing the triphenylamine dicarboxylic acid self-assembled hole transport material as described in the first aspect, comprising:

[0013] S1. The step of preparing intermediate 1 involves the reaction of methyl p-bromobenzoate and aniline in toluene via a Buchwald-Hartwig coupling reaction with sodium tert-butoxide (t-BuONa), tri-tert-butylphosphine (P(t-Bu)3), and tridibenzylacetone dipalladium (Pd2(dba)3).

[0014]

[0015] S2, the step of preparing intermediate 2 by carrying out a substitution reaction between intermediate 1 and N-bromosuccinimide (NBS) in N,N-dimethylformamide (DMF) solution.

[0016]

[0017] S3. The step of preparing the target product, a hole transport material containing triphenylamine dicarboxylic acid, by reacting intermediate 2 with an aromatic amine compound in toluene in the presence of sodium tert-butoxide, tri-tert-butylphosphine, and tridibenzylacetone dipalladium, followed by hydrolysis in sodium hydroxide solution.

[0018]

[0019] Where R1, R2 = -H, -F, -OCH3, X = empty, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbodimethyl, nitrogen-methyl, silyldimethyl.

[0020] Furthermore, in step S1, the molar ratio of aniline, methyl p-bromobenzoate, sodium tert-butoxide, tri-tert-butylphosphine, and tridibenzylacetone 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℃; and the substitution reaction time is 4–8 h.

[0022] Further, in step S3, the molar ratio of intermediate 2, aromatic amine compound, sodium tert-butoxide, tri-tert-butylphosphine, and tridibenzylacetone 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 4–12 h.

[0023] Thirdly, the present invention provides a method for synthesizing the triphenylamine dicarboxylic acid self-assembled hole transport material as described in the first aspect, comprising:

[0024] (a) The step of preparing intermediate 3 by coupling intermediate 2 and pinacol diborate in a mixed solution of potassium acetate and toluene via a catalytic coupling reaction of palladium dichloride (Pd(PPh3)2Cl2).

[0025]

[0026] (b) The step of preparing the target product, a hole transport material containing triphenylamine dicarboxyl groups, by performing a Buchwald-Hartwig coupling reaction on intermediate 3 and a brominated aromatic hydrocarbon with potassium carbonate and palladium dichloride in a toluene / ethanol / water mixture, followed by hydrolysis in a hydrochloric acid system.

[0027]

[0028] Where R1, R2 = -H, -F, -OCH3, X = empty, single bond, oxygen, sulfur, carbonyl, sulfonyl, carbodimethyl, nitrogen-methyl, silyldimethyl.

[0029] Furthermore, in step (a), the molar ratio of intermediate 2, pinacol diborate, potassium acetate, and 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 6–12 h.

[0030] Furthermore, in step (b), the molar ratio of intermediate 3, bromoaromatic 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℃ and the coupling reaction time is 4-12h.

[0031] Fourthly, the present invention provides an optoelectronic device comprising a hole transport layer prepared from a triphenylamine dicarboxylic acid self-assembled hole transport material as described in the first aspect.

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

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

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

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

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

[0037] (2) The introduction of triphenylamine carboxyl groups can adjust the frontier orbital energy level of the material, making it more compatible with the energy level of the active layer material, improving the efficiency of interfacial carrier injection and extraction, and enhancing the power conversion efficiency and stability of the device. Attached Figure Description

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

[0039] Figure 2 J / V curves of perovskite solar cells prepared using compounds 1-4 provided in this invention as hole transport materials;

[0040] Figure 3J / V curves of perovskite solar cells prepared using compounds 5-8 provided in this invention as hole transport materials;

[0041] Figure 4 J / V curves of perovskite solar cells prepared using compounds 9-11 provided in this invention as hole transport materials;

[0042] Figure 5 J / V curves of perovskite solar cells prepared using compounds 12-15 provided in this invention as hole transport materials;

[0043] Figure 6 J / V curves of perovskite solar cells prepared using compounds 16-19 provided in this invention as hole transport materials;

[0044] Figure 7 J / V curves of perovskite solar cells prepared using compounds 20-22 provided in this invention as hole transport materials;

[0045] Figure 8 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 1-4 provided in this invention as hole transport materials as a function of current density.

[0046] Figure 9 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 5-8 provided in this invention as hole transport materials as a function of current density.

[0047] Figure 10 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 9-11 provided in this invention as hole transport materials as a function of current density.

[0048] Figure 11 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 12-15 provided in this invention as hole transport materials as a function of current density.

[0049] Figure 12 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 16-19 provided in this invention as hole transport materials as a function of current density.

[0050] Figure 13 The graph shows the external quantum efficiency of perovskite light-emitting diodes prepared using compounds 20-22 provided in this invention as hole transport materials as a function of current density. Detailed Implementation

[0051] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention is provided 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 one of ordinary skill in the art to which this application pertains; the term “and / or” as used herein includes any and all combinations of one or more of the associated listed items.

[0053] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0054] This invention uses triphenylamine dicarboxylic acid as an anchoring group and introduces bridging and hole transport units into the molecular structure through a self-assembled monolayer strategy, thereby obtaining a hole transport material containing triphenylamine dicarboxylic acid. This addresses the technical problems of poor stability and inadequate device performance faced by existing organic small molecules with anchoring groups. The introduction of triphenylamine dicarboxylic acid into the hole transport material of this invention can improve the efficiency and extend the lifespan of optoelectronic devices, including perovskite solar cells, perovskite light-emitting diodes, and quantum dot light-emitting diodes, etc.

[0055] Specifically, the compounds in the examples 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. The mixture was heated under reflux to remove water for 1 hour, 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 sequentially. The mixture was heated to 80 °C and stirred for 10 hours, after which the reaction was stopped. The reaction solution was cooled to room temperature, and the pH was adjusted to neutral with dilute hydrochloric acid. The organic phase was separated and dried over anhydrous sodium sulfate. Column chromatography yielded 16.2 g of a white solid product, 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) conditions, intermediate 1 (10.0 g, 27.67 mmol) was dissolved in 90 mL of DMF solution, followed by the dropwise addition of 10 mL of a DMF mixture containing N-bromosuccinimide (5.91 g, 33.20 mmol). The reaction was continued with stirring for 4 hours, after which the reaction was stopped. 300 mL of deionized water was added, and the mixture was filtered to obtain a crude solid product. This crude product was recrystallized from 100 mL of toluene to give 9.85 g of a 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. The mixture was heated under reflux to remove water for 1 hour, then cooled to room temperature. Intermediate 2 (2.0 g, 4.54 mmol), an 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 then added sequentially. The mixture was heated to 80 °C and stirred for 15 hours, after which the reaction was stopped. The reaction solution was concentrated to obtain a crude solid product. The ester product was purified by column chromatography and then hydrolyzed under alkaline conditions with stirring for approximately 12 hours. A large amount of solid product precipitated from the reaction solution. Filtering yielded 1.30 mg of a yellow solid, 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: Same as the synthesis of intermediate 1 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 in 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. The mixture was heated under reflux to remove water for 1 hour, then cooled to room temperature. Intermediate 2 (2.0 g, 4.54 mmol), an 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 then added sequentially. The mixture was heated to 80 °C and stirred for 15 hours, after which the reaction was stopped. The reaction solution was concentrated to obtain a crude solid product. The ester product was purified by column chromatography and then hydrolyzed under alkaline conditions with stirring for approximately 12 hours. A large amount of solid product precipitated from the reaction solution. Filtering yielded 1.15 mg of a yellow solid, 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 of compound 3 was similar to that of compound 2, yielding 1.63 g of product 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 of compound 4 was similar to that of compound 2, yielding 1.51 g of product 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 of compound 5 was similar to that of compound 2, yielding 1.26 g of product 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 of compound 6 was similar to that of compound 2, yielding 1.80 g of product 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, yielding 1.47 g of product 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, yielding 1.36 g of product 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, yielding 1.66 g of product 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, yielding 1.23 g of product 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] Example 11

[0112] Synthesis of compound 11:

[0113]

[0114] The synthesis of compound 11 was similar to that of compound 2, yielding 1.47 g of product 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: Same as the synthesis of intermediate 1 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 in 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. The mixture was heated under reflux to remove water for 1 hour, then cooled to room temperature. Intermediate 2 (2.0 g, 4.54 mmol), pinacol diborate (1.38 g, 5.45 mmol), and Pd(PPh3)2Cl2 (0.04 g, 0.057 mmol) were then added sequentially. The mixture was heated to 100 °C and stirred for 12 hours, after which the reaction was stopped. The reaction solution was concentrated to obtain a crude solid product, which was purified by column chromatography to give 1.70 g of the 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] Intermediate 2 (3.31 g, 6.79 mmol) and bromoaromatic hydrocarbon (2.0 g, 6.17 mmol) were added to a 100 mL three-necked flask, followed by potassium carbonate (2.56 g, 18.51 mmol) and a mixed solution of toluene / ethanol / deionized water (2 / 1 / 1, v / v). The mixture was heated to 40 °C and Pd(PPh)3Cl2 (0.04 g, 0.057 mmol) was added. The mixture was further heated to reflux and stirred for 12 hours, after which the reaction was stopped. The reaction solution was concentrated to obtain a crude solid product, which was purified by column chromatography to obtain the ester product. The ester product was then hydrolyzed under alkaline conditions and stirred for about 12 hours. A large amount of solid product precipitated in the reaction solution. Filtration yielded 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] Example 13

[0127] Synthesis of compound 13:

[0128]

[0129] The synthesis of compound 13 was similar to that of compound 12, yielding 1.92 g of product 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] Example 14

[0131] Synthesis of compound 14:

[0132]

[0133] The synthesis of compound 14 was similar to that of compound 12, yielding 2.11 g of product in 61.8% yield. 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] Example 15

[0135] Synthesis of compound 15:

[0136]

[0137] The synthesis of compound 15 was similar to that of compound 12, yielding 1.86 g of product 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, yielding 1.96 g of product 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] Example 17

[0143] Synthesis of compound 17:

[0144]

[0145] The synthesis of compound 17 was similar to that of compound 12, yielding 2.01 g of product 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] Example 18

[0147] Synthesis of compound 18:

[0148]

[0149] The synthesis of compound 18 was similar to that of compound 12, yielding 1.76 g of product 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] Example 19

[0151] Synthesis of compound 19:

[0152]

[0153] The synthesis of compound 19 was similar to that of compound 12, yielding 2.12 g of product 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] Example 20

[0155] Synthesis of compound 20:

[0156]

[0157] The synthesis of compound 20 was similar to that of compound 12, yielding 1.85 g of product 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] Example 21

[0159] Synthesis of compound 21:

[0160]

[0161] The synthesis of compound 21 was similar to that of compound 12, yielding 1.48 g of product 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] Example 22

[0163] Synthesis of compound 22:

[0164]

[0165] The synthesis of compound 22 was similar to that of compound 12, yielding 1.99 g of product 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 analysis of the preparation process and performance testing of perovskite solar cell devices A1 to A22 and perovskite light-emitting diode devices B1 to B22 prepared by compounds 1 to 22 synthesized in this invention further details the uses and effects of the compounds of this invention. The schematic diagrams of the optoelectronic devices of this invention are shown below. Figure 1 As shown.

[0167] Application Example 1

[0168] The fabrication method for device A1, i.e., the perovskite solar cell, is as follows:

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

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

[0171] 3) Preparation of perovskite thin film (perovskite layer): The solubility of the perovskite precursor solution was 1.2 M. The perovskite thin film was prepared by a one-step anti-solvent method. Spin coating was performed in two stages, with the first stage at a speed of 1000 rpm. -1 Spin coating for 10 seconds, with an acceleration of 200 rpm. -2 The second stage is 5000 rpm. -1 Apply for 30 seconds, with an acceleration of 2000 rpm. -2 20 seconds before the end of the second stage, 600 μL of toluene was added as an antisolvent to the center of the perovskite film, and finally heated at 100°C for 30 minutes to obtain the final perovskite film.

[0172] 3) Preparation of electron transport layer (ETL) and hole blocking layer: A solution of PCBM with a concentration of 20 mg / mL was prepared using chlorobenzene. -1Two-step spin coating process (800 rpm) -1 10s; 4000 rpm -1 Anneal at 80℃ for 10 minutes (30s).

[0173] 4) Hole blocking layer preparation: Finally, a hole blocking layer (ITO) was prepared by drop-coating 120 μL of BCP isopropanol solution.

[0174] 5) Back electrode preparation: using a vacuum evaporation apparatus (<5×10⁻⁶) -4 The negative electrode is formed by evaporating 100nm of silver (Pa).

[0175] The fabrication method of device A2 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 2.

[0176] The fabrication method of device A3 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 3.

[0177] The fabrication method of device A4 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 4.

[0178] The fabrication method of device A5 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 5.

[0179] The fabrication method of device A6 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 6.

[0180] The fabrication method of device A7 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 7.

[0181] The fabrication method of device A8 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 8.

[0182] The fabrication method of device A9 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 9.

[0183] The fabrication method of device A10 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 10.

[0184] The fabrication method of device A11 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 11.

[0185] The fabrication method of device A12 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 12.

[0186] The fabrication method of device A13 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 13.

[0187] The fabrication method of device A14 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 14.

[0188] The fabrication method of device A15 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 15.

[0189] The fabrication method of device A16 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 16.

[0190] The fabrication method of device A17 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 17.

[0191] The fabrication method of device A18 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 18.

[0192] The fabrication method of device A19 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 19.

[0193] The fabrication method of device A20 is the same as that of device A1, except that a hole transport layer is fabricated on ITO using compound 20.

[0194] The fabrication method of device A21 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 21.

[0195] The fabrication method of device A22 is the same as that of device A1, except that the hole transport layer is fabricated on ITO using compound 22.

[0196] Application Comparison Example 1

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

[0198]

[0199] Perovskite solar cell performance testing: The current-voltage characteristic curve (IV) of the solar cell was recorded using a Keithley 2400 digital source meter, with a xenon lamp (Osram XBO 450) simulating AM 1.5 sunlight at an intensity of 1000 W / m². 2After calibration with silicon cells, the test temperature was 25℃. The incident photon-to-electron coverage efficiency (IPCE), also known as external quantum efficiency (EQE), was measured using an Oriel-74125 system with a 300W xenon lamp (ILC Technology, USA) as the light source and a modulation frequency of 2Hz. The JV data of the tested cells are shown in Table 1 and... Figures 2-7 As shown.

[0200] Stability test of perovskite solar cells: After the prepared perovskite solar cell device was placed under conditions of 85% relative humidity (RH) and 50℃ for 240h, the relative values ​​of its photoelectric conversion efficiency compared with the original efficiency are shown in Table 1.

[0201] Table 1

[0202]

[0203]

[0204] From Table 1 and Figures 2-7 It can be seen that: (1) When the triphenylamine carboxyl compound of the present invention is used as a hole transport material in a perovskite solar cell, the short-circuit density of the cell is greater than 20 mA / cm². -2 The open-circuit voltage is greater than 1.05V, and the filler factor is greater than 74%. The photoelectric conversion efficiency under simulated sunlight intensity of 1.5AM is greater than 17%, with the highest reaching 21.29%. Compared with the reference device A0, it shows a higher photoelectric conversion efficiency. This is mainly due to the introduction of the transport unit and triphenylamine carboxyl group, which adjusts the frontier orbital energy level of the material, making it more matched with the energy level of the active layer material, improving the interface carrier injection and extraction efficiency, and improving the device efficiency. In addition, it can passivate the structural defects of the interface, prolong the carrier lifetime in the perovskite active layer, and improve the open-circuit voltage and fill factor of the perovskite battery. (2) Due to the introduction of the transport unit and triphenylamine carboxyl group, the photostability and redox stability of the hole transport material can be improved. As can be seen from Table 1, 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 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 during the operation of the perovskite battery, and improve the battery's lifespan.

[0205] Application Example 2

[0206] The fabrication method for device B1, i.e., the perovskite light-emitting diode, is as follows:

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

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

[0209] 3) Perovskite quantum dots were spin-coated onto the transport layer at 2000 rpm / 45 s with an acceleration of 1000. A 45 nm TPBi layer was deposited as the electron transport layer using a vacuum evaporation apparatus. A 100 nm Al layer was then vacuum-deposited on the electron injection layer as the back electrode.

[0210] The fabrication method of device B2 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 2.

[0211] The fabrication method of device B3 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 3.

[0212] The fabrication method of device B4 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 4.

[0213] The fabrication method of device B5 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 5.

[0214] The fabrication method of device B6 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 6.

[0215] The fabrication method of device B7 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 7.

[0216] The fabrication method of device B8 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 8.

[0217] The fabrication method of device B9 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 9.

[0218] The fabrication method of device B10 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 10.

[0219] The fabrication method of device B11 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 11.

[0220] The fabrication method of device B12 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 12.

[0221] The fabrication method of device B13 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 13.

[0222] The fabrication method of device B14 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 14.

[0223] The fabrication method of device B15 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 15.

[0224] The fabrication method of device B16 is the same as that of device B1, except that a hole transport layer is fabricated on ITO using compound 16.

[0225] The fabrication method of device B17 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 17.

[0226] The fabrication method of device B18 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 18.

[0227] The fabrication method of device B19 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 19.

[0228] The fabrication method of device B20 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 20.

[0229] The fabrication method of device B21 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 21.

[0230] The fabrication method of device B22 is the same as that of device B1, except that the hole transport layer is fabricated on ITO using compound 22.

[0231] Application Comparison Example 2

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

[0233]

[0234] The perovskite light-emitting devices obtained above were subjected to IVL testing, and their relevant performance parameters are shown in Table 2.

[0235] Table 2

[0236]

[0237]

[0238] From Table 2 and Figures 8-13 It can be seen that: (1) When 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 intensity is greater than 10000cd / m². 2 The external quantum efficiency is greater than 11%, and even reaches 17%. Due to the introduction of transport units and triphenylamine carboxyl groups, the frontier orbital energy level of the material is adjusted to better match the energy level of the active layer material, showing good interfacial carrier injection and extraction efficiency.

[0239] The above embodiments are merely preferred embodiments of the present invention, but the implementation of the present invention is not limited to the above embodiments. Any changes, modifications, substitutions, or combinations made without departing from the spirit and principle of the present invention, such as various combinations of solutions in the embodiments, should be considered equivalent replacements and are all within the protection scope of the present invention.

Claims

1. The application of a hole transport material containing triphenylamine dicarboxylic acid as a hole transport material in perovskite solar cells or quantum dot light-emitting diodes, characterized in that, It has the following general chemical formula (I): （Ⅰ）； In the formula, R1-R2 are independently selected from hydrogen, halogen, and methoxy; L represents a single bond or phenyl; and X represents an empty bond.

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