Triphenylamine derivatives and their applications

Abstract

The present invention provides a triphenylamine derivative, which is an organic self-assembling small molecule material, whose molecular skeleton has a triphenylamine thiophene structure, and the end group is a group that can generate strong interactions with perovskite components. The triphenylamine derivative of the present invention is used to modify the NiO perovskite solar cell. x layer, which can greatly improve the energy conversion efficiency of perovskite solar cells.

Description

Technical Field

[0001] The invention belongs to the technical field of new materials, and particularly relates to a triphenylamine derivative and also relates to the application of the triphenylamine derivative. Background Art

[0002] In perovskite solar cells (PSCs), the trans (pin) structure offers advantages over the regular (nip) structure in terms of production cost and stability, and has become the mainstream structure in the industrialization of PSCs. With the introduction of self-assembled monolayer (SAM) materials, the efficiency of trans-PSC devices has reached new highs. Currently, SAM small molecule structures possess the following characteristics: the unique molecular arrangement and electronic structure of the main molecular skeleton regulate the spacing of anchor groups and charge transfer; and the molecular structure contains anchor groups such as thiol, carboxyl, and phosphate that can form certain interactions with the substrate or perovskite layer. Small molecule triphenylamine derivatives, due to their good modifiability, ease of purification, high purity, and low cost, can be adapted to perovskites with different band gaps through the introduction of substituents to achieve optimal performance. Currently, triphenylamine and carbazole derivatives are commonly used hole transport materials in trans-type devices. Although triphenylamine derivatives have excellent hole transport properties, a series of factors such as poor wettability, matching with perovskite energy levels, hygroscopicity, acidity and poor conductivity of these materials have hindered the development of high-efficiency perovskite solar cells.

[0003] Therefore, it is necessary to provide a triphenylamine-based organic self-assembled small molecule with improved acidity, hygroscopicity and conductivity to improve the performance and practical application of inverse perovskite photovoltaic devices. Summary of the Invention

[0004] The first object of the present invention is to provide a triphenylamine derivative to solve the problem of weak conductivity of triphenylamine derivatives in the prior art.

[0005] The second object of the present invention is to provide an application of the above triphenylamine derivative in the preparation of optoelectronic device structures.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A triphenylamine derivative having the following molecular structure:

[0008]

[0009] Where,

[0010] R1 is an alkyl group;

[0011] X is a phenyl group or a phenyl halogen substituent group;

[0012] R2 is an aromatic group constituting a thiophene derivative or one of a thiophene heterocycle containing a heteroatom, wherein the heteroatom refers to N, S, O, or Se;

[0013] R3 is one or more of hydroxyl, carboxyl, phosphate, sulfhydryl, amino, sulfonic acid, and boric acid.

[0014] In the present invention, R1 is a linear, branched or cycloalkyl group selected from C1-C20.

[0015] In the present invention, the halogen is one of fluorine, chlorine, bromine and iodine.

[0016] In the present invention, the aromatic group of the thiophene derivative is selected from an aryl group and a heteroaryl group containing any one or more heteroatoms of N, S, and O.

[0017] In the present invention, the thiophene heterocycle is selected from one or more of thiophene, bithiophene, halogen-substituted thiophene, aldehyde thiophene, methyl thiophene, acetylthiophene, cyanothiophene, oxyethylene thiophene, aromatic ring thiophene, and heterocyclic thiophene.

[0018] In the present invention, the thiophene heterocycle is as follows:

[0019]

[0020] In the present invention, the triphenylamine derivative is selected from the following structures:

[0021]

[0022]

[0023]

[0024]

[0025]

[0026] In some embodiments of the present invention, the triphenylamine derivative is selected from the following structures:

[0027]

[0028] A use of the above triphenylamine derivative in preparing optoelectronic device structures.

[0029] Furthermore, the optoelectronic device structure is one of a solar cell, a field effect transistor, a photodetector, a radiation detector, and a light emitting diode.

[0030] Furthermore, the solar cell includes one of a single-junction thin-film solar cell and a stacked solar cell.

[0031] Furthermore, the single-junction thin-film solar cell includes an organic solar cell, a perovskite solar cell, and a quantum dot solar cell.

[0032] The tandem solar cell includes one of an organic / perovskite tandem solar cell, a full perovskite tandem solar cell, and a perovskite / crystalline silicon tandem solar cell.

[0033] In the present invention, the triphenylamine derivative is used as a hole transport layer material in an organic solar cell or a perovskite solar cell.

[0034] The present invention has the following beneficial effects:

[0035] (1) The triphenylamine derivative of the present invention has a triphenylamine-like structure as a whole, has a thiophene derivative group, a molecular skeleton of a triphenylamine thiophene structure, and an end group that is an anchor group that can generate a strong interaction with the perovskite component. Compared with the existing triphenylamine derivatives, it has stronger acidity, hygroscopicity and conductivity.

[0036] (2) The triphenylamine derivative of the present invention is used as a hole transport layer material in a solar cell or to modify the hole transport layer, which can improve the efficiency of the solar cell device to 25.07%. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The technical solution of the present invention will be further described below in conjunction with the accompanying drawings and specific implementation methods.

[0038] Figure 1 Schematic diagram of the structure of a perovskite solar cell device;

[0039] Figure 2 JV diagram of a perovskite solar cell device prepared from the triphenylamine derivative of the present invention;

[0040] Figure 3 This is the IPCE diagram of the perovskite solar cell device prepared from the triphenylamine derivative of the present invention; DETAILED DESCRIPTION

[0041] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solutions of the present invention.

[0042] A triphenylamine derivative having the following molecular structure:

[0043]

[0044] Where,

[0045] R1 is an alkyl group;

[0046] X is a phenyl group or a phenyl halogen substituent group;

[0047] R2 is an aromatic group constituting a thiophene derivative or one of a thiophene heterocycle containing a heteroatom, wherein the heteroatom refers to N, S, O, or Se;

[0048] R3 is one or more of hydroxyl, carboxyl, phosphate, sulfhydryl, amino, sulfonic acid, and boric acid.

[0049] In the present invention, R1 is a linear, branched or cycloalkyl group selected from C1-C20.

[0050] In the present invention, the halogen is one of fluorine, chlorine, bromine and iodine.

[0051] In the present invention, the aromatic group of the thiophene derivative is selected from an aryl group and a heteroaryl group containing any one or more heteroatoms of N, S, and O.

[0052] In the present invention, the thiophene heterocycle is selected from one or more of thiophene, bithiophene, halogen-substituted thiophene, aldehyde thiophene, methyl thiophene, acetylthiophene, cyanothiophene, oxyethylene thiophene, aromatic ring thiophene, and heterocyclic thiophene.

[0053] In the present invention, the thiophene heterocycle is as follows:

[0054]

[0055] In the present invention, the triphenylamine derivative is selected from the following structures:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061] In some embodiments of the present invention, the triphenylamine derivative is selected from the following structures:

[0062]

[0063] Example 1

[0064] A triphenylamine derivative (TPA-ETCA) has the following structural formula:

[0065]

[0066] With this structure The synthetic routes of the core derivative TPA-ETCA are as follows (1)-(3):

[0067]

[0068]

[0069] Compounds 1, 2, 4, 6, 7 and palladium catalyst were purchased from Bidex Pharmaceuticals, o-xylene was purchased from Aladdin, K2CO3, KOAc, Na2SO4, methanol, tetrahydrofuran (THF) were purchased from Adamas, and 1,4-dioxane was purchased from McLean. Some solvents were deoxygenated before use, and the rest were used directly without purification.

[0070] Synthesis of compound 3: Compound 1 (9.00mmol, 2.446g), 2 (6.00mmol, 1.376g), Pd2(dba)3 (0.12mmol, 0.114g), BINAP (0.24mmol, 0.15g), t-BuONa (12mmol, 1.153g) were placed in a Schlenk tube, vacuumed and passed through N2 three times, 30mL of N2 bubbled deoxygenated o-xylene was added, and finally the reaction was placed in a 120°C oil bath with stirring. The reaction reached equilibrium after about 2 hours. After the reaction liquid temperature was cooled to room temperature, the reaction liquid was passed through silica gel to remove the palladium catalyst and inorganic salts, and the crude product was obtained. Finally, the product was separated and purified by silica gel chromatography and vacuum dried to obtain a white solid 3 (1.828g, yield: 72.5%), and used 1 The structure was characterized by H NMR. 1 H NMR (400MHz, Chloroform-d, δ (ppm)): 7.21 (dd, J = 10.5, 6.4Hz, 1H), 6.93 (d, J = 8.8Hz, 4H), 6.81 (d, J = 9.0Hz, 4H), 6.78-6.73 (m, 1H), 3.79 (s, 6H).

[0071] Synthesis of compound 5: Compound 4 (5.49mmol, 1.393g), Pd(dppf)Cl2 (0.16mmol, 0.16mg), KOAc (6.50mmol, 0.64g) and the above-obtained compound 3 (3.27mmol, 1.528g) were placed in a Schlenk, vacuumed and introduced with N2 three times, 20mL of anhydrous and oxygen-free 1,4-dioxane was added, and finally the reaction was placed in a 110°C oil bath with stirring. The reaction reached equilibrium after about 3h. After the reaction liquid temperature dropped to room temperature, the reaction liquid was passed through silica gel to remove the palladium catalyst and inorganic salts, and the crude product was obtained. Finally, the product was separated and purified by silica gel chromatography and vacuum dried to obtain a colorless viscous liquid 5 (0.76g, yield: 49.7%), and used 1 The structure was characterized by H NMR. 1 H NMR (400MHz, Chloroform-d, δ (ppm)): 7.33 (dd, J=11.7, 5.4Hz, 1H), 6.94 (d, J=9.0Hz ,4H),6.80(d,J=9.0Hz,4H),6.59(dd,J=10.4,6.4Hz,1H),3.79(s,6H),1.34(s,12H).

[0072] Synthesis of compound 8: Compound 6 (0.62mmol, 0.11mg), 7 (1.2mmol, 0.36mg), Pd (PPh3) 4 (0.01mmol, 10mg) and anhydrous K2CO3 (2.4mmol, 0.33mg) were placed in a dry Schlenk, vacuumed and passed through N2 three times, 25mL of oxygen-free toluene, 5mL of ethanol, and 1mL of water were added, and finally the reaction was placed in a 110°C oil bath with stirring. The reaction reached equilibrium after about 12h. After the reaction liquid temperature dropped to room temperature, the reaction liquid was passed through silica gel to remove the palladium catalyst and inorganic salts, and the crude product was obtained. Finally, the product was separated and purified by silica gel chromatography and vacuum dried to obtain a white solid 8 (77mg, 36.1%), which was then used 1 The structure was characterized by HNMR. 1 H NMR (400MHz, Chloroform-d, δ (ppm)): 8.03 (d, J = 8.6 Hz, 2H), 7.72 (d, J = 8.6 Hz, 2H), 4.37 (s, 4H), 3.94 (s, 3H).

[0073] Compound 9: Compounds 8 (0.22 mmol, 77 mg) and 5 (0.26 mmol, 94 mg) obtained above, Pd (PPh 3) 4 (0.0066 mmol, 7.6 mg) and anhydrous K 2 CO 3 (0.33 mmol, 45.6 mg) were placed in a Schlenk, evacuated and introduced with N 2 three times, and 16 mL of THF / H 2 O (v / v=7:1) after N 2 bubbling was added. The reaction was placed in an 80 ° C oil bath with stirring. After about 12 hours, the reaction reached equilibrium. After the reaction solution temperature dropped to room temperature, 20 mL of water was added and extracted with ethyl acetate. After drying with anhydrous sodium sulfate, the solvent was removed by rotary evaporation. Finally, the crude product was separated and purified by silica gel column chromatography and vacuum dried to obtain a yellow solid 9 (71 mg, yield: 52.4%). 1 The structure was characterized by H NMR. 1 H NMR(400MHz,Chloroform-d,δ(ppm)):8.04(d,J=8.6Hz,2H),7.84(d,J=8.4Hz,2H),7.76(dd,J=12.8,7.0Hz,1H), 7.00(d,J=9.0Hz,4H),6.85(d,J=9.0Hz,4H),6.77(dd,J=12.4,7.0Hz,1H),4.41(s,4H),3.94(s,3H),3.82(s,6H).

[0074] Synthesis of compound TPA-ETCA: Compound 9 (0.12 mmol, 71 mg) obtained above was dissolved in 10 mL of methanol and KOH (1.4 mmol, 80 mg) was added. The reaction was stirred in a 70°C oil bath. After about 12 hours, the reaction reached equilibrium. After adjusting the reaction to weak acidity with 2M hydrochloric acid, the solvent was removed by rotary evaporation. Finally, the crude product was separated and purified by silica gel column chromatography and vacuum dried to obtain yellow solid TPA-ETCA (37 mg, 51.3%). 1 The structure was characterized by H NMR. 1 H NMR (400MHz, Chloroform-d, δ (ppm)): 8.11 (d, J = 8.4Hz, 2H), 7.88 (d, J = 8.2Hz, 2H), 7.77 (s, 1H), 7.00 (s, 4H), 6.85 (d, J = 8.2Hz, 4H), 4.43 (s, 4H), 3.83 (s, 6H).

[0075] Example 2

[0076] A triphenylamine derivative (TPA-TCA) has the following structural formula:

[0077]

[0078] use 1 The structure was characterized by H NMR. 1 H NMR (400MHz, Chloroform-d, δ (ppm)): 8.12 (d, J = 8.4Hz, 2H), 7.73 (d, J = 8.2Hz, 2H), 7.44 (d, J = 3 .8Hz,1H),7.40(s,1H),7.33(d,J=12.1Hz,1H),6.98(s,4H),6.84(d,J=8.3Hz,4H),3.81(s,6H).

[0079] With this structure The synthetic route of the core derivative TPA-TCA can be referred to Example 1.

[0080] Example 3

[0081] The invention relates to an application of a triphenylamine derivative in preparing a photoelectric device structure.

[0082] In the present invention, the optoelectronic device structure can be selected from a solar cell, a field-effect transistor, a photodetector, a radiation detector, and a light-emitting diode. The solar cell can be selected from a single-junction thin-film solar cell or a tandem solar cell. The single-junction thin-film solar cell can be an organic solar cell, a perovskite solar cell, or a quantum dot solar cell. The tandem solar cell can be an organic / perovskite tandem solar cell, an all-perovskite tandem solar cell, or a perovskite / crystalline silicon tandem solar cell.

[0083] Triphenylamine derivatives are used as hole transport layer materials in organic solar cells or perovskite solar cells, or as interface modification materials for existing hole transport layers. Specifically, the cell structure can be selected from the following: 1) substrate / triphenylamine derivative / perovskite / electron transport layer / electrode; 2) substrate / electron transport layer / perovskite / triphenylamine derivative / electrode; 3) substrate / triphenylamine derivative / organic light absorbing layer / electrode / electrode; 4) substrate / electron transport layer / organic light absorbing layer / triphenylamine derivative / electrode; 5) substrate / hole transport layer / triphenylamine derivative / perovskite / electrode / electrode; 6) substrate / hole transport layer / triphenylamine derivative / organic light absorbing layer / electrode / electrode.

[0084] In this embodiment, the triphenylamine derivative is used in the perovskite solar cell process. The triphenylamine derivative is first prepared into a precursor using ethanol as a solvent. The precursor concentration is 0.3-0.5 mg / mL, and then spin-coated on a 2.25-4 cm 2The amount of spin coating on the indium tin oxide (ITO) glass sheet is 50-80 μL, the spin coating speed is 4000 rpm, the spin coating time is 30 s, and then annealing is performed at an annealing temperature of 100°C.

[0085] The compounds TPA-TCA and TPA-ETCA of Examples 1 and 2 of the present invention are used as organic self-assembly small molecule materials in perovskite solar cells. The device structure diagram of the perovskite solar cell is shown in FIG. Figure 1 From bottom to top, it is substrate, transparent oxide electrode, hole transport layer, photoactive layer, electron transport layer, hole blocking layer, and metal electrode. The photovoltaic data of related solar cell devices are shown in Table 1 and Figure 2 、 Figure 3 From Table 1 and Figure 2 、 Figure 3 It can be seen that the efficiency of perovskite solar cells using the compounds TPA-TCA and TPA-ETCA of the present invention as hole transport layers is as high as 25.07% and 25.94%, respectively, which is higher than the efficiency of perovskite solar cells using 2PACz and MeO-2PACz as hole transport layers.

[0086] Table 1 Photovoltaic data of perovskite solar cell devices based on different SAMs

[0087]

[0088] The above embodiments are only used to illustrate the present invention, and the scope of protection of the present invention is not limited to the above embodiments. Those skilled in the art can achieve the purpose of the present invention based on the contents disclosed in the present invention. Any improvements and modifications based on the concept of the present invention fall within the scope of protection of the present invention, and the specific scope of protection shall be subject to the claims.

Claims

1. A triphenylamine derivative, characterized in that It has the following molecular structure formula: Wherein, R1 is a linear, branched or cycloalkyl group selected from C1-C20; X is hydrogen or halogen; R3 is one or more of hydroxyl, carboxyl, phosphate, phosphate, sulfhydryl, amino, sulfonic acid, and boric acid.

2. The triphenylamine derivative according to claim 1, characterized in that Selected from the following structures: 、 。 3. Use of the triphenylamine derivative according to any one of claims 1 to 2 in the preparation of optoelectronic device structures.

4. The use of the triphenylamine derivative according to claim 3 in preparing a photoelectric device structure, characterized in that: The photoelectric device structure is one of a solar cell, a field effect transistor, a photodetector, a ray detector, and a light emitting diode.

5. Use of the triphenylamine derivative according to claim 4 in preparing a photoelectric device structure, characterized in that: The triphenylamine derivative is used as a hole transport layer material in an organic solar cell or a perovskite solar cell.

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