A dibenzothiophene derivative, a preparation method thereof and an application thereof

Abstract

The present invention discloses a bisbenzothiophene derivative, a preparation method thereof and an application thereof. The bisbenzothiophene derivative has a structural formula as shown in Formula (I) or Formula (II): #imgabs0# wherein, R is selected from substituted or unsubstituted C 1～30 alkyl, substituted or unsubstituted C 1～30 alkoxy, substituted or unsubstituted C 2～10 alkenyl, substituted or unsubstituted C 2～30 alkynyl, substituted or unsubstituted C 6～30 aryl; R1 and R2 are independently selected from substituted or unsubstituted C 6～30 aryl, substituted or unsubstituted C 6～30 heteroaryl. The bisbenzothiophene derivative provided by the present invention greatly improves the charge separation and transport efficiency of the device, realizes an organic solar cell with an efficiency exceeding 15%, and is of great significance for preparing large-area and high-efficiency battery devices.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor devices, and particularly to a bisbenzothiophene derivative, a preparation method thereof, and an application thereof. Background Art

[0002] In today's world, energy is an important factor promoting economic development. With the continuous development of the economy and the improvement of people's living quality, the consumption of traditional fossil energy is increasing day by day, bringing serious environmental pollution. Therefore, the development of renewable energy has become an essential way. Solar energy has a large storage capacity and a wide distribution range, and is a reliable renewable clean energy. A solar cell directly converts light energy into electrical energy, which is an ideal way to utilize solar energy. An organic solar cell is a technical means to convert this clean energy of solar energy into electrical energy. In addition, the effective utilization of solar energy is also a key measure to solve the energy problem. Organic solar cells have the advantages of light weight, adjustable color, flexibility, etc. Moreover, an organic solar cell that is inexpensive, efficient, and can be prepared on a large scale has always been the goal pursued by people.

[0003] As a new type of third-generation photovoltaic technology, organic solar cells have broad application prospects in the future energy field. The competitiveness of organic solar cells mainly depends on their cost, power generation per unit weight, and low-energy-consumption and more environmentally friendly preparation. In recent years, due to the in-depth research on high-efficiency photovoltaic materials, device optimization, and interface engineering, the bulk heterojunction (BHJ) OSCs of polymer donors and non-fullerene small molecule acceptors (SMAs) have also developed rapidly. The bulk heterojunction (BHJ) type organic solar cells formed by combining polymer donors and small molecule acceptors have a power conversion efficiency (PCEs) exceeding 18% many times. Although this type of solar cell has a high power conversion efficiency, it also has some defects: poor mechanical properties and instability under light and heat conditions, etc.

[0004] In the prior art, high-efficiency organic solar devices are all realized by small-area devices, and at the same time, the spin coating agent mainly uses harmful halogenated solvents, which is difficult to meet the requirements for future commercial mass production. If large-area thick-film devices are prepared, the energy conversion efficiency will decrease significantly. Therefore, it is very important to develop non-fullerene acceptor materials suitable for large-area OSCs. Using large-area (>1 cm 2 ) printing technology to prepare a uniform thin film with a thickness of 100 nm is a difficult task.

[0005] Therefore, the development of a fused-ring non-fullerene acceptor material that can be processed at room temperature using non-halogen solvents and has a determined molecular weight is urgently needed for the development of high-efficiency and large-area organic solar cells. It is of great significance for the preparation of low-cost and large-area organic solar cells and the promotion of their commercialization process. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, a first aspect of the present invention provides a bis(benzo[1,2-b:4,5-b']dithiophene) derivative, which can promote the device to obtain a high device efficiency and is applied to large-area organic solar cells at the same time.

[0007] A second aspect of the present invention further provides a preparation method of the bis(benzo[1,2-b:4,5-b']dithiophene) derivative.

[0008] A third aspect of the present invention further provides an application of the bis(benzo[1,2-b:4,5-b']dithiophene) derivative in large-area solar cells or organic light-emitting diodes.

[0009] A fourth aspect of the present invention further provides an active layer of a solar cell.

[0010] A fifth aspect of the present invention further provides a solar cell.

[0011] According to an embodiment of the first aspect of the present invention, a bis(benzo[1,2-b:4,5-b']dithiophene) derivative is provided, and the bis(benzo[1,2-b:4,5-b']dithiophene) derivative has a structural formula as shown in formula (I) or formula (II):

[0012]

[0013] Among them, R is selected from substituted or unsubstituted C 1～30 alkyl, substituted or unsubstituted C 1～30 alkoxy, substituted or unsubstituted C 2～10 alkenyl, substituted or unsubstituted C 2～30 alkynyl, substituted or unsubstituted C 6～30 aryl;

[0014] R1 and R2 are independently selected from substituted or unsubstituted C 6～30 aryl, substituted or unsubstituted C 6～30 heteroaryl.

[0015] The bis(benzo[1,2-b:4,5-b']dithiophene) derivative according to the embodiment of the present invention has at least the following beneficial effects:

[0016] The bis(benzo[1,2-b:4,5-b']dithiophene) derivative provided by the present invention is soluble in common solvents such as chloroform and chlorobenzene, and is easy to process; and has good thermal stability; a small molecule structure with good planarity, good film-forming property and low exciton binding energy is adopted; in addition, the bis(benzo[1,2-b:4,5-b']dithiophene) derivative greatly improves the charge separation and transport efficiency of the device, and avoids the disadvantages of the existing high-efficiency device interface layer such as moisture absorption, acidity and alkalinity, batch repeatability, and environmental instability, realizing an organic solar cell with an efficiency exceeding 14%, which is of great significance for the preparation of large-area and high-efficiency battery devices.

[0017] According to some embodiments of the present invention, R is selected from substituted or unsubstituted C 1～10alkyl, substituted or unsubstituted C 1～10 alkoxy, substituted or unsubstituted C 2～6 alkenyl, substituted or unsubstituted C 2～10 alkynyl, substituted or unsubstituted C 6～15 aryl.

[0018] According to some embodiments of the present invention, R1 and R2 are independently selected from substituted or unsubstituted C 6～15 aryl, substituted or unsubstituted C 6～15 heteroaryl.

[0019] According to some embodiments of the present invention, R1 and R2 are selected from one of the following structural formulas:

[0020]

[0021] wherein, X1 and X2 are independently selected from H, halogen, cyano, substituted or unsubstituted C 1～30 alkyl, substituted or unsubstituted C 1～30 alkoxy.

[0022] According to some embodiments of the present invention, the dibenzothiophene derivative is selected from one of the following structural formulas:

[0023]

[0024]

[0025]

[0026] According to the second aspect of the present invention, an embodiment provides a method for preparing the dibenzothiophene derivative, comprising the following steps:

[0027] S6. Add compound 5 or compound 10, add R1 compound, a first organic solvent and pyridine, and under an inert gas, obtain the dibenzothiophene derivative through a Knoevenagel reaction;

[0028]

[0029] According to some embodiments of the present invention, the first organic solvent is selected from at least one of chloroform, chlorobenzene, and toluene.

[0030] According to some embodiments of the present invention, compound 5 or compound 10 is prepared by the following method:

[0031] S5. Under an inert gas, react compound 4 or compound 9, DMF, 1,2-dichloroethane and POCl3 through a Vilsmeier-Haack reaction to obtain compound 5 or compound 10;

[0032] Among them, the structural formula of Compound 4 is as follows:

[0033]

[0034] According to some embodiments of the present invention, Compound 4 or Compound 9 is prepared by the following method:

[0035] S4. Under an inert gas, add Compound 3 or Compound 8, catalyst FeCl3, organic solvent MeNO2 and chlorobenzene and react to obtain Compound 4 or Compound 9;

[0036] Among them, the structural formulas of Compound 3 and Compound 8 are as follows:

[0037]

[0038] According to some embodiments of the present invention, Compound 3 or Compound 8 is prepared by the following method:

[0039] S3. Under a second organic solvent and an inert gas, add Compound 2 or Compound 7 and a catalyst, and carry out a Stille coupling reaction to obtain Compound 3 or Compound 8;

[0040] Among them, the structural formulas of Compound 2 and Compound 7 are as follows:

[0041]

[0042] According to some embodiments of the present invention, the second organic solvent includes at least one of toluene, tetrahydrofuran, N,N-dimethylformamide, dichloromethane, 1,4-dioxane or dimethyl sulfoxide.

[0043] According to some embodiments of the present invention, the first catalyst is at least one of tetrakis(triphenylphosphine)palladium, palladium acetate, bis(triphenylphosphine)palladium dichloride, tris(dibenzylideneacetone)dipalladium and tris(o-tolyl)phosphine or copper iodide.

[0044] According to some embodiments of the present invention, Compound 2 or Compound 7 is prepared by the following method:

[0045] S2. Under an inert gas, add Compound 1 or Compound 6, add NBS and tetrahydrofuran, and react to obtain Compound 2 or Compound 7;

[0046] According to some embodiments of the present invention, the structural formulas of Compound 1 and Compound 6 are as follows:

[0047]

[0048] According to some embodiments of the present invention, the compound 1 or compound 6 is prepared by the following method:

[0049] S1. Under an inert gas, 3,4-dibromothiophene or 3,6-dibromo[2,2'-bithiophene], 5-alkyl-2-tributylstannylthiophene, a catalyst, a ligand, and a third organic solvent are added, and through a Stille coupling reaction, compound 1 or 6 is obtained.

[0050] According to some embodiments of the present invention, the third organic solvent includes at least one of toluene, tetrahydrofuran, N,N-dimethylformamide, dichloromethane, 1,4-dioxane, or dimethyl sulfoxide.

[0051] According to some embodiments of the present invention, the second catalyst is at least one of tetrakis(triphenylphosphine)palladium, palladium acetate, bis(triphenylphosphine)palladium dichloride, tris(dibenzylideneacetone)dipalladium, tris(o-tolyl)phosphine, or copper(I) iodide.

[0052] The third aspect of the present invention provides the application of the above-mentioned bisbenzotrithiophene derivative in a large-area solar cell or an organic light-emitting diode.

[0053] According to some embodiments of the present invention, the large area means a solar cell with an area greater than 1 cm 2 .

[0054] According to some embodiments of the present invention, the large-area solar cell includes an extended-area organic solar cell and a perovskite solar cell.

[0055] The fourth aspect of the present invention provides a solar cell active layer, including a small molecule acceptor and a polymer donor, and the small molecule acceptor is selected from the above-mentioned bisbenzotrithiophene derivative.

[0056] According to some embodiments of the present invention, the polymer donor is selected from at least one of PM6, PBTB-T-2F, PBDB-T, D18, and PTQ-10.

[0057] The fifth aspect of the present invention provides an organic solar cell, which sequentially includes a substrate, a hole transport layer, an active layer, an electron transport layer, and a metal electrode; the active layer is selected from the above-mentioned solar cell active layer.

[0058] According to some embodiments of the present invention, the substrate is at least one of indium tin oxide (ITO) glass and fluorine tin oxide (FTO).

[0059] According to some embodiments of the present invention, the hole transport layer is selected from at least one of PEDOT:PSS, MoO3, V2O5, WO3, and NiO.

[0060] According to some embodiments of the present invention, the electron transport layer is selected from at least one of PFN-Br, PNDIT-F3N, PDINN or PDINO.

[0061] According to some embodiments of the present invention, the metal electrode is selected from at least one of Ag, Al or Cu.

[0062] Definitions and General Terms

[0063] As used herein, "substituted or unsubstituted" means that a group may or may not be further substituted by one or more groups selected from the following: alkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenoxy, aryloxy, benzyloxy, haloalkoxy, haloalkenoxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclic, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, phenylamino, diphenylamino, benzylamino, dibenzylamino, hydrazino, acyl, acylamino, diacylamino, acyloxy, heterocyclic, heterocycloxy, heterocyclicamino, haloheterocyclic, carboxyl ester, carboxyl, carboxylamide, mercapto, alkylthio, benzylthio, acylthio and phosphorus-containing groups.

[0064] "Substituted or unsubstituted C 1～30 alkyl" means an alkyl group having a total of 1 to 30 carbon atoms, including straight-chain C1-30 alkyl, branched-chain C1-30 alkyl and C3-30 cycloalkyl, and optionally at least one H in the alkyl is substituted by a group defined herein. For "substituted or unsubstituted C 1～10 alkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0065] "Substituted or unsubstituted C 1～30 alkoxy" means an alkoxy group having a total of 1 to 30 carbon atoms, including straight-chain C1-30 alkoxy, branched-chain C1-30 alkoxy and C2-30 cycloalkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, etc. And optionally at least one H in the alkoxy is substituted by a group defined herein. For "substituted or unsubstituted C 1～10 alkoxy" has a similar interpretation, except that the number of carbon atoms is different.

[0066] "Halogen" includes any one or more of fluorine, chlorine, bromine, iodine.

[0067] "Substituted or unsubstituted C 2～10 alkenyl" means a straight-chain or branched-chain hydrocarbon group having one or more double bonds, and the total number of carbon atoms in the group is 2 to 10. The double bond in the group can be at any position, and optionally C2～10 At least one H in the alkenyl group is replaced by a corresponding group defined herein. "Substituted or unsubstituted C 2-6 alkenyl group" has a similar interpretation, except that the number of carbon atoms is different.

[0068] "Substituted or unsubstituted C 2～30 alkynyl group" means a straight-chain or branched-chain hydrocarbon group having one or more triple bonds, and the total number of carbon atoms in the group is 2 to 30. The triple bond in the group can be at any position, and optionally C 2～30 At least one H in the alkynyl group is replaced by a corresponding group defined herein. "Substituted or unsubstituted C 2-10 alkynyl group" has a similar interpretation, except that the number of carbon atoms is different.

[0069] "Substituted or unsubstituted C 6～30 aryl group" means a fully carbon monocyclic or fused polycyclic group having a fully conjugated π-electron system. It represents a fully carbon monocyclic or fused polycyclic group of 6 to 30 carbon atoms; for example, benzene, naphthalene, indene, fluorene, etc. And optionally C 6～30 At least one H in the aryl group is replaced by a corresponding group defined herein. "Substituted or unsubstituted C 6-15 aryl group" has a similar interpretation, except that the number of carbon atoms is different.

[0070] "Substituted or unsubstituted C 6～30 heteroaryl group" means a monocyclic or fused ring group of ring atoms, containing one, two, three or four ring heteroatoms selected from N, O or S, and the remaining ring atoms are C, and further having a fully conjugated π-electron system, with a total number of carbon atoms of 6 to 30, and optionally C 6～30 At least one H in the heteroaryl group is replaced by a corresponding group defined herein. "Substituted or unsubstituted C 6-15 heteroaryl group" has a similar interpretation, except that the number of carbon atoms is different.

[0071] "*" in the present invention represents the connection site of the group.

[0072] Other features and advantages of the present invention will be described in the subsequent specification, and in part will become apparent from the specification, or will be understood by implementing the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] The above and / or additional aspects and advantages of the present invention will become apparent and be easily understood from the description of the embodiments in conjunction with the following drawings, wherein:

[0074] Figure 1 is a schematic structural diagram of the solar cell device of the present invention;

[0075] Figure 2 J-V curve of the dibenzothiophene derivative prepared in Example 1 and Example 3 applied to an organic solar cell;

[0076] Figure 3 EQE curve of the dibenzothiophene derivative prepared in Example 1 and Example 3 applied to an organic solar cell. Detailed implementation mode

[0077] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in combination with the embodiments, but the present invention is not limited to these embodiments.

[0078] The reagents, methods, and equipment used in the present invention are all conventional reagents, methods, and equipment in the technical field, unless otherwise specified.

[0079] Example 1

[0080] Example 1 provides a dibenzothiophene derivative, and its reaction equation and preparation method are as follows:

[0081]

[0082] S1. In a 250 mL round-bottom flask, weigh 3,4-dibromothiophene (5 g, 20.7 mmol) and tributyl(5-hexylthiophen-2-yl)stannane (20.77 g, 45.4 mmol), dissolve them in 100 mL of tetrahydrofuran, displace the gas, pass argon for 15 minutes, and add bis(triphenylphosphine)palladium(II) dichloride (1.2 g, 1.04 mmol) to the reaction system under argon protection. The reactants are refluxed at 80 °C for 24 hours. Cool to room temperature, rotary evaporate the tetrahydrofuran, extract with dichloromethane, rotary evaporate the solvent to obtain a crude product, and purify it by silica gel column chromatography to obtain a solid product, which is Compound 1 (6.73 g, 78%); HRMS (m / z, MALDI): Calc. for C24H32S3, [M+H]+: 416.17, found: 416.70.

[0083] S2. Add Compound 1 (4 mg, 9.6 mmol) dissolved in dry THF (40 mL) to a 250 mL round-bottom flask equipped with a stir bar, and then add NBS (3.59 g, 20.2 mmol). Then react at room temperature for 8 h. Rotary evaporate the tetrahydrofuran, extract with dichloromethane, rotary evaporate the solvent to obtain a crude product, and purify it by silica gel column chromatography to obtain a solid product, which is Compound 2 (4.91 g, 89%); HRMS (m / z, MALDI): Calc. for C24H32Br2S3, [M+H]+: 573.99, found: 574.50.

[0084] S3. In a 250 mL round-bottom flask, weigh out compound 2 (2 g, 3.4 mmol) and tributyl(thieno[3,2-b]thiophen-2-yl)stannane (3.29 g, 7.6 mmol), dissolve them in 60 mL of toluene, displace the gas, purge with argon for 15 minutes, and under argon protection, add tetrakis(triphenylphosphine)palladium Pd(PPh3)4 (0.17 g, 0.14 mmol) to the reaction system. The reactants are refluxed at 110 °C for 24 hours. Cool to room temperature, rotary evaporate the toluene, extract with dichloromethane, rotary evaporate the solvent to obtain the crude product, and purify by silica gel column chromatography to obtain a red solid, which is compound 3 (1.93 g, 80%); HRMS (m / z, MALDI): Calc. for: C 36 H 36 S7, [M+H] + : 693.10, found: 692.09.

[0085] S4. Add compound 3 (2 g, 2.89 mmol) and FeCl3 (4.67 g, 28.9 mmol) to a 250 mL sealed tube, then add MeNO2 and chlorobenzene to dissolve. React the reaction mixture at room temperature for 24 h, neutralize with sodium bicarbonate solution, extract with ethyl acetate, dry the organic phase with anhydrous sodium sulfate, and then concentrate in vacuo. Rotary evaporate the solvent to obtain the crude product, and purify by silica gel column chromatography to obtain a red solid, which is compound 4 (1.39 g, 70%); HRMS (m / z, MALDI): Calc. for: C36H32S7, [M+H]+: 689.07, found: 688.05.

[0086] S5. In a 100 mL three-necked flask, add compound 4 (0.50 g, 0.73 mmol) and anhydrous N,N-formamide (25 mL), stir for a few minutes at 0 °C, and then add phosphorus oxychloride (1.5 mL). Stir the reaction solution at 0 °C for 1 hour, then raise the temperature to 90 °C and stir overnight. Cool to room temperature, extract with dichloromethane, rotary evaporate the solvent, and purify by silica gel column chromatography to obtain compound 5 (0.46 g, 86%); HRMS (m / z, MALDI): Calc. for: C36H32O2S7, [M+H]+: 745.09, found: 744.04.

[0087] S6. In a 100-mL round-bottom flask, compound 5 (300 mg, 0.40 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (389.2 mg, 1.01 mmol) were dissolved in 50 mL of chloroform, and the gas was replaced three times. Under argon protection, 2.5 mL of pyridine was slowly added while stirring. The mixture was refluxed under argon protection for 12 h, cooled to room temperature, poured into 300 mL of anhydrous methanol, and filtered to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain a dark blue solid, which was a dibenzoterthiophene derivative (biBT-4F) (338.9 mg, 72%), HRMS (m / z, MALDI): Calc.for: C36H32F4N4O2S7, [M+H]+: 1169.41, found: 1168.08.

[0088] Example 2

[0089] Example 2 provides a dibenzoterthiophene derivative, the structural formula and preparation method of which are as follows:

[0090]

[0091] S6. Dissolve the compound 5 (300 mg, 0.40 mmol) in Example 1 and 5,6-dichloro-3-(dicyanomethylidene)indone (400 mg, 1.52 mmol) in 50 mL of chloroform, replace the gas three times, protect with argon, slowly add 2.5 mL of pyridine while stirring, and reflux the mixture under argon for 12 h. Cool to room temperature, pour into 300 mL of anhydrous methanol, filter to obtain a crude product, and separate and purify by silica gel column chromatography to obtain a dark blue solid, which is a dibenzoterthiophene derivative (biBT-4Cl) (338.9 mg, 72%), HRMS (m / z, MALDI): Calc.for: C36H32Cl4N4O2S7, [M+H]+: 1235.22, found: 1233.96.

[0092] Example 3

[0093] Example 3 provides a dibenzoterthiophene derivative, the reaction equation and preparation method of which are as follows:

[0094]

[0095] S1: In a 250 mL round-bottom flask, weigh 3,6-dibromobenzothiophene (4 g, 13.4 mmol) and tributyl(5-hexylthiophen-2-yl)stannane (13.53 g, 29.5 mmol), dissolve them in 100 mL of tetrahydrofuran, displace the gas, purge with argon for 15 minutes, and under argon protection, add bis(triphenylphosphine)palladium dichloride (0.31 g, 0.44 mmol) to the reaction system. The reactants are refluxed at 80 °C for 24 hours. Cool to room temperature, rotary evaporate the tetrahydrofuran, extract with dichloromethane, rotary evaporate the solvent to obtain the crude product, and purify by silica gel column chromatography to obtain a solid product, which is compound 6 (4.87 g, 77%); HRMS (m / z, MALDI): Calc. for: C 26 H 32 S4,[M+H] + : 472.78, found: 472.14;

[0096] S2: In a 100 mL round-bottom flask equipped with a magnetic stirrer, add compound 6 (3 g, 6.3 mmol) dissolved in dry THF (40 mL), and then add NBS (2.37 g, 13.3 mmol). Then react at room temperature for 8 h. Rotary evaporate the tetrahydrofuran, extract with dichloromethane, rotary evaporate the solvent to obtain the crude product, and purify by silica gel column chromatography to obtain a solid product, which is compound 7 (3.44 g, 86%); HRMS (m / z, MALDI): Calc. for: C 26 H 30 Br2S4,[M+H] + : 630.57, found: 629.96;

[0097] S3: In a 250 mL round-bottom flask, weigh compound 7 (3.84 g, 6.08 mmol) and tributyl(thieno[3,2-b]thiophen-2-yl)stannane (5.76 g, 13.4 mmol), dissolve them in 60 mL of tetrahydrofuran, displace the gas, purge with argon for 15 minutes, and under argon protection, add tetrakis(triphenylphosphine)palladium Pd(PPh3)4 (0.31 g, 0.44 mmol) to the reaction system. The reactants are refluxed at 80 °C for 24 hours. Cool to room temperature, rotary evaporate the tetrahydrofuran, extract with dichloromethane, rotary evaporate the solvent to obtain the crude product, and purify by silica gel column chromatography to obtain a red solid, which is compound 8; HRMS (m / z, MALDI): Calc. for: C 38 H 36 S8,[M+H] + : 749.19, found: 748.14;

[0098] S4: Add compound 8 (1.5 g, 2.01 mmol) and FeCl3 (3.24 g, 20 mmol) into a 250 mL sealed tube, then add MeNO2 and chlorobenzene to dissolve. React the reaction mixture at room temperature for 24 h. After neutralizing with sodium bicarbonate solution, extract with ethyl acetate. Dry the organic phase with anhydrous sodium sulfate and then concentrate in vacuo. Rotate to dry the solvent to obtain the crude product, and purify it by silica gel column chromatography to obtain a red solid, which is compound 9 (1.02 g, 68%); HRMS (m / z, MALDI): Calc. for: C 38 H 32 S8, [M+H] + : 745.15, found: 744.03;

[0099] S5: In a 100 mL three-necked flask, add compound 9 (0.50 g, 0.67 mmol) and anhydrous N,N-dimethylformamide (25 mL). Stir at 0 °C for a few minutes and then add phosphorus oxychloride (1.5 mL). Stir the reaction solution at 0 °C for 1 h, then raise the temperature to 90 °C and stir overnight. Cool to room temperature, extract with dichloromethane, rotate to dry the solvent, and purify by silica gel column chromatography to obtain compound 10 (440.81 mg, 82%); HRMS (m / z, MALDI): Calc. for: C 40 H 32 O2S8, [M+H] + : 801.17, found: 800.02;

[0100] S6: In a 100 mL round-bottom flask, dissolve compound 10 (300 mg, 0.37 mmol) and 5,6-difluoro-3-(dicyanomethylene)indanone (414.30 mg, 1.80 mmol) in 50 mL of chloroform. Replace the gas 3 times and protect with argon. Slowly add 2.5 mL of pyridine while stirring. The mixture is refluxed and reacted for 12 h under argon protection. Cool to room temperature, pour it into 300 mL of anhydrous methanol, and filter to obtain the crude product. Purify it by silica gel column chromatography to obtain a dark blue solid, which is the bisbenzothiophene derivative (biBTT-4F) (334.92 mg, 73%). HRMS (m / z, MALDI): Calc. for: C 64 H 36 F4N4O2S8, [M+H] + : 1225.49, found: 1224.05.

[0101] Example 4

[0102] Example 4 provides a bisbenzothiophene derivative, and its structural formula and preparation method are as follows:

[0103]

[0104] S6. In a 100 mL round-bottom flask, dissolve the compound 10 (300 mg, 0.37 mmol) prepared in Example 3 and 5,6-dichloro-3-(dicyanomethylene) indanone (400 mg, 1.52 mmol) in 50 mL of chloroform. Replace the gas three times and protect with argon. Slowly add 2.5 mL of pyridine while stirring. The mixture is refluxed for 12 h under argon protection, cooled to room temperature, poured into 300 mL of anhydrous methanol, and the crude product is obtained by suction filtration. It is separated and purified by silica gel column chromatography to obtain a dark blue solid, which is the bisbenzotri thiophene derivative (biBTT-4Cl) (334.92 mg, 73%). HRMS (m / z, MALDI): Calc. for: C 64 H 36 Cl4N4O2S8, [M + H]+: 1291.85, found: 1289.97.

[0105] Performance testing

[0106] The preparation and characterization of organic photovoltaic (OPV) devices are as follows:

[0107] As Figure 1 shown, the OPC device successively includes a substrate, a hole transport layer, an active layer, an electron transport layer, and a metal electrode. The commercially purchased indium tin oxide (ITO) glass (specification: 1.5 cm * 1.5 cm) substrate is first scrubbed with acetone, and then successively ultrasonically cleaned with detergent, water, deionized water, acetone, and isopropanol. After drying, a 30 nm thick PEDOT:PSS is spin-coated as the hole transport layer for standby. A chloroform blend solution (10 - 30 mg / mL) of the polymer donor material PM6 and biBT-4F or biBTT-4F prepared in Example 1 or 3 (weight ratio 1:1.2) and the additive chloronaphthalene (0.25% - 3%) is spin-coated on the PEDOT:PSS hole transport layer to form the active layer of the device. Finally, a layer of about 10 nm thick PNDIT-F3N is spin-coated as the electron transport layer and Ag (100 nm) as the device metal electrode to obtain a solar cell device structure: ITO / PEDOT:PSS / active layer / PNDIT-F3N / Ag).

[0108] Among them, the structures of the polymer donor material PM6 (purchased from Shuolun Organic Optoelectronic Technology (Beijing) Co., Ltd.) and the electron transport layer PNDIT-F3N (purchased from Nanjing Zhiyan Technology Co., Ltd.) used in the above organic solar cell device are as follows:

[0109]

[0110]

[0111] The energy conversion efficiency of the solar cell was measured by using the Guangyan SS-F5-3A as a solar simulator at a light intensity of 100 mW / cm 2 . The photovoltaic performance of the device was tested, and the light intensity was calibrated by a standard single-crystalline silicon solar cell (SRC-00019); the J-V curve was measured using a Keithley 2400. The open-circuit voltage, short-circuit current, and fill factor of the above solar cell device were measured, and the corresponding photoelectric conversion efficiency was calculated.

[0112] The J-V curve of the solar cell device is as Figure 2 shown. For the device with biBT-4F as the active layer acceptor, the open-circuit voltage V OC = 0.83 V, the short-circuit current J SC = 25.7 mA / cm 2 , the fill factor FF = 75%, and the conversion efficiency PCE = 16.17%; for the device with biBTT-4F as the active layer acceptor, the open-circuit voltage V OC = 0.82 V, the short-circuit current J SC = 23.96 mA / cm 2 , the fill factor FF = 74.1%, and the conversion efficiency PCE = 14.68%.

[0113] In addition, under the same conditions, for the device with the existing acceptor material Y6 (purchased from Nanjing Zhiyan Technology Co., Ltd.) as the active layer acceptor, the open-circuit voltage V OC = 0.81 V, the short-circuit current J SC = 23.4 mA / cm 2 , the fill factor FF = 73%, and the conversion efficiency PCE = 13.82%. Figure 3 The EQE curves of biBT-4F and biBTT-4F in Examples 1 and 3 applied to organic solar cells are shown. The integrated short-circuit currents obtained from the EQE curves are 24.7 mA / cm 2 and 23.4 mA / cm 2 respectively, and the error from the measured values is within 5%, indicating that the device data has high reliability.

[0114] The preparation and characterization of large-area printed OPV devices are as follows:

[0115] 20 cm 2The IT0 conductive glass was then ultrasonically cleaned successively with detergent, water, deionized water, acetone, and isopropyl alcohol. After drying, a 30-nm-thick layer of PEDOT:PSS was spin-coated on the substrate as a hole transport layer for standby. A chloroform blend solution (10 - 30 mg / mL) of the polymer donor material PM6 and Y6 or the acceptor material prepared in Example 1 (weight ratio 1:1.3), along with the additive chloronaphthalene (0.25%), was printed on the PEDOT:PSS layer to form an active layer of the device with a thickness of 300 nm. PNDIT-F3N was dissolved in a methanol solution with 0.5% acetic acid to prepare a 1 mol / mL solution, which was spin-coated on the surface of the active layer at a speed of 4000 revolutions per second, and then annealed at 100 °C for 10 min to prepare an electron transport layer with a thickness of 8 nm. Finally, an Ag electrode was prepared using a printing technique with silver paste as the raw material. A layer of silver paste was directly brushed on the surface of the prepared electron transport layer as the electrode, and the thickness of the electrode layer was 100 nm.

[0116] For the performance test of large-area devices, a point on a large-area battery was selected for testing. Under standard test conditions: AM1.5, 100 mW / cm 2 , the open-circuit voltage (V OC ) of the biBT-4F device was measured to be 0.81 V, the short-circuit current (J SC ) was 22.89 mA / cm 2 , the fill factor (FF) was 0.53, and the power conversion efficiency (PCE) was 9.13%. Meanwhile, for the device with Y6, the open-circuit voltage (VOC) was 0.69 V, the short-circuit current (J SC ) was 20.27 mA / cm 2 , the fill factor (FF) was 0.39, and the power conversion efficiency (PCE) was 5.44%.

[0117] The above has made a detailed description in conjunction with the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the knowledge scope of those of ordinary skill in the art, various changes can be made without departing from the gist of the present invention.

Claims

1. A bis-benzothiophene derivative, characterized in that, The dibenzothiophene derivative has a structural formula of formula (I) or formula (II): ； Among them, R is selected from C 1~10 alkyl; R1 and R2 are selected from the following structural formulas: ； Wherein, X1 and X2 are independently selected from halogens.

2. The dibenzothiophene derivative according to claim 1, characterized in that, The dibenzothiophene derivative is selected from one of the following structural formulas: 。 3. Use of the dibenzothiophene derivative according to claim 1 or 2 in a large-area solar cell or an organic light-emitting diode.

4. The application according to claim 3, characterized in that The large-area solar cell includes a large-area organic solar cell and a perovskite solar cell.

5. A solar cell active layer, comprising a small molecule acceptor and a polymer donor, characterized in that, The small molecule acceptor is selected from the dibenzothiophene derivatives according to claim 1 or 2.

6. The active layer of the solar cell according to claim 5, characterized in that, The polymer donor is selected from at least one of PM6, PBTB-T-2F, PBDB-T, D18, and PTQ-10.

7. An organic solar cell, characterized in that, It sequentially includes a substrate, a hole transport layer, an active layer, an electron transport layer, and a metal electrode; the active layer is selected from the solar cell active layers according to claim 5.

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