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CN-122010979-A - Organic micromolecular photovoltaic material based on benzopyrazine donor cores, and preparation method and application thereof

CN122010979ACN 122010979 ACN122010979 ACN 122010979ACN-122010979-A

Abstract

The invention provides an organic micromolecule photovoltaic material based on a benzopyrazine donor core, a preparation method and application thereof, wherein the core which enlarges the conjugation degree of a middle skeleton of a traditional receptor micromolecule Y6 is taken as a middle donor unit, the organic micromolecule photovoltaic material based on the benzopyrazine donor core is synthesized, the organic micromolecule photovoltaic material has good processability and good dissolving capacity in common organic solvents, meanwhile, the soluble organic micromolecule photovoltaic material has good accumulation on a film, the absorption of the film has obvious red shift relative to the solution, and when the organic micromolecule photovoltaic material based on the benzopyrazine donor core is used as a receptor material and is blended with a polymer donor material D18, the energy conversion efficiency is more than 18%, the open-circuit voltage is more than 0.94 and eV, and the energy loss is reduced to 0.502 eV.

Inventors

  • WEI ZHIXIANG
  • LV KUN
  • Deng Shuaijing

Assignees

  • 国家纳米科学中心

Dates

Publication Date
20260512
Application Date
20260129

Claims (10)

  1. 1. The organic small molecule photovoltaic material based on the benzopyrazine donor core is characterized by having the following structure: ; Wherein D is a donor unit and A is an acceptor unit; the donor unit is selected from any one of the structures shown in the following formula I-1 or formula I-2, wherein Representing the receptor unit attachment position: ; Wherein R 1 is selected from any one of alkyl or ketal, R 2 is selected from alkyl or silane, R 3 and R 4 are each independently selected from any one of hydrogen, halogen, alkyl, substituted or unsubstituted thiophene and substituted or unsubstituted benzene ring, the alkyl, ketal and silane groups have 5-20 carbon atoms, and X 1 -X 3 is each independently selected from sulfur atom or selenium atom.
  2. 2. The benzopyrazine donor core based organic small molecule photovoltaic material according to claim 1, wherein said donor unit is selected from any one of the following structures, wherein Representing the donor element connection position: 。
  3. 3. The benzopyrazine donor core based organic small molecule photovoltaic material according to claim 1 or 2, characterized in that said R 1 is chosen from any one of C6-C11 linear alkyl, C6-C11 branched alkyl, C6-C11 ketal or C6-C11 aromatic alkyl, preferably C9-C11 linear alkyl; Preferably, R 2 is selected from any one of C8-20 straight-chain alkyl, C8-20 branched-chain alkyl or C8-20 silane; Preferably, R 2 is selected from any one of the following structures: ; Preferably, each of R 3 and R 4 is independently selected from any one of hydrogen, fluorine, chlorine, bromine, C4-C8 straight chain alkyl, C4-C8 branched chain alkyl, thiophene, halothiophene, benzene ring, or halogenated benzene ring.
  4. 4. A benzopyrazine donor core based organic small molecule photovoltaic material according to any one of claims 1 to 3, characterized in that said acceptor unit is selected from any one of the structures shown below, wherein Representing the connection position: ; wherein R 5 、R 6 is independently selected from any one of H, F or Cl; preferably, the acceptor unit shown is selected from any one of the following structures: 。
  5. 5. The benzopyrazine donor core based organic small molecule photovoltaic material according to any one of claims 1 to 4, wherein said benzopyrazine donor core based organic small molecule photovoltaic material is selected from any one of the following M1 to M6: 。
  6. 6. the method for preparing a benzopyrazine donor core-based organic small molecule photovoltaic material according to any one of claims 1 to 5, characterized in that said preparation method comprises the following steps: (1) The preparation raw materials of the donor unit shown in the formula III-1 or the formula III-2 are mixed with trifluoro phenylboronic acid shown in the formula IV, and the compounds shown in the formula i-1 and the formula i-2 are obtained through a suzuki reaction, wherein the reaction formula is shown as follows: (2) Mixing a donor unit shown in a formula i-1 or a formula i-2, a VHA reagent and a halogenating agent to react to obtain a dialdehyde end group compound, wherein the reaction formula is shown as follows: ; (3) Reacting the dialdehyde end group compound obtained in the step (2) with an acceptor compound to obtain the benzopyrazine donor core-based organic small molecule photovoltaic material, wherein the reaction formula is as follows: wherein R 0 is selected from bromine atoms EG is selected from Wherein the carbon atom at the position of the asterisk is a carbon atom common to the double bonds attached to EG; the receptor compound is any one of the following compounds: 。
  7. 7. The process according to claim 6, wherein the molar ratio of the starting material for the preparation of the donor unit of formula III-1 or formula III-2 to the compound of formula IV is 1 (1.5-2.5); Preferably, the reaction of step (1) is carried out in the presence of a catalyst, preferably tris (dibenzylideneandenone) dipalladium; Preferably, the molar ratio of the preparation raw materials of the donor unit shown in the formula III-1 or the formula III-2 to the catalyst is 1:0.06-0.20; Preferably, the reaction of step (1) is carried out in the presence of a ligand, preferably tris (o-tolyl) phosphine; Preferably, the molar ratio of the preparation raw materials of the donor unit shown in the formula III-1 or the formula III-2 to the ligand is 1:0.24-0.35; Preferably, the reaction of step (1) is carried out in the presence of a base, preferably potassium carbonate; Preferably, the molar ratio of the preparation raw materials of the donor unit shown in the formula III-1 or the formula III-2 to the alkali is 1:4-10; preferably, in step (1), the temperature of the mixing is from 0 to 25 ℃; preferably, in step (1), the temperature of the mixing is from 0 to 5 ℃; preferably, in step (1), the temperature of the reaction is 70-95 ℃; preferably, in step (1), the temperature of the reaction is 80-85 ℃; preferably, in step (1), the reaction time is 10-24 h; Preferably, in step (1), the reaction time is 10-12 h; Preferably, in step (1), the reaction is carried out in either tetrahydrofuran or toluene solvent or a combination of both; preferably, in step (1), the reaction is carried out in tetrahydrofuran; Preferably, in step (1), the reaction is performed in a protective gas atmosphere, wherein the protective gas is any one of nitrogen, argon or helium.
  8. 8. The method of claim 6, wherein in step (2), the VHA reagent is DMF and the halogenating reagent is any one or a combination of at least two of POCl 3 、COCl 2 or SOCl 2 ; Preferably, in the step (2), the molar ratio of the preparation raw material of the donor unit shown in the formula III-1 or the formula III-2, the VHA reagent and the halogenating agent is 1 (15-25): 15-25; Preferably, in step (2), the halogenating agent is POCl 3 ; Preferably, in step (2), the temperature of the mixing is from 0 to 25 ℃; Preferably, in step (2), the temperature of the mixing is from 0 to 5 ℃; Preferably, in step (2), the temperature of the reaction is 50-85 ℃; preferably, in step (2), the temperature of the reaction is 75-85 ℃; preferably, in step (2), the reaction time is 18-48 h; preferably, in step (2), the reaction time is 18-22 h; Preferably, in step (2), the reaction is carried out in a chlorinated solvent which is any one or a combination of at least two of 1, 2-dichloroethane, dichloromethane or chloroform; Preferably, in step (2), the reaction is carried out in a chlorinated solvent, which is 1, 2-dichloroethane; preferably, in the step (2), the reaction is performed in a protective gas atmosphere, wherein the protective gas is any one of nitrogen, argon or helium; preferably, in step (3), the molar ratio of the dialdehyde end-group compound to the acceptor compound is 1 (2-10); Preferably, in step (3), the molar ratio of the dialdehyde end-group compound to the acceptor compound is 1 (4-8); Preferably, in step (3), the temperature of the reaction is from 30 to 65 ℃; preferably, in step (3), the temperature of the reaction is 60-65 ℃; Preferably, in step (3), the reaction time is 8-24 h; preferably, in step (3), the reaction time is 8-10 h; Preferably, in step (3), the reaction is performed under a basic catalyst, wherein the basic catalyst is any one of triethylamine, pyridine or piperidine; preferably, in step (3), the reaction is carried out under a basic catalyst, which is pyridine; preferably, the mass ratio of the dialdehyde end-group compound to the basic catalyst is (6-8): 100; Preferably, the mass ratio of the dialdehyde end-group compound to the basic catalyst is (7.5-8) 100; Preferably, in step (3), the reaction is carried out in a solvent which is any one or a combination of at least two of 1, 2-dichloroethane, dichloromethane or chloroform; preferably, in step (3), the reaction is carried out in a solvent which is chloroform.
  9. 9. The process according to claim 6, wherein the process for preparing the donor element compounds of formula I-1 and formula I-2 comprises the steps of: (a) Mixing a compound shown in a formula II with a reducing agent, and reacting to obtain an intermediate; (b) Mixing the intermediate obtained in the step (a) with a compound shown in a formula III, and reacting to obtain an intermediate 2; (c) Mixing the intermediate 2 obtained in the step (b) with a trifluoro phenylboronic acid compound, and obtaining donor unit compounds shown in the formula I-1 and the formula I-2 through a suzuki reaction; ; preferably, in the step (a), the molar ratio of the compound shown in the formula II to the reducing agent is 1 (10-40); Preferably, in the step (a), the molar ratio of the compound shown in the formula II to the reducing agent is 1 (30-40); Preferably, in the step (a), the reducing agent is zinc powder or sodium borohydride; preferably, in step (a), the reducing agent is zinc powder; preferably, in step (a), the temperature of the reaction is from 40 to 85 ℃; preferably, in step (a), the temperature of the reaction is 80-85 ℃; preferably, in step (a), the reaction is carried out for a period of time ranging from 24 to 48 h; preferably, in step (a), the reaction is carried out for a period of time ranging from 44 to 48 h; preferably, in step (a), the reaction is carried out in a solvent which is glacial acetic acid; preferably, in step (a), the reaction is carried out in a protective gas atmosphere, the protective gas being any one of nitrogen, argon or helium; preferably, in step (b), the molar ratio of intermediate to compound of formula III is 1 (1.5-2.5); Preferably, in step (b), the molar ratio of intermediate to compound of formula III is 1:1.5; preferably, in step (b), the temperature of the reaction is 25-85 ℃ and the time of the reaction is 24-48 h; Preferably, in step (c), the molar ratio of intermediate to trifluorophenylboronic acid compound is 1 (1.5-2.5); Preferably, in step (c), the molar ratio of intermediate to trifluorophenylboronic acid compound is 1:1.5; Preferably, the reaction in step (c) is carried out in the presence of a catalyst; Preferably, the molar ratio of intermediate to catalyst in step (c) is 1 (0.04-0.08); preferably, the reaction in step (c) is carried out in the presence of a ligand; Preferably, the molar ratio of intermediate to ligand in step (c) is 1 (0.24-0.40); Preferably, the reaction in step (c) is carried out in the presence of a base; preferably, the molar ratio of intermediate to base in step (c) is 1 (4-6); preferably, in step (c), the catalyst is tetra triphenylphosphine bar, tris (dibenzylideneandene acetone) dipalladium; preferably, in step (c), the catalyst is tris (dibenzylideneandenone) dipalladium; preferably, in step (c), the ligand is triphenylphosphine, tris (o-tolyl) phosphine; preferably, in step (c), the ligand is tris (o-tolyl) phosphine; Preferably, in step (C), the temperature of the reaction is from 70 to 95 ℃; Preferably, in step (C), the temperature of the reaction is 80-85 ℃; preferably, in step (c), the reaction is carried out for a period of time ranging from 10 to 24 h; Preferably, in step (c), the reaction is carried out for a period of time ranging from 10 to 12h; Preferably, in step (c), the reaction is carried out in a solvent, which is tetrahydrofuran; preferably, in step (c), the reaction is carried out in a protective gas atmosphere, the protective gas being any one of nitrogen, argon or helium.
  10. 10. Use of a benzopyrazine donor core based organic small molecule photovoltaic material according to any one of claims 1-5 in the preparation of photovoltaic devices; Preferably, the photovoltaic device comprises an organic solar cell; Preferably, the active layer of the organic solar cell consists of a donor material and a acceptor material, wherein the acceptor material comprises the benzopyrazine donor core-based organic small molecule photovoltaic material according to any one of claims 1 to 5; preferably, the polymeric donor material is D18, PM6; Preferably, the small molecule donor material is D18.

Description

Organic micromolecular photovoltaic material based on benzopyrazine donor cores, and preparation method and application thereof Technical Field The invention belongs to the technical field of photovoltaic materials, and particularly relates to a benzopyrazine donor core-based organic micromolecular photovoltaic material, a preparation method and application thereof. Background In recent years, organic solar cells have received attention because of their ability to be processed in solution, low cost, light weight, translucency, ease of fabrication of large area flexible thin film devices, and the like （(a) S. Gunes, H. Neugebauer, N. S. Sariciftci, Conjugated Polymer-Based Organic Solar Cells Chemical Reviews2007, 107, 1324-1338. (b) G. Li, V. Shrotriya, J. S. Huang, Y. Yao, T. Moriarty, K. Emery, Y. Yang, High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends Nature Materials2005, 4, 864-868. (c) J. H. Hou, O. Inganas, R. H. Friend, F. Gao, Organic solar cells based on non-fullerene acceptors Nature Materials 2018, 17, 119-128.）. Non-fullerene acceptor materials have significant advantages in light absorption properties, compatibility with donors, and electroluminescent properties. With the rapid development of material structure and device technology, the optimal photoelectric conversion efficiency of the organic solar cell based on the non-fullerene acceptor material reaches 19% ((a) C. Li, J. D. Zhou, J. L. Song, J. Q. Xu, H. T. Zhang, X. N. Zhang, J. Guo, L. Zhu, D. H. Wei, G. C. Han, J. Min, Y. Zhang, Z. Q. Xie, Y. P. Yi, H. Yan, F. Gao, F. Liu, Y. M. Sun, Non-fullerene acceptors with branched side chains and improved molecular packing to exceed 18% efficiency in organic solar cells Nat. Energy 2021, 6, 605-613. (b) L. Meng, Y. Zhang, X. Wan, C. Li, X. Zhang, Y. Wang, X. Ke, Z. Xiao, L. Ding, R. Xia, H. L. Yip, Y. Cao, Y. Chen, Organic and solution-processed tandem solar cells with 17.3% efficiency Science 2018, 361, 1094-1098. (c) Y. Cui, Y. Xu, H. F. Yao, P. Q. Bi, L. Hong, J. Q. Zhang, Y. F. Zu, T. Zhang, J. Z. Qin, J. Z. Ren, Z. H. Chen, C. He, X. T. Hao, Z. X. Wei, J. H. Hou, Single-Junction Organic Photovoltaic Cell with 19% Efficiency Adv. Mater. 2021, 33, 2102420.). However, the photoelectric conversion efficiency of organic solar cells is still lower than that of crystalline silicon solar cells and perovskite solar cells ((a) K. Yoshikawa, H. Kawasaki, W. Yoshida, T. Irie, K. Konishi, K. Nakano, T. Uto, D. Adachi, M. Kanematsu, H. Uzu, K. Yamamoto, Silicon heterojunction solar cell with interdigitated back contacts for a photoconversion efficiency over 26% Nat. Energy 2017, 2, 17032. (b) Z. Liu, L. Krückemeier, B. Krogmeier, B. Klingebiel, J. A. Márquez, S. Levcenko, S. Öz, S. Mathur, U. Rau, T. Unold, T. Kirchartz, Significant Advances in Energy Research ACS Energy Lett. 2018, 4, 110-117. (c) J. Z. Yao, T. Kirchartz, M. S. Vezie, M. A. Faist, W. Gong, Z. C. He, H. B. Wu, J. Troughton, T. Watson, D. Bryant, J. Nelson, Optimal State Choice for Rydberg-Atom Microwave SensorsPhys. Rev. Appl. 2015, 4, 014020.). In fact, the open circuit voltage of most high performance organic solar cells is still limited to 0.8-0.9V, the exciton dissociation and recombination process requires additional energy, and a large energy loss is an important factor ((a) L. Hong, H. Yao, Z. Wu, Y. Cui, T. Zhang, Y. Xu, R. Yu, Q. Liao, B. Gao, K. Xian, H. Y. Woo, Z. Ge, J. Hou, Regulating Bulk-Heterojunction Molecular Orientations through Surface Free Energy Control of Hole-Transporting Layers for High-Performance Organic Solar Cells Adv. Mater.2019, 31, e1903441. (b) S. Liu, J. Yuan, W. Deng, M. Luo, Y. Xie, Q. Liang, Y. Zou, Z. He, H. Wu, Y. Cao, High-efficiency organic solar cells with low non-radiative recombination loss and low energetic disorder Nature Photon.2020, 14, 300-305.). limiting the photoelectric conversion efficiency of the organic solar cells and thus it is still challenging to further reduce the loss of the organic solar cells. In order to effectively improve the performance of organic solar cells and reduce the loss of organic solar cells, it is also necessary to optimize the structure of the non-fullerene acceptor material. The benzopyrazine and the derivative thereof have the remarkable advantages of weak electron deficiency property, rigid plane structure, easy chemical modification, multiple substitution positions and the like, so that the physicochemical property ((a) C. K. Sun, C. Zhu, L. Meng, Y. F. Li, A Quinoxaline-Based D–A Copolymer Donor Achieving 17.62% Efficiency of Organic Solar Cells Adv. Mater. 2021, 2104161. (b) Z. Y. Zhang, Q. Peng, D. B. Yang, Y. Q. Chen, Y. Huang, X. M. Pu, Z. Y. Lu, Q. Jiang, Y. Liu, Novel conjugated polymers with planar backbone bearing acenaphtho[1,2-b]quinoxaline acceptor subunit for polymer solar cells Synth. Met. 2013, 175, 21-29.). of the benzopyrazine and the derivative thereof is finely adjusted, and therefore