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CN-122011030-A - Organic semiconductor material based on asymmetric fused heterocycle and preparation method and application thereof

CN122011030ACN 122011030 ACN122011030 ACN 122011030ACN-122011030-A

Abstract

The invention discloses an organic semiconductor material based on asymmetric fused heterocycle, a preparation method and application thereof, belonging to the technical field of perovskite solar cells, the self-assembled monolayer organic semiconductor material provided by the invention uses condensed rings as functional groups, and can promote SAM molecules to form more ordered and compacter-packed monolayers. The pinhole defect is reduced, and the exposed point on the substrate can be effectively reduced by better coverage. In addition, the S-doped source can effectively regulate and control the surface work function and the interface dipole, so that the transmission of carriers is promoted, the non-radiative recombination of the surface is inhibited, the energy conversion efficiency is effectively improved, and the photoelectric conversion efficiency of the perovskite solar cell exceeds 26%. In addition, the material obviously improves the long-term stability of the device, prolongs the service life, provides a new technical scheme for the high-efficiency stable perovskite solar cell, and has wide application prospect.

Inventors

  • CHEN CUIMEI
  • ZHANG CHENG

Assignees

  • 宿迁鸿锐科技有限公司

Dates

Publication Date
20260512
Application Date
20260113

Claims (9)

  1. 1. An organic semiconductor material based on an asymmetric fused heterocycle, which is characterized in that the chemical structural formula is shown as the following formula (4) or formula (8): 。
  2. 2. The method for preparing an organic semiconductor material based on an asymmetric fused heterocycle as set forth in claim 1, comprising the steps of: (1) Using a benzocarbazole compound AH as an initial raw material to perform a coupling reaction with 1, 4-dibromobutane to generate a compound 2 or 6; (2) Coupling the compound 2 or 6 with triethyl phosphite to generate a compound 3 or 7; (3) Subjecting compound 3 or 7 to hydrolysis reaction to give compound 4 or 8 as the final product; the initial raw material benzocarbazole compound AH is selected from one of the following compounds: The synthetic routes for compounds 4 or 8 are shown below, respectively: 。
  3. 3. The preparation method of the organic semiconductor material based on the asymmetric fused heterocycle, which is characterized in that in the step (1), a compound AH, 1, 4-dibromobutane, tetrabutylammonium bromide, potassium hydroxide and water are uniformly stirred and mixed, and reacted for 5-8 hours at 50-80 ℃ to generate a compound 2 or 6.
  4. 4. The method for preparing an organic semiconductor material based on an asymmetric fused heterocycle, which is characterized in that in the step (1), the molar ratio of the compound AH, the 1.4-dibromobutane, the tetrabutylammonium bromide and the potassium hydroxide is 1:18-21:0.01-0.12:10-12, and the dosage ratio of the potassium hydroxide to the water is 1 g:0.1-1.2 mL.
  5. 5. The method for preparing the organic semiconductor material based on the asymmetric fused heterocycle, which is characterized in that in the step (2), the compound 2 or 6 is dissolved in triethyl phosphite under the protection of argon, and the reaction is carried out for 10-15 hours at 150-180 ℃ to generate the compound 3 or 7.
  6. 6. The method for preparing an organic semiconductor material based on an asymmetric fused heterocycle according to claim 5, wherein in the step (2), the molar ratio of the compound 2 or 6 to the triethyl phosphite is 1:12-20.
  7. 7. The method for preparing the organic semiconductor material based on the asymmetric fused heterocycle, which is characterized in that in the step (3), under the protection of argon, the compound 3 or 7 and trimethyl bromosilane are dissolved in 1, 4-dioxane, the reaction is carried out at room temperature for 12-18 h, the solvent is removed by reduced pressure distillation, the obtained solid is added into methanol and is continuously reacted for 2-5 hours, and the precipitated solid is filtered and dried to obtain the compound 4 or 8.
  8. 8. The method for preparing an organic semiconductor material based on an asymmetric fused heterocycle as claimed in claim 7, wherein in the step (3), the molar ratio of the compound 3 or 7 to trimethylbromosilane is 1:7-11.
  9. 9. The use of an organic semiconductor material based on an asymmetric fused heterocycle in the preparation of a perovskite solar cell with an inverted structure according to claim 1.

Description

Organic semiconductor material based on asymmetric fused heterocycle and preparation method and application thereof Technical Field The invention belongs to the technical field of perovskite solar cells, relates to preparation of an organic semiconductor material, and particularly relates to application of an organic semiconductor material based on an asymmetric fused heterocycle in an inverted structure perovskite solar cell. Background Perovskite solar cells are the most promising new generation of photovoltaic technology, and the commercialization process is highly dependent on the synergistic improvement of device efficiency and long-term stability. In the cell structure, the hole transport layer plays a decisive role in the performance index. The traditional doped hole transport material is easy to cause the performance attenuation of devices due to the additive, and has difficulty in meeting the industrialization requirement. Therefore, the self-assembled monolayer material realizes high-efficiency hole extraction without doping by forming an ultrathin compact molecular coating layer, and provides a brand new solution for overcoming the stability bottleneck. Among the many SAM materials, a hole transporting layer based on [4- (9H-carbazol-9-yl) butyl ] phosphonic acid (4 PACz) has become an important reference in this field. Carbazole groups in the molecular structure provide hole transport characteristics, and butyl phosphonic acid chains can ensure anchoring and self-assembly capabilities. The battery using 4PACz as the hole transport layer is obviously superior to the traditional material in efficiency and stability, and the performance standard pole of the SAM material is established. However, with the deep research, 4PACz reveals two key limitations, namely firstly, the electronic characteristics of a molecular skeleton are still not optimal with the energy level matching between an advanced perovskite light absorption layer, interface energy loss exists, the further improvement of open-circuit voltage is limited, and secondly, a single carbazole electron donating group and alkyl chain connection mode has obvious defects in the aspects of interface dipole regulation and defect passivation capability, so that the inhibition effect on non-radiative recombination of a perovskite interface is limited. Therefore, a novel hole transport material capable of fundamentally breaking through the performance bottleneck of 4PACz on the basis of inheriting the undoped and high-stability advantages of the SAM material is urgently needed in the field. The ideal new material should have more accurate energy level matching to minimize interface loss, stronger intramolecular charge transfer characteristics to promote hole extraction efficiency, and more excellent interface passivation capability to inhibit carrier recombination. The invention aims to provide the novel self-assembled monolayer hole transport material exceeding the performance level of 4PACz, and the cooperative optimization of interface energy level regulation and defect passivation is realized through innovative molecular structure design, so that the performance of the perovskite solar cell is promoted to advance to the theoretical limit. Disclosure of Invention Aiming at the defects of the prior art, the invention provides an organic semiconductor material based on an asymmetric fused heterocycle, and the self-assembled monolayer organic semiconductor material provided by the invention uses fused rings as functional groups, so that SAM molecules can be promoted to form more ordered and compacter-packed monolayers. The pinhole defect is reduced, and the exposed point on the substrate can be effectively reduced by better coverage. In addition, O, S hetero sources are introduced to effectively regulate and control the surface work function and interface dipole, so that the transmission of carriers is promoted, the non-radiative recombination on the surface is inhibited, and the energy conversion efficiency is effectively improved. The invention is realized by the following technical scheme: In a first aspect, the invention provides an organic semiconductor material based on an asymmetric fused heterocycle, wherein the chemical structural formula is as follows: 。 in a second aspect, the present invention provides a method for preparing the above asymmetric fused heterocycle based organic semiconductor material, comprising the steps of: (1) Using a benzocarbazole compound AH as an initial raw material to perform a coupling reaction with 1, 4-dibromobutane to generate a compound 2 or 6; (2) Coupling the compound 2 or 6 with triethyl phosphite to generate a compound 3 or 7; (3) Subjecting compound 3 or 7 to hydrolysis reaction to give final product 4 or 8; the initial raw material benzocarbazole compound AH is selected from the following compounds: The synthetic routes for compounds 4 or 8 are shown below, respectively: 。 In the step (1), compound AH, 1