CN-121974883-A - Thiophene secondary urethane derivative material and preparation method and application thereof

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to a thiophene secondary urethane derivative material, a preparation method and application thereof. The molecular structural general formula of the thiophene secondary urethane derivative material is shown as the specification, wherein R 1 ～R 5 is independently selected from hydrogen or halogen, and L 1 is methyl, ethyl or isopropyl. In the thiophene secondary urethane derivative material, sulfur atoms in thiophene rings can form strong coordination bonds with Pb 2+ which is not coordinated with the surface of perovskite, N-H bonds in secondary amino groups can form hydrogen bonds with iodine vacancies in perovskite, and ester groups can promote the solubility of molecules in an organic solvent and ensure the formation of uniform passivation layers, so that the high-efficiency and omnibearing passivation of the surface of a perovskite film and the defects of grain boundaries is realized, the non-radiative recombination probability of carriers is obviously reduced, and the problems of weak strength, limited passivation effect and poor long-term stability of devices of the conventional organic micromolecular passivating agent due to the interface with perovskite are solved.

Inventors

• DING YE
• SONG RUOQI
• ZHANG YUESHUAI

Assignees

• 中茂绿能科技(西安)有限公司
• 中茂光伏科技集团有限公司

Dates

Publication Date

20260505

Application Date

20260206

Claims (9)

1. 1. The thiophene secondary urethane derivative material is characterized by having a molecular structural formula as follows: ; Wherein R 1 ～R 5 is independently selected from hydrogen or halogen, and L 1 is methyl, ethyl or isopropyl.
2. 2. The thiophene secondary urethane derivative material according to claim 1, wherein R 1 ～R 5 is independently selected from hydrogen or F, respectively, and R 1 ～R 5 is not H at the same time.
3. 3. The thiophene secondary urethane derivative material according to claim 1, wherein the thiophene secondary urethane derivative material is any one of the following compounds: 。
4. 4. A method for preparing a thiophene secondary urethane derivative material according to any one of claims 1 to 3, comprising the steps of: taking a compound shown in a formula 1 and a compound shown in a formula 2 as raw materials, and performing a coupling reaction under the action of a first catalyst, a ligand, a first base and a first solvent to obtain a compound shown in a formula 3; taking a compound shown in a formula 3 and a compound shown in a formula 4 as raw materials, and performing a coupling reaction under the action of a second catalyst, a second base and a second solvent to obtain a thiophene secondary urethane derivative material shown in a formula 5; the synthetic route of the thiophene secondary urethane derivative material is as follows: 。
5. 5. The method for preparing a thiophene secondary urethane derivative material according to claim 4, wherein the molar ratio of the compound represented by formula 1 to the compound represented by formula 2 is 1:1 to 5; the molar ratio of the compound shown in the formula 3 to the compound shown in the formula 4 is 1:1-5.
6. 6. The method for producing a thiophene secondary urethane derivative material according to claim 4, wherein the first catalyst and the second catalyst are each independently selected from tris (dibenzylideneacetone) dipalladium or tetrakis (triphenylphosphine) palladium; the ligand is ‌ -dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl; The first base and the second base are each independently selected from cesium carbonate or potassium carbonate; The first solvent is toluene, and the second solvent is a mixed solvent of tetrahydrofuran and water.
7. 7. The method for preparing a thiophene secondary urethane derivative material according to claim 4, wherein the amount of the first catalyst is 3.1% -3.2% by mole of the compound represented by formula 1; the dosage of the ligand accounts for 5.3-5.4% of the mole percentage of the compound shown in the formula 1; The molar ratio of the compound shown in the formula 1 to the first alkali is 1:2-2.2; The second catalyst accounts for 4.9-5% of the compound shown in the formula 3 in mole percent; the molar ratio of the compound shown in the formula 3 to the second base is 1:2-2.2.
8. 8. The method for producing a thiophene secondary urethane derivative material according to claim 4, wherein the coupling reaction of the compound represented by formula 3 with the thiophene secondary urethane derivative material represented by formula 5 is carried out under reflux conditions.
9. 9. Use of a thiophene secondary urethane derivative material according to any one of claims 1-3 as an interface passivating agent for perovskite thin films in the preparation of perovskite solar cells.

Description

Thiophene secondary urethane derivative material and preparation method and application thereof Technical Field The invention relates to the technical field of organic photoelectric materials, in particular to a thiophene secondary urethane derivative material, a preparation method and application thereof. Background The perovskite solar cell has the outstanding advantages of high photoelectric conversion efficiency, low preparation cost and good solution processability, and becomes a research hotspot in the photovoltaic field, and has great industrial application potential. However, perovskite thin films are prone to generate a large number of surface defects, such as uncoordinated Pb 2+, iodine vacancies and the like, and grain boundary defects, which can cause severe carrier non-radiative recombination, so that open-circuit voltage and filling factor of a battery are remarkably reduced, and improvement of photoelectric conversion efficiency is restricted. Meanwhile, the existence of the defects can accelerate photodegradation, thermal degradation and water-oxygen degradation of the perovskite material, and seriously affect the long-term stability of the battery, which is a key problem to be solved in the process of perovskite solar cell industrialization. In order to solve the above problems, researchers have developed various defect passivation strategies, wherein organic small molecule passivating agents are widely focused due to the characteristics of strong structural adjustability, low preparation cost and good compatibility with perovskite. The organic micromolecule passivating agent reported at present mainly comprises amine compounds, carboxylic acids, thiols, urea compounds and the like, and the compounds realize the passivation effect through coordination or hydrogen bonding between functional groups and perovskite surface defects. However, the existing passivating agents generally have the problems that the interaction strength of part of the passivating agents and perovskite is insufficient, the passivating effect is limited, the solubility of part of the passivating agents is poor, a uniform passivating layer is difficult to form, the stability of part of the passivating agents is poor, the part of the passivating agents is easy to decompose or migrate in the long-term use process, and the stability of the battery is not remarkably improved. Disclosure of Invention The invention provides a thiophene secondary urethane derivative material, a preparation method and application thereof, and aims to solve the technical problems of limited passivation effect and poor long-term stability of devices caused by weak action strength with perovskite interfaces, poor solubility and insufficient chemical stability of the conventional organic micromolecule passivating agent. Thiophene secondary urethane derivatives are multifunctional organic molecules containing multiple functional groups such as thiophene rings, secondary amino groups, ester groups and the like, pi electrons of the thiophene rings can form pi-pi interaction with perovskite crystal lattices, N-H bonds of the secondary amino groups can form hydrogen bonds or coordination bonds with perovskite surface defects, and the ester groups can regulate the solubility of the molecules and the interfacial compatibility of the molecules with perovskite films. In view of the good conjugated electron effect of thiophene compounds and the strong coordination capability of sulfur atoms, the invention aims to apply thiophene secondary urethane derivatives as interface passivating agents of perovskite films to perovskite solar cells. In order to achieve the above object, the technical scheme of the present invention is as follows. The first aspect of the invention provides a thiophene secondary urethane derivative material, wherein the molecular structural general formula of the thiophene secondary urethane derivative material is shown as follows: ; Wherein R 1～R5 is independently selected from hydrogen or halogen, and L 1 is methyl, ethyl or isopropyl. Preferably, R 1～R5 is independently selected from hydrogen or F, and R 1～R5 is not simultaneously H. Preferably, the thiophene secondary urethane derivative material is any one of the following compounds: 。 The second aspect of the invention provides a preparation method of a thiophene secondary urethane derivative material, comprising the following steps: The method comprises the steps of taking a compound shown in a formula 1 and a compound shown in a formula 2 as raw materials, carrying out coupling reaction under the action of a first catalyst, a ligand, a first base and a first solvent to obtain a compound shown in a formula 3, carrying out coupling reaction under the action of a second catalyst, a second base and a second solvent to obtain a thiophene secondary urethane derivative material shown in a formula 5 by taking the compound shown in the formula 3 and the compound shown in a formula 4 as raw ma