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CN-121985717-A - Benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivative thereof for passivating perovskite layer, and preparation and application thereof

CN121985717ACN 121985717 ACN121985717 ACN 121985717ACN-121985717-A

Abstract

Benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivative thereof passivate a perovskite layer, and preparation and application thereof, and belong to the technical field of perovskite solar cells. And forming an interface modification layer on the surface of the perovskite through a solution spin coating process, so as to realize in-situ passivation. The ammonium salt and the derivative thereof can effectively passivate the surface defects of the perovskite film, such as passivating uncoordinated Pb 2+ and filling iodine vacancies, so as to inhibit non-radiative recombination of a perovskite layer, promote extraction of carriers, and further improve the open circuit voltage and filling factor of the perovskite solar cell. Meanwhile, the large-volume interval cations can be gathered at the grain boundary, so that the quality of the grain boundary is improved, and the ion migration is inhibited. In addition, the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and the derivative thereof are used as passivation layers, so that the erosion of moisture to the perovskite layer can be blocked, and the humidity stability of the device is obviously enhanced. The method improves the photoelectric performance and stability of the perovskite solar cell, and is suitable for preparing the perovskite solar cell with high efficiency and stability.

Inventors

  • YU ZE
  • Yang Xuemi

Assignees

  • 大连理工大学

Dates

Publication Date
20260505
Application Date
20260127

Claims (9)

  1. 1. The three-dimensional perovskite layer modified by the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and the derivative thereof is characterized in that the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and the derivative thereof passivate the defects of a perovskite film in situ, and the structural general formula of the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt is as follows: ; Wherein A 1 、A 2 is any one of oxygen, sulfur and selenium, R 1 -R 12 is any one of hydrogen, alkyl chain of C 1 -C 8 , hydroxyl, alkoxy, dimethylamino, trifluoromethyl, trifluoromethoxy, halogen atom, formyl, acetyl, nitro, cyano, phenyl, biphenyl, naphthyl and amido, n is an integer of 1-8, and X is any one of halogen atoms.
  2. 2. The three-dimensional perovskite layer modified by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 1, wherein the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt is selected from the following structures: ; ; 。
  3. 3. The three-dimensional perovskite layer modified by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 1 is characterized in that the preparation method of the three-dimensional perovskite layer comprises the following steps: And dissolving benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof in an organic solvent to obtain an ammonium salt solution, spin-coating the ammonium salt solution on the surface of 3D perovskite to obtain a perovskite layer passivated by ammonium salt, wherein the structural general formula of the 3D perovskite layer is Cs (FA, MA) 1-x PbI 3-y B y , wherein FA is formamidine cation CH (NH 2 ) 2+ , MA is methylamine cation CH 3 NH 3 + , x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.6.
  4. 4. The three-dimensional perovskite layer modified by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 3, wherein the concentration of the ammonium salt solution is 1-6 mg/mL, and the organic solvent is one or more mixed solvents of isopropanol, chloroform, acetonitrile, toluene and chlorobenzene.
  5. 5. The three-dimensional perovskite layer modified by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 4, wherein the spin-coating speed is 3000-6000 rpm, the spin-coating time is 25-40 s, and the annealing temperature after spin-coating is 80-120 ℃.
  6. 6. A perovskite solar cell with in-situ passivation of benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof is characterized in that the cell comprises the three-dimensional perovskite layer according to any one of claims 1-5.
  7. 7. The method for preparing the perovskite solar cell with the in-situ passivation of the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and the derivatives thereof according to claim 6 is characterized by comprising the following steps: (1) Cleaning the conductive glass substrate; (2) Preparing an electron transport layer on the cleaned glass substrate by a chemical deposition method; (3) Spin-coating perovskite precursor liquid on the electron transport layer, annealing, and obtaining a perovskite film passivated by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to the steps; (4) Spin-coating a hole transport layer on the three-dimensional perovskite layer of any one of claims 1-3, the components of the hole transport layer comprising Sipro-ome tad solution, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]; (5) A metal electrode was deposited by vacuum on the perovskite thin film spin-coated with the hole transport layer.
  8. 8. The method for preparing a perovskite solar cell with in-situ passivation of benzo-penta-aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 7, wherein the Sipro-OMeTAD solution in the step (4) comprises 2,2', 7' -tetra-2, 2', 7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, lithium bis (trifluoromethane) sulfonyl imide, 4-tert-butylpyridine and tris [ 4-tert-butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt [ III ] (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methane sulfonyl amide salt, and the solvent of the solution is chlorobenzene or acetonitrile.
  9. 9. The method for preparing a perovskite solar cell with in-situ passivation of benzo-penta-aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof according to claim 8, wherein in the step (5), the electrode is gold, silver or copper electrode.

Description

Benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivative thereof for passivating perovskite layer, and preparation and application thereof Technical Field The invention belongs to the technical field of perovskite solar cells, and relates to an in-situ passivation method of a perovskite film and a preparation process of the perovskite solar cell. Background Solar energy is used as a renewable energy source, and can be converted into electric energy through a solar cell. The development of solar cells has been three generations, wherein perovskite solar cells are subordinate to third generation solar cells, and the perovskite solar cells are widely focused by the scientific community due to the advantages of adjustable band gap, simple preparation, low cost and the like. The mixed perovskite thin film prepared by the solution method generally has a large number of defects, the defects can form high-density deep level trap states, and under the condition of higher carrier concentration, the deep level defects can cause obvious non-radiative recombination, so that the open circuit voltage and the filling factor of the device are reduced, and the photoelectric conversion efficiency and the long-term stability of the device are severely restricted. Therefore, it is important to develop an effective defect passivation strategy. Wherein, large-size organic cations containing alkyl or aryl ammonium halide are used as passivating agents, and the passivating agent has simple and convenient operation and remarkable passivating effect, thus becoming one of the most widely used passivating methods at present. First, the hydrophobicity of the alkyl chain effectively insulates the perovskite layer from moisture attack. Secondly, large-volume cations cannot enter perovskite crystal lattices due to size limitation, are selectively adsorbed on the surface or crystal boundary of the perovskite, and cover uncomplexed Pb 2+ or halogen vacancy defects, so that formation of non-radiative recombination centers is inhibited, and meanwhile, positive charges of the large cations can neutralize surface negative charges and reduce defect state density. In addition, the accumulation of such cations at grain boundaries can block the migration paths of Pb 2+ and I -, reducing hysteresis effects and performance decay caused by ion migration. The organic ammonium salt is typically an insulator, which impedes carrier migration at the interface between the perovskite layer and the transport layer, increases series resistance, reduces the fill factor of the device, and efficiency, and the energy level of a portion of the ammonium salt does not match the perovskite layer or the transport layer, resulting in a decrease in charge extraction efficiency, and thus a reduction in short circuit current. Therefore, the design and application of the functionalized ammonium halide salt molecular passivating agent have important significance for improving the performance of the perovskite solar cell. Disclosure of Invention The invention provides a method for forming an in-situ passivation layer on a three-dimensional perovskite and application of the method to a perovskite solar cell. The method adopts benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof as passivation materials, can effectively passivate defects in perovskite films, inhibit carrier non-radiative recombination caused by deep level traps, remarkably improve photoelectric conversion efficiency and long-term stability of devices, and provide a feasible path for commercial application of the devices. In order to solve the problems of defects and the like in the perovskite thin film, the invention adopts the technical scheme that the three-dimensional perovskite layer modified by benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof is provided, the defects of the perovskite thin film are passivated in situ by the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof, and the structural general formula of the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt is as follows: Wherein A 1、A2 is any one of oxygen, sulfur and selenium, R 1-R12 is any one of hydrogen, alkyl chain of C 1-C8, hydroxyl, alkoxy, dimethylamino, trifluoromethyl, trifluoromethoxy, halogen atom, formyl, acetyl, nitro, cyano, phenyl, biphenyl, naphthyl and amido, n is an integer of 1-8, and X is any one of halogen atoms. Further, the benzo five-membered aromatic heterocyclic carbazolyl ammonium salt has the following structure: further, the preparation method of the three-dimensional perovskite layer comprises the following steps: And dissolving benzo five-membered aromatic heterocyclic carbazolyl ammonium salt and derivatives thereof in an organic solvent to obtain an ammonium salt solution, spin-coating the ammonium salt solution on the surface of 3D perovskite to obtain