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CN-116056531-B - Perovskite film based on phosphate group micromolecules, preparation method thereof and photovoltaic cell application

CN116056531BCN 116056531 BCN116056531 BCN 116056531BCN-116056531-B

Abstract

The invention belongs to the technical field of perovskite solar cells, and discloses a perovskite film containing a phosphate group small molecule additive, a preparation method thereof and a trans-perovskite solar cell, which comprises the following steps of S1, dissolving metal halide and organic ammonium salt halide in an organic solvent to prepare a perovskite ABX 3 precursor solution, wherein A is Cs + , methylamine ions or formamidine ions, B is Pb 2+ , X is halogen ions including Cl ‑ ,Br ‑ ,I ‑ , S2, adding the phosphate group small molecule additive into the perovskite precursor solution of S1 to prepare a precursor solution containing small molecule doping, S3, depositing the precursor solution containing the small molecule doping of S2 on a conductive substrate, and annealing to obtain the perovskite film. The invention uses the phosphoric acid group micromolecule additive to realize the preparation of the trans-perovskite solar cell device without the hole transmission layer, and the cell device has excellent photovoltaic performance, the photoelectric conversion efficiency is more than 25 percent, and the cell device has excellent long-term stability.

Inventors

  • HE ZHUBING
  • LI ZHAONING
  • TAN QIN

Assignees

  • 南方科技大学

Dates

Publication Date
20260508
Application Date
20230110

Claims (8)

  1. 1. The preparation method of the perovskite film containing the phosphate group small molecule additive is characterized by comprising the following steps: S1, dissolving metal halide and organic ammonium salt halide in an organic solvent to prepare perovskite ABX 3 precursor solution, wherein A is Cs + , methylamine ion or formamidine ion, B is Pb 2+ , and X is halogen ion; S2, adding a phosphate group small molecule additive into the perovskite precursor solution of S1 to prepare a precursor solution containing small molecule doping; s3, depositing the precursor solution containing the small molecule doping of the S2 on a conductive substrate, and annealing to obtain a perovskite film; The phosphate-based small molecule additive is selected from one of the following structures: 。
  2. 2. The preparation method of claim 1, wherein the concentration of the phosphate-based small molecule additive in the precursor solution is 0.1-10 mg/mL.
  3. 3. The method according to claim 1, wherein the organic solvent is at least one selected from DMSO, DMF, NMP, THF and isopropanol.
  4. 4. The method of claim 1, wherein the conductive substrate is indium tin oxide conductive glass, fluorine doped tin dioxide conductive glass, flexible conductive substrate PET/ITO or PEN/ITO.
  5. 5. The method according to claim 1, wherein the deposition method is an anti-solvent assisted spin coating method, and the anti-solvent is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, 2-butanol, pentanol, isopentanol, ethylene glycol, glycerol, acetone, butanone, methyl ether, anisole, diethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, acetonitrile, acrylonitrile, chloroform, chlorobenzene, dichlorobenzene, toluene, meta-xylene, trimethylbenzene, benzotrifluoride, ethyl acetate, carbon tetrachloride, dichloroethane, carbon disulfide, and cyclohexane.
  6. 6. The method according to claim 1, wherein the annealing is performed in one step at 80 to 150 ℃ for 1 to 60 minutes or in two steps at 50 to 100 ℃ for 1 to 60 minutes and 90 to 150 ℃ for 1 to 60 minutes.
  7. 7. The perovskite film containing the phosphate group small molecule additive, wherein the perovskite film is prepared by the preparation method of any one of claims 1-6.
  8. 8. A trans-perovskite solar cell comprising a perovskite thin film and an electron transport layer, a metal electrode, overlying the perovskite thin film, the perovskite thin film as defined in claim 7.

Description

Perovskite film based on phosphate group micromolecules, preparation method thereof and photovoltaic cell application Technical Field The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite film based on phosphate group micromolecules, a preparation method thereof and a photovoltaic cell application. Background The solar energy is inexhaustible, and is an important clean renewable energy source. Solar cells are based on photovoltaic effect, and can directly convert solar energy into electric energy required by modern society, and are receiving extensive attention from the academia and industry. At present, the development of Perovskite Solar Cells (PSCs) is particularly attractive, the photoelectric conversion efficiency of a single device reaches 25.7%, and the perovskite solar cell is one of photovoltaic technologies with the most application prospect. In general, a Hole Transport Layer (HTL) is an essential component for obtaining a highly efficient stable PSC, and its role includes extracting holes generated from a perovskite light absorbing layer and transporting them to a corresponding electrode, to improve hole transport efficiency and reduce recombination loss during transport. In the trans PSC, the HTL serves as a growth substrate of the perovskite thin film, also has an important influence on the crystal quality of the perovskite thin film, and ultimately determines the photovoltaic performance of the perovskite solar cell. However, the introduction of the hole transport layer also brings about problems such as voltage loss due to interface level mismatch, poor wettability affecting perovskite thin film crystallization, high temperature treatment, and an increase in process complexity leading to an increase in manufacturing cost. Therefore, the development of perovskite solar cells with high efficiency and stability without a hole transport layer is of great importance. The prior art mainly focuses on the regulation and control of perovskite energy level to realize energy level matching with an ITO conductive glass substrate, but surface defects at an interface are not effectively passivated, so that energy loss of a device at the interface caused by carrier recombination is particularly serious, and the performance of the device is not kept for a long time. Disclosure of Invention The invention aims to provide a perovskite film based on a phosphate group micromolecule extrusion effect, aiming at a plurality of problems existing in the traditional hole transport layer, the invention utilizes the top-down crystallization extrusion process of the perovskite film to form a hole extraction interface at the lower interface to replace the traditional HTL, the introduced phosphate-based micromolecular additive achieves a synergistic passivation effect on bulk phase and interface defects through coordination interaction in the perovskite crystallization process, so that a high-efficiency stable trans-perovskite solar cell device is obtained. In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the perovskite film containing the phosphate group small molecule additive comprises the following steps: S1, dissolving metal halide and organic ammonium salt halide in an organic solvent to prepare perovskite ABX 3 precursor solution, wherein A is Cs +, methylamine ion or formamidine ion, B is Pb 2+, and X is halogen ion including Cl -,Br-,I-; S2, adding a phosphate group small molecule additive into the perovskite precursor solution of S1 to prepare a precursor solution containing small molecule doping; S3, depositing the precursor solution containing the small molecular doping of the S2 on a conductive substrate, and annealing to obtain the perovskite film. The stannous ion of the tin-based perovskite is easy to oxidize, and special requirements are brought to the additive, for example, the additive is preferably a reducing passivating agent, and the lead-based perovskite is not considered, so that the lead-based perovskite is taken as a suitable object. Further, the chemical structure of the phosphate group small molecule additive is G-L-A, wherein G is a functional group comprising phenoxazine, phenothiazine, acridine and derivatives thereof, L is a connecting group, A is an anchoring group, and the structure of the additive is as follows: Wherein R is (C1-C4) alkyl or halogen, L is (C2-C12) alkyl, A is phosphate group. Further, the phosphate-based small molecule additive is selected from one of the following structures: A preferred small molecule phosphate additive is 2BrDMAcPA (4- [2, 7-dibromo-9, 9-dimethylacridone-10 (9H) -yl ] butyl phosphate). Further, the concentration of the phosphate-based small molecule additive in the precursor solution is 0.1-10 mg/mL. Further, the addition of the phosphate-based small molecule additive to the perovskite precursor solution of S1 requires stirrin