CN-115666200-B - Preparation method of low-dimensional perovskite thin film and solar cell thereof

CN115666200BCN 115666200 BCN115666200 BCN 115666200BCN-115666200-B

Abstract

The invention relates to the technical field of perovskite solar cells and discloses a preparation method of a low-dimensional perovskite thin film and a solar cell thereof, wherein the preparation method of the low-dimensional perovskite thin film comprises the following steps of firstly, weighing p-fluorophenylethylamine iodide, iodomethylamine, lead iodide, iodoformamidine, methyl amine chloride and lead chloride, and dispersing the p-fluorophenylethylamine iodide, iodomethylamine, lead iodide, iodoformamidine, methyl amine chloride and lead chloride in a mixed solution composed of dimethylformamide and dimethyl sulfoxide to obtain a low-dimensional perovskite precursor solution; and secondly, dropwise adding the low-dimensional perovskite precursor solution on a substrate, rapidly spin-coating for 10-20s, and then carrying out reverse cooling annealing treatment on the low-dimensional perovskite precursor solution to obtain the low-dimensional perovskite film. The method rapidly forms the low-dimensional perovskite wet film through high-rotation-speed spin coating, and adopts the reverse-sequence cooling annealing process to treat the low-dimensional perovskite wet film, so that the low-dimensional perovskite wet film with a multiphase structure and vertical growth can be prepared, the repeatability is good, and the preparation cost of a battery device is reduced. The reverse sequence cooling annealing process disclosed by the invention is simple in preparation process and suitable for industrial production.

Inventors

XIE ZHONGQI
JIANG QINGSONG
WU YUE
WEI MENGYUAN
ZHAO YA
WANG CHUNXIANG
YANG XIAO
XUN WEI

Assignees

淮阴工学院

Dates

Publication Date: 20260505
Application Date: 20221216

Claims (10)

1. The preparation method of the low-dimensional perovskite film is characterized by comprising the following steps of: Firstly, weighing and mixing p-fluorophenylethylamine iodine, iodomethylamine, lead iodide, iodoformamidine, methyl amine chloride and lead chloride to obtain mixed powder, adding dimethylformamide and dimethyl sulfoxide into the mixed powder, and stirring to obtain a low-dimensional perovskite precursor solution; And secondly, dropwise adding the low-dimensional perovskite precursor solution on a substrate, spin-coating at a rotation speed of 5000-6000rpm for 10-20 seconds, and then performing reverse-order cooling annealing treatment to obtain the low-dimensional perovskite film, wherein the reverse-order cooling annealing treatment is that the low-dimensional perovskite film is heated for 4-10 seconds at 110-140 ℃ and then heated for 5-10 minutes at 70-90 ℃.
2. The method for producing a low-dimensional perovskite thin film according to claim 1, wherein in the first step, the stoichiometric molar ratio of lead iodide, methyl amine chloride and lead chloride is 10:1:1; And/or in the first step, the stoichiometric molar ratio of the p-fluorophenylethylamine iodine, the iodomethylamine, the iodoformamidine and the lead iodide is 2:0.9 (n-1): 0.1 (n-1): n, wherein n is the number of octahedral layers in the inorganic layer, and n is a natural number of more than 0 and less than or equal to 10.
3. The method for producing a low-dimensional perovskite thin film according to claim 1, wherein in the first step, the concentration of the low-dimensional perovskite precursor solution is 1 to 1.2mol/L.
4. The method for producing a low-dimensional perovskite thin film according to claim 1, wherein in the first step, the volume ratio of dimethylformamide to dimethyl sulfoxide is 95:5.
5. The method for producing a low-dimensional perovskite thin film according to claim 1, wherein in the first step, the stirring treatment is stirring at room temperature for 3 to 12 hours.
6. A perovskite solar cell is characterized by sequentially comprising ITO conductive glass, a hole transport layer, a low-dimensional perovskite film, an electron transport layer, a hole blocking layer and a metal electrode layer from bottom to top, wherein the low-dimensional perovskite film is prepared by the method of any one of claims 1-5.
7. The perovskite solar cell according to claim 6, wherein the hole transport layer is made of nickel oxide film, abbreviated as NiO x film; and/or the electron transport layer is made of PCBM; And/or the hole blocking layer is made of BCP; and/or the metal electrode layer is made of any one of silver and gold, and the thickness of the metal electrode layer is 60-100nm.
8. The perovskite solar cell of claim 6, wherein the hole transport layer is further provided with a PTAA modification layer.
9. A method of manufacturing a perovskite solar cell as claimed in any one of claims 6 to 8, comprising the steps of: Sequentially carrying out ultrasonic cleaning on the ITO conductive glass by using a cleaning agent, deionized water and alcohol, carrying out ozone treatment on the cleaned ITO conductive glass for 15-20 minutes, then dripping a NiO x solution on the ozone-treated ITO conductive glass, spin-coating at a rotating speed of 4000-5000rpm for 25-35 seconds, and annealing the spin-coated film at 230-280 ℃ for 40-60 minutes to obtain the hole transport layer; preparing a low-dimensional perovskite film on the hole transport layer; Step three, dripping PCBM solution on the low-dimensional perovskite film, spin-coating at a rotating speed of 2000-3000rpm for 55-65 seconds, and annealing the spin-coated film at 80-90 ℃ for 8-12 minutes to obtain the electron transport layer; Dripping BCP solution on the electron transport layer, spin-coating at 3000-4000rpm for 25-35 seconds, and annealing the spin-coated film at 80-90 ℃ for 8-12 minutes to obtain the hole blocking layer; and fifthly, vacuum thermal evaporation of a metal electrode layer on the hole blocking layer to obtain the perovskite solar cell.
10. The method of manufacturing a perovskite solar cell according to claim 9, wherein in the second step, a PTAA modification layer is first formed on the hole transport layer, and then a low-dimensional perovskite thin film is formed on the PTAA modification layer; Wherein a PTAA modifying layer is prepared on the hole transport layer by the following specific steps: and dripping PTAA solution on the hole transport layer, spin-coating at a rotating speed of 4500-5500rpm for 55-65 seconds, and annealing the spin-coated film at 90-110 ℃ for 8-12 minutes to obtain the PTAA modification layer.

Description

Preparation method of low-dimensional perovskite thin film and solar cell thereof Technical Field The invention relates to the technical field of perovskite solar cells, in particular to a preparation method of a low-dimensional perovskite thin film and a solar cell thereof. Background The organic-inorganic hybrid perovskite material plays a role in the development of solar cells because of the advantages of high light absorption, low binding energy, high defect tolerance, high carrier mobility, long carrier diffusion length and the like. At present, the photoelectric conversion efficiency of three-dimensional perovskite solar cell authentication reaches 25.7%, but the low stability of the three-dimensional perovskite solar cell authentication is required to be further optimized and improved. Thus, the stability of three-dimensional battery devices has hindered its commercialization process. Interestingly, low-dimensional perovskite solar cells show very good stability due to their hydrophobic nature of the organic spacer cations, and thus have a good commercial application prospect. The low-dimensional perovskite film is a semiconductor material with a multiple quantum well structure due to the existence of a multiphase structure. The multi-quantum well structure has quantum confinement effect, so that the low-dimensional perovskite material has the defects of low absorption coefficient, low carrier mobility, high exciton binding energy and the like, and the photovoltaic performance of the low-dimensional perovskite solar cell is poor. Research shows that regulating and controlling the multiphase structure in the low-dimensional perovskite film is one of simple and effective methods for improving the photovoltaic performance of battery devices. When the multiphase structure in the low-dimensional perovskite film is vertical to the growth of the substrate, the carrier separation, transmission and extraction are facilitated, and the photovoltaic performance of the battery device is effectively improved. The growth mode of the multiphase structure is regulated and controlled by strategies such as additive engineering, solvent engineering, heat treatment engineering and the like. The heat treatment engineering strategy generally comprises continuous annealing treatment, sequential heating annealing treatment, thermal spin coating treatment and other processes. The continuous annealing process is a common annealing process, so that the multiphase structure in the low-dimensional perovskite film is arranged in disorder, and the short-circuit current density in the battery device is mainly reduced. The sequential temperature-increasing annealing process, while promoting grain growth of the low-dimensional perovskite, does not promote vertical growth of the multiphase structure in the low-dimensional perovskite. Through verification, the thermal spin coating process can effectively regulate and control the vertical growth of the multiphase structure in the low-dimensional perovskite, and is beneficial to improving the short-circuit current density of the battery device. But the thermal spin coating process has a problem in that the repeatability is difficult to control. The invention patent CN 108183166B discloses a fluctuation annealing process and a perovskite solar cell prepared by the process, and the fluctuation thermal annealing process is adopted to enable perovskite crystal grains to grow fast, slow, fast and slow, so that the perovskite active layer crystal grains can grow, and in the link of slow growth, a self-assembly process can be formed among the perovskite crystal grains, so that the contact between the crystal grains is more compact and uniform. However, the wave thermal annealing process provided by the invention is effective for the three-dimensional perovskite film, but is not applicable for the low-dimensional perovskite film. In the process of forming the low-dimensional perovskite thin film, multiphase structures with different n values are easy to form quickly, and if the high temperature time is long, the low-dimensional perovskite thin film can be seriously damaged. Therefore, it is the subject of our research to find an effective way to grow low-dimensional perovskite thin films efficiently. Disclosure of Invention Aiming at the problems in the prior art, the invention provides the preparation method of the low-dimensional perovskite film and the solar cell thereof, which rapidly form the low-dimensional perovskite wet film through high-rotation-speed spin coating and adopt the reverse sequence cooling annealing process for treatment, thereby being beneficial to preparing the low-dimensional perovskite film with a multiphase structure for vertical growth, having good repeatability and reducing the preparation cost of a cell device. The reverse sequence cooling annealing process disclosed by the invention is simple in preparation process and very suitable for industrial production. The in