CN113675345A - Perovskite light absorption layer thin film and surface defect passivation method thereof - Google Patents

Perovskite light absorption layer thin film and surface defect passivation method thereof Download PDF

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CN113675345A
CN113675345A CN202110965420.3A CN202110965420A CN113675345A CN 113675345 A CN113675345 A CN 113675345A CN 202110965420 A CN202110965420 A CN 202110965420A CN 113675345 A CN113675345 A CN 113675345A
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perovskite
thin film
film
light absorption
absorption layer
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殷立雄
李潞瑶
韩浪
刘长青
黄剑锋
郭瑶
李书航
赵津
陈禹飞
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Shaanxi University of Science and Technology
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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Abstract

The invention discloses a perovskite light absorption layer thin film and a method for passivating surface defects thereof, comprising the following steps of: 1. will PbI2、FAI、PbBr2Dissolving MABr and CsIb in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution; 2. dissolving pyrrole in an organic solvent to prepare an additive solution; step 3, dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s‑1Is accelerated to a rotational speed of 1000rpm and rotated for 10s, and then at 2000rpm s‑1Accelerating the acceleration to 5500rpm and rotating for 25s to prepare the perovskite thin film; quickly dripping the additive solution obtained in the step (2) on the surface of the perovskite thin film in the first 5s after the high-speed rotation is stopped; drying in argon atmosphere to obtain the perovskite thin film. Pyrrole additive is introduced to the surface of the perovskite light absorption layer film, so that the surface defect density of the perovskite light absorption layer film is reduced and the perovskite light absorption layer film is provided with pyrrole additiveThe surface forms a hydrophobic layer.

Description

Perovskite light absorption layer thin film and surface defect passivation method thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite light absorption layer thin film and a surface defect passivation method thereof.
Background
In the face of the increasingly serious problem of exhaustion of traditional fossil energy, the search for and development of novel clean and renewable energy sources becomes a new mission and challenge for researchers in the twenty-first century. At present, researchers have put more and more attention on the development and utilization of new energy sources such as solar energy, wind energy, water energy, tidal energy, geothermal energy, biomass energy and the like. For effective development and utilization of solar energy, a reliable means is mainly to design and manufacture a solar cell device and utilize the photovoltaic effect of a semiconductor to realize conversion of solar energy into electric energy.
Since the last century, through a great deal of experimental exploration, the first generation silicon-based solar photovoltaic devices based on p-n junctions came out, and the theoretical basis related to the first generation silicon-based solar photovoltaic devices is gradually improved along with the increasing maturity of the device manufacturing technology. However, the development of silicon-based solar energy has not been able to satisfy the higher pursuit of people, and the thin film, high quality, low cost, simple process and the like become the direction of people to further pursue.
Perovskite solar cells have many advantages as third generation solar cells compared to conventional silicon-based solar cells. The preparation method has the advantages of low cost, simple preparation process, solution processing and extremely rapid development, realizes the rapid leap of the photoelectric conversion efficiency from 3.8% to 25.5% in short decades, and becomes the object of attention and research of a plurality of researchers.
However, despite this, perovskite solar cells are not yet commercially available. One of the main reasons for this is that the light absorbing layer film of the device has defects. In the process of preparing the thin film by the solution method, a large number of defects such as Pb2+ defects, Pb-I reverse site defects, organic cation-related defects and the like are generally generated on the grain boundary and the surface of the thin film, and the defects serve as centers of charge recombination, so that serious non-radiative recombination and interface recombination are caused, and the performance of the device is prevented from being further improved. In order to solve the problems, additives are usually introduced in the film preparation process, and the defects of under-coordinated ions on the surface and the grain boundary of the perovskite film are passivated through coordination bonds and ionic bonds.
Liu et al, 2019, entitled "perovskite: an additive for enhancing the efficacy and reactivity of perovskite nanoparticles" of Journal of Materials Chemistry A, first reported modifying defects of perovskite thin films with Pyrrole, by introducing Pyrrole additives into perovskite precursor solutions, such that Pyrrole forms coordination bonds with perovskite precursor components, thereby suppressing Pb at grain boundaries inside perovskite thin films2+Formation of defects and organic cation related defects. However, the method is not enough to modify the defects at the grain boundary, and the defect density on the surface of the perovskite thin film is far higher than the defect density in the thin film, thus seriously affecting the efficiency of the device.
Therefore, there is a need to improve the film preparation process, and try to introduce additive molecules into the surface of the perovskite film to passivate the surface defects of the perovskite film, so as to obtain a high-quality perovskite film, and further improve the photoelectric conversion efficiency and stability of the perovskite solar cell.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to introduce the pyrrole additive into the surface of the perovskite light absorption layer film, so that the defect density of the surface of the film can be reduced, a hydrophobic layer is formed on the surface of the film, the corrosion of moisture on the film is delayed, and the high-quality perovskite light absorption layer film is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
step 1, 0.460-0.530 g of PbI20.170-0.190 g of FAI and 0.075-0.085 g of PbBr20.015-0.025 g of MABr and 0.015-0.020 g of CsI are dissolved in 800 under stirringPreparing perovskite precursor solution from mixed solvent of mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO);
step 2, dissolving pyrrole into an organic solvent to prepare a solution with a concentration of 0.1-30.0 mmol L-1The surface additive solution of (1);
step 3, uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step (2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying in an argon atmosphere to obtain the surface modified perovskite light absorption layer film.
The stirring in the step 1 is continuously carried out for more than 4.5 hours.
The organic solvent in the step 2 is at least one of isopropanol, ethanol, diethyl ether, anisole, ethyl acetate, toluene, chlorobenzene or trichlorotoluene.
And 3, drying in an argon atmosphere, and annealing at 70-160 ℃ for 1-120 minutes.
After the surface defect passivation of the perovskite light absorption layer film obtained by the method for surface defect passivation of the perovskite light absorption layer film, the stable photoluminescence peak intensity of the film near 766nm is reduced, the peak position blue shift is realized, the surface defect density of the light absorption layer film is reduced, and the quality of the light absorption layer film is obviously improved.
After surface defect passivation, the light absorption characteristics of the light absorption layer film in the wavelength range of 500-800 nm are obviously enhanced, and the light absorption layer film has good sunlight utilization rate.
After the pyrrole additive is introduced, a hydrophobic layer is formed on the surface of the light absorption layer film, so that the corrosion of water to the perovskite battery is delayed, and the light absorption layer film has good humidity stability.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention firstly prepares the calcium and the titaniumUniformly dripping the ore precursor solution on an FTO conductive glass substrate, and then carrying out spin coating by using a spin coater to prepare the perovskite light absorption layer film, wherein the core is that organic solvent for dissolving pyrrole is quickly dripped on the surface of the perovskite light absorption layer film 5s before the high-speed spin coating of the spin coater, pyrrole molecules are dynamically added to the surface of the perovskite light absorption layer film by the spin coating, and the perovskite light absorption layer film with passivated surface defects is obtained after drying. The perovskite thin film is in an intermediate state from the beginning of spin coating to the drying, and pyrrole with N atoms and Pb in the perovskite component is introduced on the surface of the perovskite thin film through an organic solvent2+The interaction forms N-Pb chemical bond, effectively inhibits the surface Pb of the perovskite in the crystallization process2+The formation of defects improves the film quality, and the light absorption performance is obviously improved. Meanwhile, pyrrole forms a uniform hydrophobic layer on the surface of the perovskite thin film, so that water molecules in the air are prevented from corroding the thin film, and the humidity stability of the thin film is enhanced.
2. At present, a plurality of methods for introducing additives into the surface of the perovskite thin film to passivate defects comprise a spin coating method, a spraying method, a blade coating method and the like. Compared with other methods, the spin coating method is easy to realize small amount and uniform coverage of additive molecules on the surface of the film, and the addition amount of the additive can be effectively controlled. When the surface modification is generally performed by adopting a spin coating method, in order to avoid dissolution or deterioration of the perovskite due to a solvent in an additive solution, the method is generally divided into two steps, namely, the perovskite is firstly spin-coated, and after the perovskite is heated for 10-15 min on a heating table, the additive layer is spin-coated. According to the invention, the surface additive solution is dynamically dripped in the perovskite spin coating process, and the spin coating machine is used for spin coating for 5s at a high speed, so that the time of the additive pyrrole acting on the surface of the perovskite film is advanced, meanwhile, the time of the additive solution staying on the film is very short, and the solvent in the surface additive solution is ensured not to generate negative influence on the perovskite.
After surface defect passivation, the measured stable photoluminescence peak intensity of the film near 766nm is reduced, the peak position is blue-shifted, the surface defect density of the light absorption layer film is reduced, the quality of the light absorption layer film is obviously improved, the light absorption characteristic of the light absorption layer film in the wavelength range of 500-800 nm is obviously enhanced, and the light absorption layer film has good sunlight utilization rate. After the pyrrole additive is introduced, the hydrophobic layer is formed on the surface of the light absorption layer film, so that the corrosion of water to the perovskite battery is delayed, and the light absorption layer film has good humidity stability.
Assembling the perovskite solar cell. Firstly, spin-coating TiO on cleaned FTO/Glass substrate2Annealing the electron transport layer for 30min at 450 ℃ by adopting a muffle furnace; then, the substrate was transferred into a glove box, and the perovskite solar cell light absorption layer and 2,2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group prepared according to the present invention were spin-coated under an argon atmosphere, respectively]-a 9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer; and finally, moving the substrate out of the glove box, oxidizing for 18h, coating a carbon electrode by adopting a blade coating method, and assembling the perovskite solar cell.
The assembled perovskite solar cell device adopts the perovskite thin film with passivated surface defects as the light absorption layer of the device, so that the photoelectric conversion efficiency of the perovskite solar cell device is further improved, and the humidity stability of the device is obviously enhanced.
Drawings
FIG. 1: XRD spectrums of the perovskite thin films prepared in the embodiment 4 and the comparative example 1 of the invention;
FIG. 2: SEM photograph a of the perovskite thin film prepared in comparative example 1 of the present invention;
FIG. 3: SEM photograph b of the perovskite thin film prepared in the embodiment 4 of the invention;
FIG. 4: the perovskite thin films prepared in the embodiments 1 to 5 of the invention have UV-vis absorption spectra;
FIG. 5: the perovskite thin film prepared in the embodiment 4 of the invention has fluorescence excitation spectrum;
FIG. 6: the perovskite thin films prepared in the embodiment 4 and the comparative example 1 of the invention have fluorescence emission spectra;
FIG. 7: the photograph of the contact angle of the perovskite thin film prepared in comparative example 1 of the present invention;
FIG. 8: the photograph of the contact angle of the perovskite thin film prepared in the embodiment 1 of the invention;
FIG. 9: the photograph of the contact angle of the perovskite thin film prepared in the embodiment 2 of the invention;
FIG. 10: the photograph of the contact angle of the perovskite thin film prepared in the embodiment 3 of the invention;
FIG. 11: the photograph of the contact angle of the perovskite thin film prepared in the embodiment 4 of the invention;
FIG. 12: the photograph of the contact angle of the perovskite thin film prepared in the embodiment 5 of the invention;
FIG. 13: the perovskite thin film prepared in the embodiments 1-5 and the comparative example 1 of the invention is applied to a Photoelectric Conversion Efficiency (PCE) statistical graph of a perovskite solar cell device;
FIG. 14: short-circuit current density (J) of perovskite thin film prepared in inventive examples 1-5 and comparative example 1 applied to perovskite solar cell devicesc) A statistical chart;
FIG. 15: application of perovskite thin films prepared in examples 1 to 5 and comparative example 1 of the present invention to open circuit voltage (V) of perovskite solar cell deviceoc) A statistical chart;
FIG. 16: the perovskite thin film prepared in the embodiments 1-5 and the comparative example 1 of the invention is applied to a Fill Factor (FF) statistical chart of a perovskite solar cell device;
FIG. 17: photographs of perovskite thin films prepared in example 4 and comparative example 1 before and after the humidity aging test were taken.
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1
(1) 0.507g of PbI2、0.172g FAI、0.081g PbBr20.023g of MABr and 0.020g of CsI are dissolved in a mixed solvent of 800mLN, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Adding pyrrole into chlorobenzene to prepare into L with the concentration of 3mmol-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 100 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 2
(1) 0.507g of PbI2、0.172g FAI、0.081g PbBr20.023g of MABr and 0.020g of CsI are dissolved in a mixed solvent of 800mLN, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Adding pyrrole into chlorobenzene to prepare into L with the concentration of 6mmol-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 100 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 3
(1) 0.507g of PbI2、0.172g FAI、0.081g PbBr20.023g of MABr and 0.020g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5h to prepare a perovskite precursor solution.
(2) Adding pyrrole into chlorobenzene to prepare into L with the concentration of 9mmol-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 100 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 4
(1) 0.507g of PbI2、0.172g FAI、0.081g PbBr20.023g of MABr and 0.020g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5h to prepare a perovskite precursor solution.
(2) Adding pyrrole into chlorobenzene to prepare L with the concentration of 12mmol-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 100 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 5
(1) 0.507g of PbI2、0.172g FAI、0.081g PbBr20.023g of MABr and 0.020g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5h to prepare a perovskite precursor solution.
(2) Adding pyrrole into chlorobenzene to prepare L with the concentration of 15mmol-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 100 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 6
(1) 0.46g of PbI2、0.18g FAI、0.078g PbBr20.017g of MABr and 0.016g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and the mixture is stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Pyrrole was added to isopropanol to give a concentration of 0.1mmol L-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 70 ℃ and carrying out annealing treatment for 120min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 7
(1) 0.50g of PbI2、0.175g FAI、0.075g PbBr20.020g of MABr and 0.018g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Adding pyrrole into ethanol to prepare 20mmol L-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 90 ℃ and carrying out annealing treatment for 90min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 8
(1) 0.48g of PbI2、0.19g FAI、0.085g PbBr20.024g of MABr and 0.015g of CsI are dissolved in a mixed solvent of 800mLN, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Pyrrole was added to diethyl ether to give 24mmol L-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 120 ℃ and carrying out annealing treatment for 60min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 9
(1) 0.53g of PbI2、0.183g FAI、0.083g PbBr20.018g of MABr and 0.017g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Pyrrole was added to anisole to prepare a solution having a concentration of 26mmol L-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 140 ℃ and carrying out annealing treatment for 20min to obtain the surface modified perovskite solar cell light absorption layer film.
Example 10
(1) 0.51g of PbI2、0.185g FAI、0.080g PbBr20.025g of MABr and 0.019g of CsI are dissolved in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) under stirring, and stirred for more than 4.5 hours to prepare a perovskite precursor solution.
(2) Adding pyrrole into trichlorotoluene to prepare a solution with the concentration of 30mmol L-1The additive solution of (1).
(3) Uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step 2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; and then drying the film in an argon atmosphere, drying the film at 160 ℃, and carrying out annealing treatment for 1min to obtain the surface modified perovskite solar cell light absorption layer film.
Comparative example 1
The preparation method comprises the following steps:
(1) 0.507g PbI2、0.172g FAI、0.081g PbBr2Dissolving 0.023g of MABr and 0.020g of CsI raw materials in a mixed solvent of 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO), and stirring for more than 4.5h to prepare a perovskite precursor solution;
(2) spin coating perovskite precursors on conductive glass substratesSolution, start the spin coater, first 1000rpm s-1Accelerating to the rotation speed of 1000rpm and rotating at low speed for 10 s; then at 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film;
(3) 150 μ L of chlorobenzene was quickly dropped in the center of the conductive glass substrate 5s before the end of the high-speed spin coating by the spin coater.
(4) Drying and annealing for 60min at 100 ℃ in an argon atmosphere to obtain the perovskite light absorption layer film.
FIG. 1 is an XRD spectrum of perovskite thin films prepared according to example 4 of the present invention and comparative example 1, and XRD test results show that the light absorbing layer thin film after pyrrole passivation in example 4 has PbI at 12.7 °2The diffraction peak is enhanced, which shows that the perovskite and PbI of the passivated film2The degree of phase separation of (a); a moderate amount of phase separation can self-passivate the perovskite thin film defects, which is beneficial to the performance of the thin film. Comparing the diffraction peaks of the perovskite phase in the passivated film and the unpassivated film, the diffraction peaks of the passivated film are sharper, the peak intensity is increased, and the peak positions are not obviously different, which shows that the crystallinity of the perovskite film is enhanced by the passivation treatment, and the crystal structure of the perovskite phase is not changed.
FIG. 2 is an SEM photograph of a perovskite thin film prepared in comparative example 1 of the present invention, and FIG. 3 is an SEM photograph of a perovskite thin film prepared in example 4 of the present invention; by comparing SEM photographs of the passivated and unpassivated films, it can be seen that the surface of the film modified with pyrrole is relatively flat, and no obvious holes are seen. We conclude that this is probably because pyrrole forms coordination bonds with perovskite surface defect sites, so that the surface defect density of the passivated film is reduced and the film quality is improved.
FIG. 4 is a UV-vis absorption spectrum of the perovskite light absorption layer thin films prepared in examples 1 to 5 of the present invention, wherein the surface additive solution concentrations in examples 1 to 5 are as follows: 3mmol L-1、6mmol L-1、9mmol L-1、12mmol L-1And 15mmol L-1(ii) a As can be seen from FIG. 4, as the pyrrole concentration increases, the perovskiteThe light absorption intensity of the mineral film in the wavelength range of 500-800 nm is obviously enhanced, the absorption edge is red-shifted, and the concentration of the surface additive is 12mmol L-1In this case, the perovskite thin film exhibits an optimum light absorption characteristic, which is advantageous for improving the efficiency of utilization of sunlight by the light absorbing layer. However, when the surface additive concentration was 15mmol L-1In the meantime, the light absorption characteristics of the film are degraded, which may be caused by excess pyrrole remaining on the surface of the film.
FIG. 5 shows the fluorescence excitation spectrum of the perovskite thin film prepared in example 4 of the present invention, and it can be seen that the thin film shows a fluorescence excitation peak at 626 nm. Fluorescence emission spectra (i.e., steady-state photoluminescence spectra) of the films of example 4 and comparative example 1 measured under this excitation are shown in fig. 6, and both the passivated and unpassivated films show a single peak around 766nm, exhibiting photoluminescence characteristics typical of perovskite thin film materials. Compared with the two films, the photoluminescence peak intensity of the passivated film is reduced, and the peak position is slightly blue-shifted, which shows that the defect density of the perovskite film is reduced after pyrrole passivation.
FIG. 7 is a photograph of a contact angle of a perovskite thin film prepared according to comparative example 1 of the present invention; FIGS. 8 to 12 are photographs showing contact angles of perovskite thin films prepared in examples 1 to 5 of the present invention. Comparing FIGS. 7-12, the contact angle of the perovskite thin film increases with the increase of the concentration of the pyrrole additive solution, and the concentration of pyrrole is 12mmol L-1At this time, the contact angle of the film reached a maximum, increasing from 51.0 ° to 77.9 ° of the original, unpassivated film, indicating that the pyrrole enhanced the hydrophobicity of the perovskite film, which is beneficial for improving the humidity stability of the perovskite film.
Fig. 13 to 16 are performance test box plots of the application of the perovskite light absorption layer thin films prepared in examples 1 to 5 of the present invention and comparative example 1 to a perovskite solar cell device. Fig. 13, 14, 15, and 16 are respectively the Photoelectric Conversion Efficiency (PCE) and the short-circuit current density (J) of the perovskite solar cellsc) Open circuit voltage (V)oc) And a Fill Factor (FF) statistic map. J of the device with increasing additive concentrationsc、VocFF and PEC all show a tendency to increase and then decreasePotential at an additive concentration of 12mmol L-1The time reaches a maximum value. The introduction of a proper amount of pyrrole additive is further proved to effectively passivate the defects on the surface of the perovskite thin film, so that the efficiency of the device is improved.
FIG. 17 is a photograph of perovskite thin films prepared in example 4 of the present invention and comparative example 1 before and after humidity aging test. To more intuitively verify the moisture stability of perovskite thin films, we will be unpassivated and passivated (pyrrole additive concentration 12mmol L)-1) The film of (2) was subjected to a humidity aging test in air with a water content of > 95%. The experimental result shows that the color of the unpassivated film is changed from black to brown after 2.5 hours, and the unpassivated film is obviously degraded; and the color of the passivated film still does not change greatly after 5.0 h. It is further demonstrated that the moisture stability of the perovskite thin film is significantly improved due to the introduction of pyrrole.

Claims (8)

1. A method for passivating surface defects of a perovskite light absorption layer film is characterized by comprising the following steps:
step 1, 0.460-0.530 g of PbI20.170-0.190 g of FAI and 0.075-0.085 g of PbBr20.015-0.025 g of MABr and 0.015-0.020 g of CsI are dissolved in 800mL of N, N-Dimethylformamide (DMF) and 200mL of dimethyl sulfoxide (DMSO) mixed solvent under stirring to prepare a perovskite precursor solution;
step 2, dissolving pyrrole into an organic solvent to prepare a solution with a concentration of 0.1-30.0 mmol L-1The surface additive solution of (1);
step 3, uniformly dripping the perovskite precursor solution on an FTO conductive glass substrate, starting a spin coater, and firstly, rotating at 1000rpm s-1Acceleration to 1000rpm and low speed rotation for 10s, followed by 2000rpm s-1Accelerating to 5500rpm and rotating at high speed for 25s to prepare the perovskite thin film; dropwise adding the surface additive solution obtained in the step (2) on the surface of the perovskite thin film in the first 5s of the stop of the high-speed rotation of the spin coater; then drying in argon atmosphere to obtain the surface modified perovskite light absorption layerA film.
2. The method for passivating surface defects of a perovskite light absorption layer thin film according to claim 1, wherein the continuous stirring of step 1 is performed for 4.5 hours or more.
3. The method for passivating surface defects of a perovskite light absorption layer thin film according to claim 1, wherein the organic solvent in the step 2 is at least one of isopropanol, ethanol, diethyl ether, anisole, ethyl acetate, toluene, chlorobenzene or trichlorotoluene.
4. The method for passivating surface defects of a perovskite light absorption layer thin film according to claim 1, wherein the step 3 is performed by drying in an argon atmosphere and then annealing at 70-160 ℃ for 1-120 minutes.
5. A perovskite light-absorbing layer thin film obtained by the method for passivating surface defects of a perovskite light-absorbing layer thin film according to any one of claims 1 to 4.
6. The perovskite light-absorbing layer film as claimed in claim 5, wherein after surface defect passivation, the film has a reduced steady-state photoluminescence peak intensity around 766nm, a blue shift of the peak position, a reduced surface defect density of the light-absorbing layer film, and a significantly improved quality of the light-absorbing layer film.
7. The perovskite light-absorbing layer thin film as claimed in claim 5, wherein the light-absorbing layer thin film has a significantly enhanced light-absorbing property in a wavelength range of 500 to 800nm after surface defect passivation, and has a good solar light utilization rate.
8. The perovskite light-absorbing layer thin film according to claim 5, wherein after the pyrrole additive is introduced, a hydrophobic layer is formed on the surface of the light-absorbing layer thin film, so that the corrosion of water to the perovskite cell is delayed, and the light-absorbing layer thin film has good humidity stability.
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