Method for preparing inverted perovskite solar cell module modified by means of passivation

Abstract

The present application belongs to the technical field of the manufacture of photovoltaic cells, and relates to a method for preparing an inverted perovskite solar cell module modified by means of passivation. The method comprises the steps of the cleaning of a substrate, the preparation of nickel oxide, the passivation of nickel oxide, the cleaning of a passivation layer, the preparation of a perovskite layer, the preparation of an electron transport layer and the preparation of a top electrode. In the present method, high-valence nickel ions and chemical reactive groups, which are present on the surface of the nickel oxide and harmful to perovskite, can be effectively treated by means of simple coating and the cleaning of a perovskite material with an organic solvent, thereby improving the transmittance of a nickel oxide thin film, enhancing the hole extraction capability of the nickel oxide thin film, and reducing the interface recombination loss; the surface of the passivated nickel oxide thin film does not need a complex surface treatment any longer, and the perovskite having been subjected to secondary coating can thoroughly spread out on the surface of nickel oxide, thereby leading to significantly reduced macroscopic holes and microscopic pinholes, an increased grain size and a reduced defect density; and while the passivation effect is achieved, an increase in equipment costs and raw material costs due to the introduction of other passivators is also avoided.

Description

A method for preparing a passivated modified inverse perovskite solar cell module Technical Field

[0001] The present application relates to the technical field of photovoltaic cell manufacturing, and in particular to a method for preparing a passivated modified inverse perovskite solar cell module. Background Art

[0002] Perovskite solar cell technology has developed rapidly in recent years, with the rapid growth of power conversion efficiency (PCE) exceeding 26% in ten years, which has attracted widespread attention from experts in related fields. Among perovskite cells, inverse perovskite cells have more potential value than their formal structures and are more compatible with commercial development. In inverse perovskite cells, NiO x Hole transport layer is widely used due to its low cost and easy large-area preparation, but the wet-processed NiO x Usually requires energy-intensive annealing, which is not conducive to large-scale industrial preparation. x They are usually substoichiometric because they readily undergo redox reactions in the deposition chamber, leading to enhanced hole density and hole mobility, and vacuum processing can produce large-area NiO x Thin film is beneficial to the industrialization process.

[0003] However, NiO prepared by vacuum method x Thin films also have problems that restrict their application. x The relatively hydrophobic surface of the NiO film weakens the adhesion of the perovskite precursor, which leads to shrinkage of the perovskite wet film and pinholes in the dry film during large-area coating. Commonly used hydrophilic methods will lead to the x A large amount of highly oxidized Ni (Ni 3+ and Ni 4+ ) and chemically reactive hydroxyl groups (NiOOH and -Ni(OH)2), which react with the A-site cations and halide ions in the perovskite, leading to the decomposition of the perovskite material. x The film cannot be stored in air for a long time. Long-term storage will cause granular substances to appear on the surface of nickel oxide, resulting in low quality of the coated perovskite film. xSurface engineering often uses interface modification layers, such as small molecules or expensive p-type organic semiconductors, to reduce interface defects and promote energy-level alignment. For example, Chinese patent CN111223990A uses alkali metal halide-based passivation of nickel oxide to strengthen the adhesion between the nickel oxide and the perovskite layer, reducing pores on the nickel oxide surface. Meanwhile, Chinese patent CN115942765A employs another method to prepare a Ni2O3-rich nickel oxide layer and a dilute Ni2O3 nickel oxide layer, enhancing the spreading effect of the perovskite precursor and thus achieving a large, uniform, and dense perovskite film. However, these methods require complex preparation processes and high energy consumption, severely restricting the industrial production of large-area modules.

[0004] Therefore, it is necessary to improve the manufacturing method of inverse perovskite solar cell modules to avoid the above problems.

[0005] Summary of the Invention

[0006] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0007] The present application provides a method for preparing a passivated modified inverse perovskite solar cell module, directly using the same material as the perovskite light-absorbing layer as a passivator for the nickel oxide hole transport layer. For the production of large-area products, while achieving the passivation effect, the types of raw materials are reduced, avoiding the introduction of other passivants that lead to increased equipment costs and raw material costs.

[0008] The present application provides a method for preparing a passivated modified inverse perovskite solar cell module. The inverse perovskite solar cell module includes a conductive substrate, a hole transport layer, a perovskite light absorbing layer, an electron transport layer, and a top electrode stacked in sequence from bottom to top. The hole transport layer material is passivated modified nickel oxide. The preparation method includes the following steps:

[0009] S1. Substrate cleaning: The conductive substrate is subjected to P1 laser scribing, and then the surface of the conductive substrate is cleaned and dried for standby use;

[0010] S2. Preparation of nickel oxide: The conductive substrate is transferred to a PVD device, the sputtering chamber is evacuated, O2 and Ar are introduced, the sputtering power is turned on, and a doped nickel oxide target is used for sputtering to obtain a nickel oxide film;

[0011] S3 nickel oxide passivation: the nickel oxide film was plasma treated for 1 minute and then coated with a first perovskite film having a coating thickness of 100-500nm;

[0012] S4. Cleaning the passivation layer: The passivated nickel oxide substrate is left for at least 24 hours, and then the first perovskite film is cleaned with an organic solvent to obtain a hole transport layer;

[0013] S5. Preparation of perovskite layer: coating a second perovskite film on the surface of the hole transport layer to a thickness of 400-600 nm, removing the solvent and annealing the film at a temperature of 100-150°C for 10-30 min to obtain the perovskite light absorbing layer;

[0014] S6. Preparation of electron transport layer: coating an electron transport layer on the surface of the second perovskite film, and then performing P2 laser scribing on the half-cell on which the electron transport layer is prepared;

[0015] S7. Preparation of the top electrode: A top electrode is prepared on the outside of the electron transport layer, wherein the thickness of the top electrode is 100-300 nm, and then P3 laser scribing is performed on the battery device after the top electrode is prepared;

[0016] The first perovskite film and the second perovskite film are made of the same material and both contain FA + 、MA + 、Cs + 、Sn 2+ or Pb 2+ At least two cations and I - 、Cl - or Br - At least one anion in.

[0017] Specifically, the cleaning method of step S1 is to sequentially ultrasonicate the conductive substrate in deionized water, glass detergent, acetone, and ethanol for 15 minutes, and then treat it with plasma for 1 minute.

[0018] Specifically, the sputtering conditions of step S2 are: the flow rate of O2 is 0.5-5% of the flow rate of Ar, the sputtering power is 3-4.5kW, and the NiO x The target material is doped with one or two of Cu, Mg, Li, Ag, K and Na.

[0019] Specifically, the line width of P1 laser scribing is 10-30nm, the line width of P2 laser scribing is 100-400nm, and the line spacing between it and the P1 laser scribing profile is 10-100nm, and the line width of P3 laser scribing is 50-120nm, and the line spacing between it and the P2 laser scribing profile is 10-100nm.

[0020] Specifically, the solvent used to clean the first perovskite film in step S4 is one of N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO).

[0021] Specifically, the electron transport layer includes a transport layer and a barrier layer located outside the transport layer, and the transport layer is C prepared by evaporation. 60 Or PCBM prepared by coating, the transmission layer has a thickness of 30-60 nm, the barrier layer is BCP prepared by evaporation or SnO2 prepared by ALD, and the barrier layer has a thickness of 10-60 nm.

[0022] Specifically, the top electrode preparation method includes evaporating Ag, Cu, Au or preparing one or more of ITO, AZO, and FTO by PVD.

[0023] Compared with the related art, this application has the following beneficial effects.

[0024] 1. The passivation process is simple and energy-saving: the first perovskite film can be combined with NiO x The high oxidation state Ni (Ni 3+ and Ni 4+ ) and chemically reactive hydroxyl groups (-NiOOH and -Ni(OH)2) to achieve the passivation effect without increasing the types of raw materials or requiring complex double-layer nickel oxide sputtering process adjustments. The control requirements for the secondary cleaning endpoint are low, which is more beneficial for the quality control of large-area modules and avoids additional equipment utilization and energy waste.

[0025] 2. Good passivation effect on nickel oxide: Sputtered nickel oxide contains a large amount of high-valent Ni and reactive groups that are harmful to perovskite. Ion migration in perovskite can effectively reduce such harmful substances. After cleaning the perovskite, the black Ni of the nickel oxide film can be visually seen. 4+ The transmittance of the film is improved, the defect density is reduced, and the charge mobility of nickel oxide is improved. The secondary coating of perovskite on the passivated nickel oxide film has a larger grain size and a better crystal orientation. At the same time, the buried interface defects are reduced, which effectively suppresses the interface non-radiative recombination and improves the efficiency and stability of the module.

[0026] 3. Stronger adhesion between nickel oxide and perovskite: Perovskite does not spread well on nickel oxide films before passivation, often resulting in numerous visible holes, requiring complex surface treatments such as plasma treatment and UV-ozone treatment. After perovskite passivation and organic solvent cleaning, many harmless hydrophilic groups remain on the surface of the nickel oxide film, eliminating the need for complex surface treatment. The secondary coating of perovskite spreads well on the nickel oxide surface, leaving no visible holes. Microscopically, the number of perovskite pinholes is also reduced.

[0027] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a manufacturing flow chart of an inverse perovskite solar cell module;

[0029] FIG2 is the transmission spectrum of the nickel oxide hole transport layer film before and after passivation in Example 1;

[0030] FIG3 is a scanning electron microscope (SEM) image of the nickel oxide hole transport layer film before and after passivation in Example 1;

[0031] FIG4 is a water drop angle test diagram of the nickel oxide hole transport layer film before and after passivation in Example 1;

[0032] FIG5 is the fluorescence (PL) spectrum of the perovskite light absorbing layer before and after passivation in Example 1;

[0033] FIG6 is a scanning electron microscope (SEM) image of the perovskite film prepared on the nickel oxide hole transport layer before and after passivation in Example 1;

[0034] FIG7 is a JV performance test curve of the inverse perovskite solar cell module before and after passivation in Example 1;

[0035] FIG8 is a stability test curve of the photoelectric conversion efficiency of the inverse perovskite solar cell module before and after passivation in Example 1.

[0036] The numbers in the figure indicate: 1-conductive substrate; 2-hole transport layer; 3-perovskite light absorbing layer, 3a-first perovskite film, 3b-second perovskite film; 4-electron transport layer, 41-transport layer, 42-blocking layer; 5-top electrode. DETAILED DESCRIPTION

[0037] The present application is further described in detail below with reference to specific embodiments.

[0038] Examples 1-12:

[0039] As shown in FIG1 , the inverse perovskite solar cell module includes a conductive substrate 1, a hole transport layer 2, a perovskite light absorbing layer 3, an electron transport layer 4 and a top electrode 5 stacked in sequence from bottom to top. The hole transport layer 2 is made of passivated modified nickel oxide.

[0040] The above inverse perovskite solar cell module is made by the following steps:

[0041] S1. Substrate cleaning: The conductive substrate 1 is laser scribed P1, and then the surface of the conductive substrate 1 is cleaned and dried for standby use;

[0042] The specific cleaning method is: the conductive substrate 1 is ultrasonically treated in deionized water, glass detergent, acetone and ethanol for 15 minutes respectively, and then treated with plasma for 1 minute.

[0043] The conductive substrate 1 is a doped tin oxide film layer coated on a glass material. The surface needs to be smooth and free of dirt in order to better deposit the hole transport layer 2, so it needs to be cleaned first. In this embodiment, deionized water is used to dissolve water-soluble impurities, and the glass cleaner has a weak alkalinity that can remove some oxides on the conductive substrate 1. Acetone and ethanol can dissolve oily substances. Ultrasound can help impurities break down from the conductive substrate 1 and then be dissolved by various solvents. Plasma treatment can also remove oxides and pollutants on the surface. In practical applications, the ultimate goal is to clean the surface of the conductive substrate 1. The solvent used and the treatment time can vary according to the cleanliness requirements and size of the inverse perovskite solar cell module.

[0044] S2. Preparation of nickel oxide: The conductive substrate 1 is transferred to the PVD equipment, the sputtering chamber is evacuated, O2 and Ar are introduced, the sputtering power is turned on, and the doped nickel oxide target is sputtered to obtain a nickel oxide film. The sputtering conditions are: the flow rate of the introduced O2 is 0.5-5% of the Ar flow rate, the sputtering power is 3-4.5kW, and the NiO x The target material is doped with one or two of Cu, Mg, Li, Ag, K and Na.

[0045] In this step, electrons, accelerated by the electric field, collide with argon atoms as they fly toward the substrate, ionizing a large number of argon ions and electrons. The argon ions, accelerated by the electric field, bombard the target material, sputtering a large number of target atoms. These neutral target atoms (or molecules) are deposited on the substrate to form a film. Doping elements can improve the electrical properties of thin films.

[0046] S3. Nickel oxide passivation: Plasma-treat the nickel oxide film for 1-5 minutes and then coat the first perovskite film with a coating thickness of 100-500 nm. The first perovskite film contains FA + 、MA + 、Cs + 、Sn 2+ or Pb 2+ At least two cations and I - 、Cl - or Br - At least one anion in.

[0047] The coating method of the first perovskite film can be blade coating, spray coating, slit coating, etc. x There is a large amount of highly oxidized Ni (Ni 3+ and Ni 4+) and chemically reactive hydroxyl groups (-NiOOH and -Ni(OH)2). If these components are not eliminated by passivation, they will cause serious interface recombination between the hole transport layer 2 and the perovskite light absorbing layer 3, resulting in a decrease in the electrical performance of the device. The ions in the perovskite film will migrate over time, and the ions that migrate to the interface will undergo redox reactions and halogenation reactions on the surface of the nickel oxide, which can eliminate high-oxidation state Ni and chemically reactive hydroxyl groups. At the same time, since the material of the first perovskite film 3a is the material used for the perovskite light absorbing layer 3, while achieving passivation, the type of raw materials is not increased, and the introduction of other passivating agents to increase equipment costs and raw material costs is avoided. It is particularly suitable for use in large-area inverted perovskite solar cell modules. During actual coating, if the thickness of the perovskite material is too thin, it will not be fully coated, and it cannot be guaranteed that every hole on the hole transport layer 2 is covered, and the protective effect is incomplete; if the thickness is too large, it will affect the sufficiency of the reaction, resulting in incomplete passivation and waste of cleaning agent, so it is preferably 100-500nm. The coated perovskite film can serve as a barrier layer to isolate the influence of water and oxygen in the ambient atmosphere on nickel oxide, thus preventing nickel oxide from undergoing physical and chemical reactions when stored in the air.

[0048] The passivation process is simple and has low energy consumption. The perovskite light-absorbing layer 3 is simply coated to treat the surface states and chemically reactive groups on the sputtered nickel oxide surface that are harmful to the perovskite. There is no need to add a passivation layer, nor is there a need for complex double-layer nickel oxide sputtering process adjustments, thus avoiding the use of additional equipment and energy waste. The passivation effect on nickel oxide is good: the sputtered nickel oxide contains a large amount of high-valent Ni and reactive groups that are harmful to the perovskite. The ions in the perovskite can effectively reduce such harmful substances. After cleaning the perovskite, the black Ni of the nickel oxide film can be visually seen. 4+ The transmittance of the film is improved, the defect density is reduced, and the charge mobility of nickel oxide is improved. The secondary coating of perovskite on the passivated nickel oxide film has a larger grain size and a better crystal orientation. At the same time, the buried interface defects are reduced, which effectively suppresses the interface non-radiative recombination and improves the efficiency and stability of the module.

[0049] S4. Cleaning the passivation layer: The passivated nickel oxide substrate is placed for more than 24 hours, and then the first perovskite film is cleaned with an organic solvent to obtain a hole transport layer 2; the solvent for cleaning the first perovskite film is one of DMF, NMP or DMSO.

[0050] Because the first perovskite film in step S4 mainly plays a passivation role, the amount used is enough to cover the entire nickel oxide film. In the end, except for the part that reacts with the harmful group, the other parts need to be cleaned with an organic solvent. For large-area device production, the nickel oxide and perovskite interface must be passivated to achieve the purpose of improving device performance, but the introduction of a new passivator requires additional supporting coating equipment, while the use of perovskite avoids the introduction of other passivators, which leads to an increase in equipment cost and raw material cost. In step S4, DMF, NMP and DMSO are solvents specifically for perovskite materials. In order to reduce the difficulty of processing, generally only one reagent is used, and the first perovskite film is basically completely washed away without damaging the hole transport layer 2. Even if a trace of the first perovskite film remains on the surface of the hole transport layer 2, because it is the same material as the perovskite light absorption layer 3, there is no problem with compatibility, so the control requirements for the secondary cleaning endpoint are relatively low, which is more beneficial for quality control of large-area modules.

[0051] S5. Perovskite coating: A second perovskite film is coated on the surface of the hole transport layer 2 with a coating thickness of 400-600 nm. After removing the solvent, annealing is performed at a temperature of 100-150°C and an annealing time of 10-30 minutes to obtain a perovskite light absorption layer 3. The material of the second perovskite film 3b is the same as that of the first perovskite film 3a.

[0052] Here, the second perovskite film 3b is deposited only on the areas previously covered by the hole transport layer 2, using conventional coating thickness and process. However, because the previous passivation process has already removed harmful substances from the nickel oxide film's surface and improved its surface wettability, further surface modification methods such as UV-ozone treatment or plasma treatment are not required, resulting in a superior perovskite film.

[0053] S6. Preparation of electron transport layer 4: Electron transport layer 4 is plated on the surface of the second perovskite film 3b, and then P2 laser scribing is performed on the half cell on which the electron transport layer 4 is prepared.

[0054] The electron transport layer 4 includes a transport layer 41 and a barrier layer 42 located outside the transport layer 41. The transport layer 41 is a C 60 (fullerene) or PCBM (fullerene derivative) prepared by coating, the transmission layer 41 has a thickness of 30-60nm, the barrier layer 42 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) prepared by vapor deposition or SnO2 prepared by atomic layer deposition (ALD), and the barrier layer 42 has a thickness of 10-60nm.

[0055] S7, preparation of top electrode 5: preparing a top electrode 5 on the outside of the electron transport layer 4, the top electrode 5 having a thickness of 100-300 nm, and then performing P3 laser scribing on the battery device having the top electrode 5 prepared;

[0056] The top electrode 5 is prepared by evaporating Ag, Cu, Au or preparing indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), or fluorine-doped tin oxide (FTO) by physical vapor deposition (PVD).

[0057] The line width of P1 laser scribing is 10-30nm, the line width of P2 laser scribing is 100-400nm, and the line spacing between it and the P1 laser scribing profile is 10-100nm, and the line width of P3 laser scribing is 50-120nm, and the line spacing between it and the P2 laser scribing profile is 10-100nm.

[0058] The above are the linear dimensions that can be achieved while ensuring product yield based on existing process capabilities.

[0059] According to the parameters in Table 1, passivated modified inverse perovskite solar cell modules were manufactured. The module size was 100 mm × 100 mm, and the number of effective sub-cells was 7.

[0060] Table 1: Process parameters of Examples 1-12

[0061] The product test results of Example 1 are shown in Figures 3 to 8.

[0062] As shown in Figure 2, the transmittance of the nickel oxide film before passivation was 77%, while the transmittance of the nickel oxide film after passivation modification was 82%, demonstrating enhanced light transmittance. Higher light transmittance means that the perovskite film can absorb more light, increasing the current of the perovskite module. Sputtered nickel oxide films generally appear black due to the participation of oxygen in the sputtering process, which increases the high-valent nickel content in the sputtered film. After passivation, the nickel oxide's light transmittance is enhanced, and the black color of the film becomes lighter, which directly indicates that the high-valent nickel in the nickel oxide is reduced to low-valent nickel by ions in the perovskite.

[0063] The left picture in Figure 3 is the XRD spectrum of the nickel oxide hole transport layer film after storage in the air for a period of time. The spectrum shows that island-shaped micron-sized visible particles appear on the nickel oxide film, which will have an adverse effect on the subsequent coating of the perovskite film layer, and these particulate matter will become recombination centers, leading to the decomposition of the perovskite. The right picture in Figure 3 is the XRD spectrum of the nickel oxide hole transport layer film after passivation. The film has no obvious holes and island-shaped particles, and the nickel oxide particles are dense and uniform.

[0064] The left picture in Figure 4 is a water drop angle test diagram of the nickel oxide hole transport layer before passivation. The test water drop angle is 35.35°. The right picture is a side view of the water drop angle of the nickel oxide hole transport layer after passivation. The test water drop angle is 25.46°. It can be seen that the nickel oxide film after passivation has better surface wettability, which is conducive to better coating and spreading of the perovskite film, and reduces the perovskite holes caused by poor surface wettability.

[0065] In Figure 5, the perovskite film prepared on the passivated nickel oxide film has more significant fluorescence quenching, showing that the passivated nickel oxide film has a stronger hole extraction ability and higher hole mobility, indicating that the non-radiative recombination at the interface between perovskite and nickel oxide is suppressed.

[0066] The perovskite film prepared on nickel oxide before passivation modification (left image) in Figure 6 has a large number of pinholes at the grain boundaries, which will serve as a path for charge recombination and the starting point for degrading device performance. In contrast, increasing the surface energy after passivation modification improves the stacking of the perovskite film on nickel oxide. At the same time, the perovskite film prepared on nickel oxide after passivation modification has significantly reduced macroscopic holes and microscopic pinholes, increased grain size, and reduced defect density, resulting in a high-efficiency inverse perovskite solar cell module.

[0067] As shown in Figure 7, passivation can increase the module current from 0.1238A to 0.1263A, reflecting the enhanced hole mobility of the nickel oxide layer. The open circuit voltage is increased from 7.16V to 7.48V, and the fill factor is increased from 62.95% to 65.30%. The final efficiency is increased by about 1.5%, which is a significant improvement in photoelectric performance.

[0068] As shown in Figure 8, this stability test curve is based on an unpackaged module, which was stored in an inert gas atmosphere with a humidity of 20% during the test. The module efficiency was tracked for 1000 hours. The inverse perovskite solar cell module based on the nickel oxide hole transport layer before passivation modification had a photoelectric conversion efficiency decayed to 75.9% of the initial value after 1000 hours, while the inverse perovskite solar cell module based on the nickel oxide hole transport layer after passivation modification had a photoelectric conversion efficiency decayed to 82.1% of the initial value after 1000 hours, showing the improved stability of the passivated perovskite module and indicating a reduction in the perovskite buried interface defect density.

[0069] The above tests prove that the passivation treatment of this process brings about improved product performance.

[0070] The above are only some embodiments of the present application. For those skilled in the art, several modifications and improvements can be made without departing from the inventive concept of the present application, and these all fall within the scope of protection of the present application.

Claims

1. A method for preparing a passivated modified inverse perovskite solar cell module, wherein the inverse perovskite solar cell module comprises a conductive substrate, a hole transport layer, a perovskite light absorbing layer, an electron transport layer, and a top electrode stacked in sequence from bottom to top, wherein the hole transport layer material is passivated modified nickel oxide, comprising the following steps: S1. Substrate cleaning: The conductive substrate is subjected to P1 laser scribing, and then the surface of the conductive substrate is cleaned and dried for standby use; S2. Preparation of nickel oxide: The conductive substrate is transferred to a PVD device, the sputtering chamber is evacuated, O2 and Ar are introduced, the sputtering power is turned on, and a doped nickel oxide target is used for sputtering to obtain a nickel oxide film; S3 nickel oxide passivation: the nickel oxide film was plasma treated for 1 minute and then coated with a first perovskite film having a coating thickness of 100-500nm; S4. Cleaning the passivation layer: The passivated nickel oxide substrate is left for at least 24 hours, and then the first perovskite film is cleaned with an organic solvent to obtain a hole transport layer; S5. Preparation of perovskite layer: coating a second perovskite film on the surface of the hole transport layer to a thickness of 400-600 nm, removing the solvent and annealing the film at a temperature of 100-150°C for 10-30 min to obtain the perovskite light absorbing layer; S6. Preparation of electron transport layer: coating an electron transport layer on the surface of the second perovskite film, and then performing P2 laser scribing on the half-cell on which the electron transport layer is prepared; S7. Preparation of the top electrode: A top electrode is prepared on the outside of the electron transport layer, wherein the thickness of the top electrode is 100-300 nm, and then P3 laser scribing is performed on the battery device after the top electrode is prepared; The first perovskite film and the second perovskite film are made of the same material and both contain FA + 、MA + 、Cs + 、Sn 2+ or Pb 2+ At least two cations and I - 、Cl - or Br - At least one anion in.

2. The preparation method according to claim 1, wherein The cleaning method of step S1 is to sequentially ultrasonicate the conductive substrate in deionized water, glass detergent, acetone and ethanol for 15 minutes respectively, and then treat it with plasma for 1 minute.

3. The preparation method according to claim 1, wherein The sputtering conditions of step S2 are: the flow rate of O2 is 0.5-5% of the flow rate of Ar, the sputtering power is 3-4.5kW, NiO x The target material is doped with one or two of Cu, Mg, Li, Ag, K and Na.

4. The preparation method according to claim 1, wherein The line width of P1 laser scribing is 10-30nm, the line width of P2 laser scribing is 100-400nm, and the line spacing between it and the first laser scribing profile is 10-100nm, and the line width of P3 laser scribing is 50-120nm, and the line spacing between it and the P2 laser scribing profile is 10-100nm.

5. The preparation method according to claim 1, wherein The solvent used to clean the first perovskite film in step S4 is one of DMF, NMP or DMSO.

6. The preparation method according to claim 1, wherein The electron transport layer includes a transport layer and a barrier layer outside the transport layer. The transport layer is C prepared by evaporation. 60 Or PCBM prepared by coating, the barrier layer is BCP prepared by evaporation or SnO2 prepared by ALD, the thickness of the transmission layer is 30-60nm, and the thickness of the barrier layer is 10-60nm.

7. The preparation method according to claim 1, wherein The top electrode preparation method includes evaporating Ag, Cu, Au or preparing one or more of ITO, AZO, and FTO by PVD.

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