WO2020248864A1

WO2020248864A1 - Passivator, passivation method therefor and method for preparing semiconductor film

Info

Publication number: WO2020248864A1
Application number: PCT/CN2020/093814
Authority: WO
Inventors: 颜步一; 姚冀众
Original assignee: 杭州纤纳光电科技有限公司
Priority date: 2019-06-12
Filing date: 2020-06-01
Publication date: 2020-12-17
Also published as: CN112086564A

Abstract

Disclosed are a passivator, and a method for preparing a semiconductor film using the passivator. The passivator is at least one of an imidazolium salt ionic liquid, a pyridinium salt ionic liquid, a quaternary ammonium salt ionic liquid, a pyrrolidinium salt ionic liquid, a piperidinium salt ionic liquid, a functionalized ionic liquid, a ferrocene organic substance, a metal phthalocyanine compound, a metal acetylacetone compound, an organic metal, a halogen bond compound and an organic boride. Depositing the passivator between a semiconductor film and an interface material in contact therewith, and/or adding the passivator to raw materials for preparing the semiconductor film provides a uniform and stable reaction environment for the passivator and the semiconductor film material, so that the crystal growth of the semiconductor film can be controlled during the preparation process thereof, thereby greatly improving the stability of the semiconductor film.

Description

Passivation agent and its passivation method and method for preparing semiconductor film

Technical field

The invention belongs to the technical field of semiconductor preparation, and particularly relates to a passivation agent and a passivation method thereof and a method for preparing a semiconductor film.

Background technique

In recent years, a perovskite solar cell has received widespread attention. The perovskite has an ABX ₃ type cubic octahedron structure. As shown in Figure 1, this perovskite solar cell uses organic metal halide as the light absorption layer. The thin-film solar cell prepared by the material has simple process, low production cost, stability and high conversion rate. Since 2009, the photoelectric conversion efficiency has increased from 3.8% to more than 22%, which is higher than the existing commercial crystalline silicon solar cells and has a greater cost advantage.

Compared with other traditional solar cells, perovskite solar cells are more susceptible to moisture, oxygen, temperature, light and other factors, and perovskite solar cells are prone to ion migration under light, especially the migration of halogen ions. This phenomenon leads to the hysteresis effect of the battery and the deterioration of the device performance. Among them, the surface of the perovskite active layer, the surface of the transport layer, and the perovskite grain boundary are precisely the places most prone to degradation or ion migration.

The instability of perovskite solar cells mainly comes from the ion migration inside the perovskite material, the ion migration induced by the interface mismatch, and the perovskite material caused by the reaction of the metal electrode with the migration ions in the perovskite after diffusion. Degenerate. Therefore, inhibiting ion migration within the perovskite material and on the surface between the perovskite material and its interface layer has become a key means to improve the stability of the perovskite material.

As shown in Figure 1, the perovskite material is essentially a mixed organic-inorganic ionic crystal, including organic cation A, metal cation B and halogen anion X. To inhibit ion movement, it is not possible to simply inhibit only one ion , And the movement of these three ions needs to be suppressed at the same time.

In the process of the movement of the above three ions, the organic cation A has the ability to give a proton, so it can be regarded as a Lewis acid. The metal cation B has a similar ability and is also a Lewis acid. The halogen ion X is in this system. Treat as Lewis base. The process of organic cation A or metal cation B giving protons, or halogen ion X giving electrons is the beginning of ion migration. Therefore, in order to inhibit ion migration, it is necessary to prevent the three ions in the perovskite material from giving protons or Electronic process.

On the other hand, in addition to the potential risk of ion migration inside the perovskite material, when the surface of the perovskite material forms an interface with other materials, the interface material may also catalyze the above process. Especially when the interface material has basic centers (such as inorganic metal oxides, such as ZnO, NiO, etc.), the exposed basic centers will accelerate the process of giving protons by the acid groups of the perovskite (such as the A group). This induces ion migration.

From the above point of view, to inhibit ion migration, it is necessary to balance the acid-base system in the perovskite material and the perovskite material and its interface environment, which we call the passivation balance process. To achieve this process, it is necessary to: 1) the perovskite material, and/or 2) introduce a properly balanced acid-base system into the perovskite interface.

technical problem

The technical problem to be solved by the present invention is to provide a passivation agent and its passivation method and a method for preparing a semiconductor thin film. The semiconductor thin film is further post-treated, and the semiconductor thin film is prepared through solution post-treatment or chemical vapor deposition post-treatment or The post-treatment method of vacuum evaporation adds some passivating agent to the semiconductor film and deposits between the semiconductor film and the interface material in contact with it.

In order to achieve this goal, we have searched for a series of materials with both Lewis acid properties and Lewis base properties. They are used as passivation materials and added to the perovskite material and/or deposited on the perovskite material and its interface. Among the materials, the stability of the prepared perovskite solar cell is greatly improved.

Technical solutions

The present invention is realized by providing a passivation agent, which is deposited between the semiconductor film and the interface material in contact with it, and/or added to the raw material for preparing the semiconductor film. The molecule has the characteristics of both Lewis acid and Lewis base, that is, it has both electron-rich groups to donate electrons and electron acceptor sites. Among them, the molecules with electron-rich groups to donate electrons usually contain N, P For compound molecules of any one of, O, and S, the electron acceptor site is generally a metal cation with an empty orbital or an electron-poor group.

Specifically, the passivating agent is imidazole salt ionic liquid, pyridine salt ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, pyrrolidine salt ionic liquid, piperidine salt ionic liquid, functional At least one of the ionic liquids, or at least one of the ferrocene organics, or at least one of the metal phthalocyanine compounds, or at least one of the metal acetylacetone compounds, or organic metal At least one of them is either at least one of halogen bond compounds or at least one of organoborides.

The present invention is achieved in this way and also provides a passivation method, which deposits the passivation agent as described above between the semiconductor film and the interface material in contact with it, and/or adds it to the raw material for preparing the semiconductor film.

The present invention is realized in this way, and also provides a method for preparing a semiconductor thin film. The semiconductor thin film to be prepared is a perovskite thin film of a perovskite solar cell, which includes the following steps:

Step 1. Add the passivation agent AD as described above to the solvent S and stir to obtain the passivation agent solution AD-S;

Step 2. Evenly coat the passivation agent solution AD-S on the surface of the prepared perovskite film layer;

Step 3. Then the substrate coated with the passivator solution AD-S is dried, and after drying, a passivation layer is obtained on the perovskite film layer;

Wherein, the solvent S in step 1 includes amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, aromatics At least one of hydrocarbon solvents.

Step I: Add the passivation agent AD as described above to the solvent S and stir to obtain the passivation agent solution AD-S;

Step II, uniformly coat the passivator solution AD-S on the surface of the hole transport layer or electron transport layer that has been prepared;

Step III: Then, the substrate coated with the passivator solution AD-S is dried, and after drying, a passivation layer is obtained on the hole transport layer or the electron transport layer.

Step 1. Add the passivation agent AD as described above to the precursor solution PS for preparing the perovskite film layer to obtain the perovskite precursor solution AD-PS containing the passivator AD;

Step 2: The perovskite precursor solution AD-PS is subjected to the preparation of the conventional perovskite film layer to obtain the perovskite film layer containing the passivator.

Beneficial effect

Compared with the prior art, the passivation method of the passivation agent of the present invention and the method for preparing a semiconductor film, the passivation agent is deposited between the semiconductor film and the interface material in contact with it, and/or added to the preparation of the semiconductor film Among the raw materials, it provides a uniform and stable reaction environment for the passivator and the semiconductor film material, which can control the crystal growth of the semiconductor film during the preparation process, and improve the quality, uniformity and repeatability of the semiconductor film formation. The method of the invention is applied to the technical field of perovskite solar cell preparation and greatly improves the stability of the perovskite solar cell.

Description of the drawings

Figure 1 is a schematic diagram of the molecular structure in a perovskite film in the prior art;

2 is a comparison curve of the open circuit voltage change of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius;

Figure 3 is a comparison curve of short-circuit current changes between the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius;

Figure 4 is a comparison curve of the fill factor changes of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius;

Figure 5 is a comparison curve of the efficiency change of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent under the condition of continuous heating at 85 degrees Celsius;

Figure 6 shows the open circuit voltage change of the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent under the condition of continuous exposure to simulated standard sunlight intensity (1 sun) Situation comparison curve;

Figure 7 shows the short-circuit current change of the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent under the condition of continuous exposure to simulated standard sunlight intensity (1 sun) Situation comparison curve;

Figure 8 shows the change of the fill factor of the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent under the condition of continuous irradiation of simulated standard sunlight intensity (1 sun) Situation comparison curve;

Figure 9 shows the open circuit efficiency change of the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent under the condition of continuous irradiation of simulated standard sunlight intensity (1 sun) Situation comparison curve;

FIG. 10 is a current-voltage comparison diagram of the perovskite solar cell prepared in Example 12 (with passivation agent added) and the perovskite solar cell without passivation agent.

The best mode of the invention

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the following further describes the present invention in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.

Please refer to FIG. 2 for a preferred embodiment of the passivation agent of the present invention. The passivation agent is deposited between the semiconductor film and the interface material in contact with it, and/or is added to the raw material for preparing the semiconductor film. The passivating agent is imidazole salt ionic liquid, pyridine salt ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, pyrrolidine salt ionic liquid, piperidine salt ionic liquid, functionalized ionic liquid At least one of the ferrocene-based organic compounds, or at least one of the metal phthalocyanine compounds, or at least one of the metal acetylacetonate compounds, or at least one of the organometallic compounds One is either at least one of halogen bond compounds or at least one of organoborides.

The imidazole ionic liquid includes 1-hexyl-2,3-dimethylimidazolium hexafluorophosphate (1-hexyl-2,3-dimethylimidazolium hexafluorophosphate), 1-hexadecyl-2,3-dimethylimidazolium hexafluorophosphate (1-hexadecyl-2,3-dimethylimidazolium hexafluorophosphate), 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate (1-hexyl-2,3-dimethylimidazolium tetrafluoroborate), 1-hexyl-2,3-dimethylimidazolium bromide (1-hexyl-2,3-dimethylimidazolium bromide), 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-butyl-2,3-dimethylimidazolium) bis(trifluoromethylsulfonyl)amine), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate), 1-butyl-2,3-dimethylimidazolium chloride salt (1-butyl-2,3-dimethylimidazolium chloride), 1-hexadecyl-3-methylimidazolium bromide (1-hexadecyl-3-methylimidazolium bromide), 1-hexadecyl-3-methylimidazolium chloride (1-hexadecyl-3-methylimidazolium chloride) , 1-tetradecyl-3-methylimidazolium bromide (1-tetradecyl-3-methylimidazolium bromide), 1-tetradecyl-3-methylimidazolium chloride (1-tetradecyl-3-methylimidazolium chloride), 1 -Dodecyl-3-methylimidazolium hexafluorophosphate (1-dodecyl-3-methylimidazolium hexafluorophosphate), 1-dodecyl-3-methylimidazolium tetrafluoroborate (1-dodecylimidazolium tetrafluoroborate), 1- 1-dodecyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-decyl -3-methylimidazolium hexafluorophosphate (1-decyl-3-methylimidazolium hexfluorophosphate), 1-decyl-3-methylimidazolium tetrafluoroborate (1-decyl-3-methylimidazolium tetrafluoroborate), 1-decyl 1-decyl-3-methylimidazolium bromide, 1-decyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide Methylimidazole bis(trifluoromethanesulfonyl)imide salt (1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-octyl-3-methylimidazolium hexafluorophosphate (1-octyl-3-methylimidazolium hexafluorophosphate), 1-octyl-3-methylimidazolium tetrafluoroborate (1-octyl-3-methylimidazolium tetrafluoroborate), 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium brimide), 1-octyl-3-methylimidazolium chloride (1-octyl-3-methylimidazolium chloride), 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-hexyl -3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide), 1-hexyl-3-methylimidazolium hexafluorophosphate (1-hexyl-3-methylimidazolium hexafluorophosphate), 1-hexyl-3-methylimidazolium tetrafluoroborate (1-hexyl-3-methylimidazolium tetrafluoroborate), 1-hexyl-3-methylimidazolium bromide (1-hexyl-3-methylimidazolium brimide), 1-hexyl-3-methylimidazolium chloride, 1-pentyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium chloride, 1-pentyl-3-methylimidazolium hexafluorophosphate, 1-pentyl-3-methylimidazolium tetrafluoroborate (1-pentyl-3-methylimidazolium tetrafluoroborate), 1-pentyl-3-methylimidazolium bromide, 1 -Pentyl-3-methylimidazolium chloride (1-pentyl-3-methylimidazolium chloride), 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-Propyl-3- MethyliMidazoliuM bis(trifluoroMethylsulfonyl)imide), 1-propyl-3-methylimidazole hexafluorophosphate (1-propyl-3-methyl imidazolium hexafluorophosphate), 1-butyl-3-methylimidazolium acetate (1-butyl-3-methylimidazolium acetate), 1-butyl-3-methylimidazolium tosylate (1-butyl-3-methylimidazolium tosylate), 1-butyl-3-methylimidazolium tosylate (1-butyl- 3-methylimidazolium thiocyanate), 1-butyl-3-methylimidazolium trifluoroacetate (1-butyl-3-methylimidazolium trifluoroacetate), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (1 -butyl-3-methylimidazolium trifluoromethansulfonate), 1-butyl-3-methylimidazolium dicyanamide), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-butyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide), 1-butyl-3-methylimidazolium perchlorate perchlorate), 1-butyl-3-methylimidazolium dihydrogen phosphate, 1-butyl-3-methylimidazolium dihydrogen phosphate (1-butyl-3-methylimidazolium dihydrogen phosphate) hydrogen sulfate), 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium hexafluorophosphate ), 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium tetrafluoroborate), 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) , 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-propane 3-methylimidazolium iodide (1-propyl-3-methylimidazolium iodide), 1-propyl-3-methylimidazolium tetrafluoroborate, 1-propyl -3-methylimidazolium bromide (1-propyl-3-methylimidazolium bromide), 1-propyl-3-methylimidazolium chloride, 1-ethyl-3-methyl 1-Ethyl-3-methylimidazolium acetate, 1-Ethyl-3-methylimidazolium tosylate, 1-Ethyl-3-methylimidazolium tosylate, 1-Ethyl-3-methylimidazolium tosylate -Methylimidazole thiocyanate (1-Ethyl-3-methylimidazolium thiocyanate), 1-Ethyl-3-methylimidazolium trifluoroacetate (1-Ethyl-3-methylimidazolium trifluoroacetate), 1-ethyl- 3-Methylimidazolium trifluoromethanesulfonate (1-Ethyl-3-methylimidazolium trifluoromethanesulfonate) , 1-Ethyl-3-methylimidazolium dicyanamide (1-Ethyl-3-methylimidazolium dicyanamide), 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium dicyanamide (1- Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-Ethyl-3-methyl-1H-imidazolium perchlorate perchlorate), 1-Ethyl-3-methylimidazolium hydrogen sulfate (1-Ethyl-3-methylimidazolium hydrogen sulfate), 1-Ethyl-3-methylimidazolium nitrate (1-Ethyl-3-methylimidazolium nitrate) , 1-ethyl-3-methylimidazolium hexafluorophosphate (1-ethyl-3-methylimidazolium hexafluorophosphate), 1-ethyl-3-methylimidazolium iodine, 1 -Ethyl-3-methylimidazolium bromide (1-ethyl-3-methylimidazolium bromide), 1-ethyl-3-methylimidazolium chloride, 1-ethyl- 3-methylimidazolium tetrafluoroborate (1-ethyl-3-methylimidazolium tetrafluoroborate).

The pyridine salt ionic liquid includes N-octyl pyridine bromide (N-octyl pyridinium bromide), N-hexyl pyridinium bis(trifluoromethyl sulfonyl)imide), N-hexyl pyridinium hexafluorophosphate, N-hexyl pyridinium hexafluorophosphate (N-hexyl pyridinium tetrafluoroborate), N-hexyl pyridinium bromide, N-butyl pyridinium bis(trifluoromethanesulfonyl) imide salt (N-butyl pyridinium bis(trifluoromethyl sulfonyl)imide), N-butyl pyridinium hexafluorophosphate, N-butyl pyridinium hexafluorophosphate pyridinium tetrafluoroborate), N-butyl pyridinium bromide, N-ethylpyridinium bis(trifluoromethanesulfonyl) imide salt (N-ethyl pyridinium bis(trifluoromethyl sulfonyl)imide), N-ethylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate tetrafluoroborate), N-ethylpyridinium bromide.

The quaternary ammonium salt ionic liquid includes tributylmethylammonium bis(trifluoromethanesulfonyl)imide salt (Tributylmethylammonium bis(trifluoromethyl sulfonyl)imide), tributylmethylammonium chloride chloride), N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate (N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate).

The quaternary phosphonium salt ionic liquid tributylhexylphosphonium bis(trifluoromethanesulfonyl)imide (Tributylhexylphosphonium) bis(trifluoromethyl sulfonyl)imide), tributylhexylphosphonium bromide Bromide), tetrabutylphosphonium bis(trifluoromethanesulfonyl) imide salt (Tetrabutylphosphonium bis(trifluoromethyl sulfonyl)imide), Tetrabutylphosphonium bromide (Tetrabutylphosphonium bromide), tributyl ethyl phosphine bis (trifluoromethanesulfonyl) imide salt (Ethyltributylphosphonium bis(trifluoromethyl sulfonyl)imide), tributylethyl phosphonium bromide (Ethyltributylphosphonium bromide).

The pyrrolidine salt ionic liquid includes N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide salt (N-butyl-N-methylpyrrolidinium) bis(trifluoromethyl sulfonyl)imide), N-butyl-N-methylpyrrolidinium bromide (N-butyl-N-methylpyrrolidinium bromide).

The piperidine salt ionic liquid includes N-butyl-N-methylpiperidine bis(trifluoromethanesulfonyl) imide salt (1-Butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide), N-butyl-N-methylpiperidinium bromide (1-Butyl-1-methylpiperidinium Bromide).

The functionalized ionic liquid includes guanidine hydrochloride, guanidine carbonate, and tetramethylguanidine lactate. lactate), tetramethylguanidine trifluoromethanesulfonate (tetramethylguanidine trifluoromethanesulfonate), tetramethylguanidine hydrogen sulfate hydrogensulfate), tetramethylguanidine hydrochloride (tetramethylguanidine chloride), 1-carboxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-carboxyethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide), 1-carboxyethyl-3-methylimidazolium nitrate (1-carboxyethyl-3-methylimidazolium nitrate), 1-carboxyethyl-3-methylimidazolium hydrogensulfate (1-carboxyethyl-3-methylimidazolium hydrogensulfate), 1-carboxyethyl-3-methylimidazolium bromide (1-carboxyethyl-3-methylimidazolium bromide) ), 1-carboxyethyl-3-methylimidazolium chloride (1-carboxyethyl-3-methylimidazolium chloride), 1-carboxymethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1 -carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonate)imine), 1-carboxymethyl-3-methylimidazolium nitrate (1-carboxymethyl-3-methylimidazolium nitrate), 1-carboxymethyl-3-methylimidazolium hydrogensulfate (1-carboxymethyl-3-methylimidazolium hydrogensulfate), 1-carboxymethyl-3-methylimidazolium bromide ), 1-carboxymethyl-3-methylimidazolium chloride (1-carboxymethyl-3-methylimidazolium chloride), 1-ethyl acetate-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt ( 1-((ethoxycarbonyl)methyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-((ethoxycarbonyl)methyl)-3-methylimidazolium hexafluorophosphate), 1-((ethoxycarbonyl)methyl)-3-methylimidazolium tetrafluoroborate), 1-((ethoxycarbonyl)methyl)-3-methylimidazolium bromide), 1-((ethoxycarbonyl)methyl)-3-methylimidazolium chloride, 1-benzyl-3-methylimidazole bis(trifluoromethanesulfonyl ) Imine salt (1-Benzyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-Benzyl-3-methylimidazolium hexafluorophosphate (1-Benzyl-3-methylimidazolium hexafluorophosphate), 1-Benzyl-3-methylimidazolium tetrafluoroborate (1-Benzyl-3-methylimidazolium tetrafluoroborate), 1-Benzyl-3-methylimidazolium bromide (1-Benzyl-3-methylimidazolium bromide), 1-Benzyl-3-methylimidazolium chloride (1-Benzyl-3-methylimidazolium chloride), 1-ethyl ethyl ether-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (1-Ethoxyethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-Ethoxyethyl-3-methylimidazolium hexafluorophosphate), 1-Ethoxyethyl-3-methylimidazolium tetrafluoroborate (1-Ethoxyethyl-3-methylimidazolium tetrafluoroborate), 1-Ethoxyethyl-3-methylimidazolium bromide (1-Ethoxyethyl-3-methylimidazolium bromide), 1-Ethyl methyl ether-3-methylimidazolium hexafluorophosphate (1-Methoxyethyl-3-methylimidazolium hexafluorophosphate), 1-Ethyl methyl ether-3-methylimidazolium hexafluorophosphate ( 1-Methoxyethyl-3-methylimidazolium tetrafluoroborate), 1-ethyl methyl ether-3-methylimidazolium bromide (1-Methoxyethyl-3-methylimidazolium bromide), 1-vinyl-3-butylimidazolium bistrifluoromethane Sulfonimide salt (1-vinyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide), 1-vinyl-3-butylimidazolium hexafluorophosphate (1-vinyl-3-butylimidazolium hexafluorophosphate), 1-vinyl-3-butylimidazolium tetrafluoroborate (1-vinyl-3-butylimidazolium tetrafluoroborate), 1-vinyl-3-butylimidazolium bromide (1-vinyl-3-butylimidazolium bromide), 1-vinyl-3-ethylimidazolium bistrifluoromethanesulfonimide salt (1-vinyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide), 1-vinyl-3-ethylimidazolium hexafluorophosphate (1-vinyl-3-ethylimidazolium hexafluorophosphate), 1-vinyl-3-ethylimidazolium tetrafluoroborate (1-vinyl-3-ethylimidazolium tetrafluoroborate), 1-vinyl-3-ethylimidazolium bromide (1-vinyl-3-ethylimidazolium bromide), 1-vinyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt (1-vinyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-vinyl-3-methylimidazolium iodide), 1-allyl-3-butyl imidazolium bis(trifluoromethanesulfonyl) imide salt (1-allyl-3-butyl imidazolium) bis(trifluoromethylsulfonyl)imide), 1-allyl-3-butyl imidazole hexafluorophosphate imidazolium hexafluorophosphate), 1-allyl-3-butyl imidazole tetrafluoroborate (1-allyl-3-butyl imidazolium tetrafluoroborate), 1-allyl-3-butyl imidazole bromide (1-allyl-3-butyl imidazolium bromide), 1-allyl-3-ethylimidazole bis(trifluoromethanesulfonyl) imide salt (1-allyl-3-ethyl imidazolium bis(trifluoromethylsulfonyl)imide), 1-allyl-3-ethylimidazole hexafluorophosphate (1-allyl-3-ethyl imidazolium hexafluorophosphate), 1-allyl-3-ethyl imidazole tetrafluoroborate (1-allyl-3-ethyl imidazolium tetrafluoroborate), 1-allyl-3-ethyl imidazole bromide (1-allyl-3-ethyl imidazolium bromide), 1-allyl-3-ethyl imidazole chloride salt (1-allyl-3-ethyl imidazolium chloride), 1-allyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt (1-allyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide), 1-allyl-3-methyl hexafluorophosphate (1-allyl-3-methyl imidazolium hexafluorophosphate), 1-allyl-3-methyl imidazole tetrafluoroborate (1-allyl-3-methyl imidazolium tetrafluoroborate), 1-allyl-3-methyl imidazole bromide (1-allyl-3-methyl imidazolium bromide), 1-allyl-3-methyl imidazole chloride salt (1-allyl-3-methyl imidazolium chloride), 1-cyanopropyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt (1-cyanopropyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide), 1-cyanopropyl-3-methylimidazole nitrate (1-cyanopropyl-3-methyl imidazolium nitrate), 1-cyanopropyl-3-methyl hexafluorophosphate (1-cyanopropyl-3-methyl imidazolium hexafluorophosphate), 1-cyanopropyl-3-methyl tetrafluoroborate (1-cyanopropyl-3-methyl imidazolium tetrafluoroborate), 1-cyanopropyl-3-methylimidazole chloride salt (1-cyanopropyl-3-methyl imidazolium chloride), 1,2-dimethyl-3-hydroxyethyl imidazole p-toluenesulfonate (1,2-dimethyl-3-hydroxyethyl imidazolium tosylate), 1,2-dimethyl-3-hydroxyethyl imidazole bis(trifluoromethanesulfonyl) imide salt (1,2-dimethyl-3-hydroxyethyl imidazolium bis(trifluoromethylsulfonyl)imide), 1,2-dimethyl-3-hydroxyethylimidazole hexafluorophosphate (1,2-dimethyl-3-hydroxyethyl imidazolium hexafluorophosphate), 1,2-dimethyl-3-hydroxyethyl imidazole tetrafluoroborate (1,2-dimethyl-3-hydroxyethyl imidazolium tetrafluoroborate), 1-hydroxyethyl-2,3-dimethylimidazole chloride salt (1-hydroxyethyl-2,3-dimethyl imidazolium chloride), 1-hydroxyethyl-3-methylimidazole bisulfate (1-hydroxyethyl-3-methyl imidazolium thiocyanate), 1-hydroxyethyl-3-methylimidazole p-toluenesulfonate (1-hydroxyethyl-3-methyl imidazolium tosylate), 1-hydroxyethyl-3-methylimidazolium tosylate (1-hydroxyethyl-3-methyl imidazolium dicyanamide), 1-hydroxyethyl-3-methylimidazole bis(trifluoromethanesulfonyl) imide salt (1-hydroxyethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide), 1-hydroxyethyl-3-methylimidazole perchlorate (1-hydroxyethyl-3-methyl imidazolium perchlorate), 1-hydroxyethyl-3-methylimidazole nitrate (1-hydroxyethyl-3-methyl imidazolium nitrate), 1-hydroxyethyl-3-methylimidazolium hexafluorophosphate (1-hydroyethyl-3-methylimidazolium hexafluorophosphate), 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate (1-hydroxyethyl-3-methylimidazolium tetrafluoroborate), 1-hydroxyethyl-3-methylimidazolium chloride salt (1-hydroxyethyl-3-methylimidazolium chloride), trimethylhydroxyethylammonium bis(trifluoromethanesulfonyl)imide salt (2-hydroxyethyl trimethylammonium bis(trifluoromethylsulfonyl)imine), 2-hydroxyethyl trimethylammonium phosphate hexafluorophosphate), trimethylhydroxyethylammonium tetrafluoroborate (2-hydroxyethyl trimethylammonium tetrafluoroborate), trimethylhydroxyethylammonium chloride (2-hydroxy-N,N,N- trimethyl ethylanammonium chloride), N-butylsulfonate pyridinium tosylate, N-butylsulfonate trifluoromethanesulfonate pyridinium trifluoromethanesulfonate), N-butylsulfonic pyridinium hydrogensulfate, pyridinium butylsulfonate, N-propylsulfonate pyridinium tosylate), N-propylsulfonate trifluoromethanesulfonate pyridinium trifluoromethanesulfonate), N-propylsulfonate pyridinium hydrogensulfate, pyridinium propylsulfonate, 1-butanesulfonic acid-3-methylimidazole trifluoroacetic acid Salt (1-butylsulfonate-3-methylimidazolium trifluoroacetate), 1-butylsulfonate-3-methylimidazolium trifluoromethanesulfonate (1-butylsulfonate-3-methylimidazolium trifluoromethanesulfonate), 1-butylsulfonate-3-methylimidazolium hydrogen sulfate bisulfate), 1-butylsulfonate-3-methylimidazolium dihydrogen phosphate), 1-butylsulfonate-3-methylimidazolium chloride, 1-butylsulfonate-3-methylimidazolium ), 1-propylsulfonate-3-methylimidazolium trifluoroacetate, 1-propylsulfonate-3-methylimidazolium trifluoroacetate (1 -propylsulfonate-3-methylimidazolium trifluoromethanesulfonate), 1-propylsulfonate-3-methylimidazolium hydrogen sulfate (1-propylsulfonate-3-methylimidazolium hydrogensulfate), 1-propylsulfonate-3-methylimidazolium dihydrogen phosphate (1-propylsulfonate-3-methylimidazolium dihydrogen phosphate), 1-propylsulfonate-3-methylimidazolium chloride salt (1-propylsulfonate-3-methylimidazolium chloride), 1-propylsulfonate -3-methylimidazolium (1-propylsulfonate -3-methylimidazolium), 1-aminopropyl-3-methylimidazolium nitrate (1-aminopropyl-3-methylimidazolium nitrate) , 1-aminopropyl-3-methylimidazole bis(trifluoromethanesulfonyl) imide salt (1-aminopropylimidazolium bis(trifluoromethylsulfonyl)imine), 1-aminopropylimidazolium hexafluorophosphate (1-aminopropylimidazolium hexafluorophosphate), 1-aminopropyl-3-methylimidazolium tetrafluoroborate (1-aminopropyl-3-methylimidazolium tetrafluoroborate), 1-aminopropyl-3-methylimidazolium bromide (1-aminopropyl-3-methylimidazolium bromide), 1-aminoethyl-3-methylimidazolium nitrate (1-aminoethyl-3-methylimidazolium nitrate), 1-aminoethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt ( 1-(2-aminoethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-aminoethyl-3-methylimidazolium hexafluorophosphate (1-aminoethyl-3-methylimidazolium hexafluorophosphate), 1-aminoethyl-3-methylimidazolium tetrafluoroborate (1-aminoethyl-3-methylimidazolium tetrafluoroborate), 1-aminoethyl-3-methylimidazole bromide (1-aminoethyl-3- methylimidazolium bromide).

The ferrocene organics include 1,1'-bis(dicyclohexylphosphine)-ferrocene, ferrocene acetic acid, N,N-dimethyl ferrocene methylamine, acetyl ferrocene, two Ferrocene carboxylic acid, 6-(ferrocenyl) hexyl mercaptan, 1,1′-bis(dichlorophosphorus) ferrocene, 1,1′-bis(diisopropylphosphine) ferrocene, 1, 1'-bis(diphenylphosphine)ferrocene, (S)-(-)-N,N-dimethyl-1-ferrocenylethylamine, 1,1'-bis(di-tert-butyl Phosphino)ferrocene, 1,1'-ferrocene dicarboxylic acid, (S)-(+)-N,N-dimethyl-1-(2-biphenylphosphino)ferrocene ethylamine , (R)-(-)-N,N-dimethyl-1-(2-biphenylphosphino)ferroceneethylamine, (R)-N,N-dimethyl-1-[(S )-1',2-bis(diphenylphosphino)ferrocenyl)ethylamine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphine)ferrocene , 1,1'-bis(di-tert-butylphosphine)ferrocene dichloropalladium, (S)-1-(diphenylphosphino)-2-[(S)-4-isopropyloxa Azolin-2-yl]ferrocene, 1,1'-diacetylferrocene, (R)-N-diphenylphosphine-N-methyl-(S)-2-(diphenylphosphine )Ferrocenyl ethylamine, (S)-N,N-dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine, 1, 1′-bis(di-cyclohexylphosphino)ferrocene palladium dichloride, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, [1,1′-bis (Diphenylphosphine)ferrocene]cobalt(II) dichloride, (S)-1-{(RP)-2-[bis(2-furyl)phosphino]ferrocenyl}ethyl dichloride (3,5-Xylyl)phosphinoferrocenecarboxylic acid, N-succinimide ester.

The metal phthalocyanine compound includes copper (II) phthalocyanine, iron (II) phthalocyanine, lead phthalocyanine (II), aluminum phthalocyanine, cobalt phthalocyanine (II), dilithium phthalocyanine, and dichlorophthalocyanine Tin (IV), zinc phthalocyanine, copper perfluorophthalocyanine.

The metal acetylacetonate includes zirconium acetylacetonate, iron acetylacetonate, zinc acetylacetonate, copper acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, hafnium acetylacetonate, aluminum acetylacetonate, and rhodium acetylacetonate bis(ethylene) (I), rhodium dicarbonyl acetylacetonate, vanadium acetylacetonate, cadmium acetylacetonate, calcium acetylacetonate, vanadyl acetylacetonate, molybdenum acetylacetonate, iridium dicarbonyl acetylacetonate (I), bis(hexafluoroacetylacetone) copper ( II) Hydrate, tin acetylacetonate, bis(2,4-pentanedionate) tin(IV) dichloride, palladium(II) hexafluoroacetylacetonate, terbium(III) acetylacetonate, iridium acetylacetonate( Ⅲ), acetylacetonate platinum (II), bis (2,4-pentanedione) manganese, tris (2,4-pentanedionate) chromium (III), bis (acetylacetonate) palladium (II), double ( Acetylacetonyl) diisopropyl titanate, silver acetylacetonate, yttrium (III) acetylacetonate, lanthanum acetylacetonate, gallium acetylacetonate (III), barium acetylacetonate, ruthenium acetylacetonate, magnesium acetylacetonate, manganese acetylacetonate, Acetylacetone (norbornadiene) rhodium, acetylacetonate bis(2-phenylpyridine)iridium.

The organic metal includes two-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine) copper (II)] chloride, bromotris (triphenylphosphine) copper (I ), copper gluconate, copper tartrate (II) hydrate, copper citrate, copper pyrophosphate, copper acetate, copper thiophene-2-carboxylate, copper 8-hydroxyquinoline salt, chlorine [1,3-bis(2 ,6-Diisopropylphenyl)imidazole-2-ylidene) copper(I), disodium copper ethylenediaminetetraacetate, copper(II) dimethyldithiocarbamate, bis(2,2,6 ,6,-Tetramethyl-3,5-Heptanedioic Acid) Copper, Bis(6,6,7,7,8,8,8,-Heptafluoro-2,2-Dimethyl-3,5 -Octanedionate) copper, copper(II)-TBTA complex, 1,5-cyclooctadiene (hexafluoro-2,4-pentanedione) copper(I), dimethyldithioamino Copper formate, magnesium citrate, iron (III) diethyldithiocarbamate, disodium ethylenediaminetetraacetic acid calcium analgin (Na), disodium manganese diaminetetraacetic acid, stannous isooctanoate, triphenyl Base tin chloride, dimethyl tin dichloride, dimethyl tin oxide, trimethyl (4-pyridyl) tin, trimethyl (2-pyridyl) tin, monochlorodiethyl aluminum, bis( 2-ethylhexanoic acid) aluminum hydroxy, aluminum glycine, 2-thienyl zinc bromide.

The halogen bond compound includes 4-iodonitrobenzene, 1-fluoro-3-iodo-5-nitrobenzene, 2-nitro-3,5-difluoroiodobenzene, 4-bromo-2-fluorobenzonitrile , 4-Bromo-2,3,5,6-tetrafluorobenzoic acid, 4-bromo-2,3-difluorobenzonitrile, 4 4'-dibromooctafluorobiphenyl.

The organic borides include tetrabutylammonium borohydride, 3-nitrophenylboronic acid, trimethyl borate, 3-thiopheneboronic acid, 3-furanboronic acid, 4-formylphenylboronic acid, 3-aminophenylboronic acid, 4- Mercaptophenylboronic acid, 4-(bromomethyl)phenylboronic acid, 4-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, 5-aldehyde-2-methoxyphenylboronic acid, 5-formaldehyde furan -2-boronic acid, 2-fluoro-5-bromopyridine-3-boronic acid, 2-fluoropyridine-3-boronic acid, 2,5-dichloropyridine-4-boronic acid, benzothiophene-2-boronic acid, 3-quinone Phosphoboronic acid, thiophene-2-boronic acid pinacol ester, 4-aminophenylboronic acid pinacol ester, 3-ethoxycarbonylphenylboronic acid pinacol ester, 4-methoxycarbonylphenylboronic acid pinacol ester, 3-methyl Oxyphenyl boronic acid, 4-phenylether phenyl boronic acid, 3,5-dimethylisoxazole-4-boronic acid pinacol ester, 6-isopropoxypyridine-3-boronic acid pinacol ester, 3 ,6-Dihydro-2H-pyran-4-boronic acid pinacol ester, pyrimidine-5-boronic acid, 5-aldehyde-2-thiophene boronic acid, 4-fluoro-3-aldehyde phenylboronic acid, 2-cyano Phenylboronic acid, 1,3-propane diester, 3,5-dicarboxyphenylboronic acid, (2,6-dimethylpyridin-4-yl)boronic acid 2-(Methoxycarbonyl)phenylboronic acid, phenylboronic acid, triethyl borate, 3-fluoro-4-aldehyde phenylboronic acid, 4-carboxyphenylboronic acid, sodium tetraborate, 4-fluorophenylboronic acid, 3-iodine Phenylboronic acid, 2-fluorophenylboronic acid, 4-isopropoxyphenylboronic acid, 4-vinylbenzeneboronic acid, 4'-(4,4,5,5-tetramethyl-1,3,2-dioxide Pentaborane-2-yl)acetanilide, 3-bromophenylboronic acid, N-methyldiaminoethanol ester, 2,6-dichloropyridine-3-boronic acid, tris(4-chlorophenyl) borate, tris( 2-cyanoethyl) borate, triethanolamine borate, 4,4,5,5-tetramethyl-2-[3-(trifluoromethoxy)phenyl]-1,3,2-di Oxalane, 4-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]morpholine, 4,4 ,5,5-Tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxaborolane, 5-(4,4,5,5-tetramethyl-1, 3,2-Dioxaborolan-2-yl)oxindole, 1-(tert-butoxycarbonyl)-4-(4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl)pyrazole, 4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl )Thiophene, 2-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, 2-(4-methoxy Benzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane, 3-methyl-2-(4,4,5,5-tetramethyl-1 ,3,2-Dioxaborane-2-yl)thiophene, N,N-diethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxane Pentaborane-2-yl)aniline, 2-bromo-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine, 2-cyano 1,3-propanediol phenylboronic acid, 2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine .

The invention also discloses a passivation method, which deposits the passivation agent as described above between the semiconductor film and the interface material in contact with it, and/or adds it to the raw material for preparing the semiconductor film.

The invention also discloses a method for preparing a semiconductor thin film. The semiconductor thin film to be prepared is a perovskite thin film of a perovskite solar cell, which comprises the following steps:

Step 1. Add the passivator AD as described above to the solvent S and stir to obtain the passivator solution AD-S, wherein the mass volume ratio of the passivator AD to the solvent S is 0.1 mg/mL to 100 mg/mL.

Step 2. Evenly coat the passivator solution AD-S on the surface of the prepared perovskite film layer.

Step 3. Then dry the substrate coated with the passivator solution AD-S, and the drying conditions are: 60℃~200℃, baking for 0.1 minute to 100 minutes, and then on the perovskite film layer A passivator layer is obtained.

In step 1, the solvent S is N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), At least one of 1,8-diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), chlorobenzene (CB), and toluene.

The present invention also discloses another method for preparing a semiconductor film, which is characterized in that the semiconductor film to be prepared is a perovskite film of a perovskite solar cell, which comprises the following steps:

Step I: Add the passivator AD as described above to the solvent S and stir to obtain the passivator solution AD-S, wherein the mass volume ratio of the passivator AD to the solvent S is 0.1 mg/mL-100 mg/mL.

Step II: uniformly coat the passivator solution AD-S on the surface of the hole transport layer or the electron transport layer that has been prepared.

Step III. Then dry the substrate coated with the passivator solution AD-S, and the drying conditions are: baking at a temperature of 60 ℃ ~ 300 ℃ for 0.1 minutes to 100 minutes, after drying, in the hole transport layer or electron A passivator layer is obtained on the transmission layer.

The invention also discloses another method for preparing a semiconductor thin film, including the following steps:

Step 1. Add the passivation agent AD as described above to the precursor solution PS (including the one-step perovskite precursor solution or the two-step precursor solution) for preparing the perovskite thin film layer to obtain Perovskite precursor solution AD-PS containing passivator AD.

In step 1, the ratio of adding the passivation agent AD to the precursor solution PS for preparing the perovskite film is: the molar ratio of the passivation agent AD to the total halogen of the precursor solution PS is 1:100,000~ 1:1.

Embodiments of the invention

The method of the present invention will be further described below in conjunction with specific embodiments.

Example 1

Embodiment 1 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(1) Clean the ITO transparent conductive glass and treat the surface with plasma for use.

(2) Prepare CuI hole transport layer on ITO, adopt slit coating method, thickness 30nm.

(3) Add the passivating agent-1-octyl-3-methylimidazole bromide to methanol solvent to prepare a solution with a mass volume ratio of 1 mg/mL. The solution was evenly coated on the surface of the hole transport layer material, and then baked at 100 degrees for 5 minutes.

(4) Prepare a perovskite layer on the hole transport layer coated with a passivator, and use a co-evaporation method to obtain a FAMACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 500 nm.

(5) An electron transport layer PCBM is prepared on the perovskite film layer, and a PCBM layer with a thickness of 10 nm is obtained by the slit coating method.

(6) An electrode layer Ag is prepared on the electron transport layer, and an electrode layer with a thickness of 200 nm is obtained by using an evaporation method. Continue and finally prepare perovskite solar cells.

Example 2

Embodiment 2 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(3) Prepare a perovskite layer on the hole transport layer, and use a co-evaporation method to obtain a FAMACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 500 nm.

(4) Add the passivating agent-1-octyl-3-methylimidazole bromide to methanol solvent to prepare a solution with a mass volume ratio of 1mg/mL. The solution was evenly coated on the perovskite film layer, and then baked at 100 degrees for 5 minutes.

(6) An electrode layer Ag is prepared on the electron transport layer, and an electrode layer with a thickness of 200 nm is obtained by an evaporation method. Continue and finally prepare perovskite solar cells.

Example 3

Embodiment 3 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(1) Clean the ITO transparent conductive glass and prepare it for use after plasma treatment of the surface.

(2) NiO hole transport layer is prepared on ITO, using slit coating method, thickness 30nm.

(3) Add passivating agent-1-hexyl-2,3-dimethylimidazole tetrafluoroborate to the perovskite precursor solution PS, the molar ratio of the passivation agent to the total halogen in the solution PS 1:1000, mix well.

(4) Prepare a perovskite layer using the solution PS obtained in step (3) on the hole transport layer, and use a doctor blade coating method to obtain FAMACsPb(I _X Br _1-X ) ₃ perovskite with a thickness of 500 nm.

(5) An electron transport layer ZnO is prepared on the perovskite film layer, and a ZnO layer with a thickness of 100 nm is obtained by spraying.

(6) An electrode layer Al is prepared on the electron transport layer, and an electrode layer with a thickness of 200 nm is obtained by an evaporation method. Continue and finally prepare perovskite solar cells.

Example 4

Embodiment 4 of a method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(1) Clean the FTO transparent conductive glass and prepare it for use after plasma treatment of the surface.

(2) Preparation of SnO electron transport layer on FTO, using vacuum evaporation method, thickness 50nm.

(3) Add the passivation agent—1-butyl-3-methylimidazole tetrafluoroborate to the precursor solution PS1 of the two-step perovskite. PS1 is the DMF solution of lead iodide with a molar concentration of 1.2 mol/L, the molar ratio of the passivation agent to the total halogen in the solution PS1 is 1:2000, and the mixture is uniformly mixed to obtain the precursor solution PS1-AD.

(4) Prepare the perovskite layer on the electron transport layer, using inkjet printing method, and spray the precursor solution PS1-AD and the precursor solution PS2 on the electron transport layer at the same time. PS2 is a mixed isopropanol of MAI, FAI and CsI Solution to obtain a CsFAMAPbI ₃ perovskite film layer with a thickness of 400 nm.

(5) A hole transport layer C60 is prepared on the perovskite film layer, and a C60 layer with a thickness of 50 nm is obtained by an evaporation method.

(6) An electrode layer Ag is prepared on the electron transport layer, and an electrode layer with a thickness of 150 nm is obtained by an evaporation method. Continue and finally prepare perovskite solar cells.

Example 5

Embodiment 5 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(1) Clean the AZO transparent conductive glass and prepare it for use after plasma treatment of the surface.

(2) A CuSCN hole transport layer was prepared on AZO, using a bar coating method, with a thickness of 75nm.

(3) Add the passivation agent-1-propyl-3-methylimidazole tetrafluoroborate to the perovskite precursor solution PS1, which is a solution of lead iodide and lead bromide mixed in DMF, The molar concentration is 0.9 mol/L, the molar ratio of the passivating agent to the total amount of halogen (iodine and bromine) in the solution PS1 is 1:5000, and the mixture is evenly mixed to obtain the precursor solution PS1-AD.

(4) Prepare the perovskite layer on the hole transport layer, adopt the method of coating post-treatment, first spray the precursor solution PS1-AD on the hole transport layer, and then heat and dry it at 100 degrees The ethanol solution mixed with FAI and CsI is sprayed on the surface to obtain a FACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 600 nm.

(5) Prepare the electron transport layer SnO on the perovskite film layer, and use the atomic layer deposition method to obtain a dense SnO electron transport layer with a thickness of 10 nm.

(6) An electrode layer Cu is prepared on the electron transport layer, and a sputtering method is used to obtain an electrode layer with a thickness of 300 nm. Continue and finally prepare perovskite solar cells.

Example 6

Embodiment 6 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(1) Clean the BZO transparent conductive glass and prepare it for use after plasma treatment of the surface.

(2) Prepare a TiO ₂ electron transport layer on BZO by spraying method with a thickness of 120nm.

(3) Two passivating agents, passivating agent A: 1-dodecyl-3-methylimidazole tetrafluoroborate and passivating agent B: 1-octyl-3-methylimidazole tetrafluoroborate The acid salt was added to the one-step perovskite precursor solution PS containing PbI ₂ , FAI and CsI at a concentration of 1.2 mol/L at the same time. The total molar amount of passivator A and passivator B was equal to the total amount of halogen in the solution PS. The molar ratio of the amount is 1:500, and the mixture is evenly mixed to obtain the solution PS-AD12.

(4) Prepare the perovskite thin film layer on the electron transport layer, adopt one-step coating method, coat PS-AD12 on the electron transport with slits, and undergo vacuum heating treatment and methylamine gas atmosphere treatment to obtain a thickness of 380nm The FAMACsPbI ₃ perovskite film layer.

(5) A hole transport layer Spiro-OMeTAD was prepared on the perovskite film layer, and a hole transport layer with a thickness of 100 nm was obtained by the slit coating method.

(6) Au and Ag electrode layers are prepared on the hole transport layer, and an electrode layer of Au with a thickness of 20 nm and Ag with a thickness of 150 nm is obtained by an evaporation method. Continue and finally prepare perovskite solar cells.

Example 7

Embodiment 7 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(4) Prepare the perovskite film layer on the hole transport layer, and adopt the co-evaporation method to obtain the FAMACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 500 nm.

(5) An electron transport layer PCBM is prepared on the perovskite film layer, and a PCBM electron transport layer with a thickness of 10 nm is obtained by the slit coating method.

Example 8

Embodiment 8 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(3) Add passivation agent AD to the perovskite precursor solution PS (including one-step perovskite precursor solution or two-step precursor solution), passivator AD and perovskite precursor solution The molar ratio of the total amount of halogen in PS is 1:100000~1:1.

Example 9

Embodiment 9 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(3) Prepare a perovskite film layer on the hole transport layer, and use a co-evaporation method to obtain a FAMACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 500 nm.

Example 10

Embodiment 10 of a method for preparing a perovskite layer solar cell of the present invention includes the following steps:

Example 11

Embodiment 11 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(5) Prepare the electron transport layer PCBM on the perovskite layer, and use the slit coating method to obtain a PCBM electron transport layer with a thickness of 10 nm

Example 12

Embodiment 12 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(5) An electron transport layer PCBM is prepared on the perovskite film layer, and a slit coating method is used to obtain a PCBM electron transport layer with a thickness of 10 nm.

Example 13

Embodiment 13 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

Example 14

Embodiment 14 of the method for preparing a perovskite-layer solar cell of the present invention includes the following steps: (1) The ITO transparent conductive glass is cleaned, and the surface is plasma-treated for use.

(3) Prepare a perovskite film layer on the transmission layer, and adopt a co-evaporation method to obtain a FAMACsPb(I _X Br _1-X ) ₃ perovskite film layer with a thickness of 500 nm.

(4) Add the passivating agent-1-octyl-3-methylimidazole bromide to methanol solvent to prepare a solution with a mass volume ratio of 1mg/mL. The solution was evenly coated on the surface of the perovskite film layer, and then baked at 100 degrees for 5 minutes.

Example 15

Embodiment 15 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(3) Add the passivator AD to the perovskite precursor solution PS (including the one-step perovskite precursor solution or the two-step precursor solution), the moles of AD and the total halogen in the solution PS The ratio is 1:100000~1:1.

(5) Prepare the electron transport layer PCBM on the perovskite film layer, and use the slit coating method to obtain a PCBM electron transport layer with a thickness of 10 nm

Example 16

Embodiment 16 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

Example 17

Embodiment 17 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(5) An electron transport layer PCBM is prepared on the perovskite film layer, and a slit coating method is adopted to obtain a PCBM electron transport layer with a thickness of 10 nm.

Example 18

Embodiment 18 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

Example 19

Embodiment 19 of the method for preparing a perovskite layer solar cell of the present invention includes the following steps:

(3) Add the passivating agent-1-octyl-3-methylimidazole bromide to methanol solvent to prepare a solution with a mass volume ratio of 1 mg/mL. The solution was evenly coated on the hole transport layer material, and then baked at 100 degrees for 5 minutes.

(4) Prepare a perovskite thin film layer on the hole transport layer, and use a co-evaporation method to obtain a FAMACsPb(I _X Br _1-X ) ₃ perovskite thin film layer with a thickness of 500 nm.

(6) An electrode layer Ag is prepared on the electron transport layer, and an electrode layer with a thickness of 200 nm is obtained by an evaporation method.

Then, a comparative test is performed to illustrate the technical effect of the present invention.

As shown in Fig. 2, the comparison of the open circuit voltage change of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius. It can be seen from the figure that the open circuit voltage of the perovskite solar cell with passivation agent does not decay under 1000 hours of continuous heating, while the open circuit voltage of the perovskite solar cell without passivator decays after 500 hours. More than 10%. The perovskite solar cell with passivating agent has excellent open circuit voltage performance under continuous heating at 85 degrees Celsius.

As shown in Figure 3, the comparison of the short-circuit current changes of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius. It can be seen from the figure that the short-circuit current of the perovskite solar cell with passivation agent decays less than 5% under 1000 hours of continuous heating, while the voltage of the perovskite solar cell without passivator decays after 500 hours. More than 20%. The perovskite solar cell with passivating agent has excellent short-circuit current performance under continuous heating at 85 degrees Celsius.

As shown in Figure 4, the comparison of the fill factor changes of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent added under continuous heating at 85 degrees Celsius. It can be seen from the figure that the fill factor of the perovskite solar cell with passivation agent attenuates less than 15% under 1000 hours of continuous heating, while the fill factor of the perovskite solar cell without passivator attenuates after 500 hours Just over 30%. The perovskite solar cell with passivating agent has excellent fill factor performance under continuous heating at 85 degrees Celsius.

As shown in Figure 5, the comparison of the efficiency change of the perovskite solar cell prepared in Example 3 (with passivation agent added) and the perovskite solar cell without passivation agent under continuous heating at 85 degrees Celsius. It can be seen from the figure that the fill factor of the perovskite solar cell with passivator attenuates less than 10% under 1000 hours of continuous heating, while the fill factor of the perovskite solar cell without passivator attenuates after 500 hours Just over 50%. The perovskite solar cell with passivation agent has excellent efficiency performance under the condition of continuous heating at 85 degrees Celsius.

As shown in Figure 6, the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent are simulated under continuous irradiation of standard sunlight intensity (1 sun) Comparison of open circuit voltage changes. It can be seen from the figure that the open circuit voltage of the perovskite solar cell with passivation agent does not decay under 1000 hours of continuous irradiation, while the open circuit voltage of the perovskite solar cell without passivation agent decays after 500 hours. More than 5%. The perovskite solar cell with passivation agent has excellent open circuit voltage performance under the condition of simulating standard sunlight intensity (1 sun).

As shown in Figure 7, the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent are simulated under continuous irradiation of standard sunlight intensity (1 sun) Comparison of short-circuit current changes. It can be seen from the figure that the short-circuit current of the perovskite solar cell with passivating agent decays less than 10% under 1000 hours of continuous heating, while the voltage of the perovskite solar cell without passivator decays after 500 hours. More than 30%. The perovskite solar cell with passivating agent has excellent short-circuit current performance under the simulating standard sunlight intensity (1 sun) continuous irradiation.

As shown in Figure 8, the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent are simulated under continuous irradiation of standard sunlight intensity (1 sun) Comparison of changes in fill factor. It can be seen from the figure that the fill factor of the perovskite solar cell with passivator attenuates less than 10% under 1000 hours of continuous heating, while the fill factor of the perovskite solar cell without passivator attenuates after 500 hours Just over 30%. The perovskite solar cell with passivating agent has excellent fill factor performance under the condition of simulating standard sunlight intensity (1 sun).

As shown in Figure 9, the perovskite solar cell prepared in Example 5 (with passivation agent added) and the perovskite solar cell without passivation agent are simulated under continuous irradiation of standard sunlight intensity (1 sun) Comparison of efficiency changes. It can be seen from the figure that the fill factor of the perovskite solar cell with passivator attenuates less than 10% under 1000 hours of continuous heating, while the fill factor of the perovskite solar cell without passivator attenuates after 500 hours Just over 50%. The perovskite solar cell with passivating agent has excellent efficiency performance under the condition of simulating standard sunlight intensity (1 sun) continuous irradiation.

As shown in FIG. 10, the current-voltage comparison diagram of the perovskite solar cell prepared in Example 12 (with passivation agent added) and the perovskite solar cell without passivation agent. It can be seen from the figure that the current-voltage comprehensive performance of the perovskite solar cell has been improved after the passivation agent is added.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included in the protection of the present invention. Within range.

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Claims

A passivation agent, characterized in that the passivation agent is deposited between the semiconductor film and the interface material in contact with it, and/or is added to the raw material for preparing the semiconductor film, and is contained in the molecules of the passivator material. The electron-rich group provides electrons and electron acceptor sites. The molecule with the electron-rich group provides electrons is usually a compound molecule containing any one of N, P, O, and S. The electron The acceptor site is a metal cation with an empty orbital or an electron-poor group.
The passivating agent of claim 1, wherein the passivating agent is imidazole salt ionic liquid, pyridine salt ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, pyrrolidine salt At least one of ionic liquids, piperidine salt ionic liquids, and functionalized ionic liquids, or at least one of ferrocene organics, or at least one of metal phthalocyanine compounds, or metal acetyl At least one of the acetone compounds is either at least one of the organometallics, or at least one of the halogen bond compounds, or at least one of the organoborides.
The passivating agent of claim 2, wherein the imidazole ionic liquid comprises 1-hexyl-2,3-dimethylimidazole hexafluorophosphate, 1-hexadecyl-2,3-di Methylimidazole hexafluorophosphate, 1-hexyl-2,3-dimethylimidazole tetrafluoroborate, 1-hexyl-2,3-dimethylimidazole bromide, 1-butyl-2,3- Dimethylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-butyl-2,3-dimethylimidazole tetrafluoroborate, 1-butyl-2,3-dimethylimidazole chloride salt , 1-hexadecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole chloride, 1-tetradecyl-3-methylimidazole bromide, 1-tetradecyl-3 -Methylimidazole chloride, 1-dodecyl-3-methylimidazole hexafluorophosphate, 1-dodecyl-3-methylimidazole tetrafluoroborate, 1-dodecyl-3-methyl Imidazole bromide, 1-dodecyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole hexafluorophosphate, 1-decyl-3-methylimidazole tetrafluoroborate, 1 -Decyl-3-methylimidazole bromide, 1-decyl-3-methylimidazole chloride, 1-octyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-octyl 3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole bromide, 1-octyl-3-methyl Imidazole chloride salt, 1-hexyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole tetrafluoro Borate, 1-hexyl-3-methylimidazole bromide, 1-hexyl-3-methylimidazole chloride, 1-pentyl-3-methylimidazole hexafluorophosphate, 1-pentyl-3- Methylimidazole tetrafluoroborate, 1-pentyl-3-methylimidazole bromide, 1-pentyl-3-methylimidazole chloride, 1-propyl-3-methylimidazole bis(trifluoromethane Sulfonyl) imide salt, 1-propyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole p-toluene Sulfonate, 1-butyl-3-methylimidazole thiocyanate, 1-butyl-3-methylimidazole trifluoroacetate, 1-butyl-3-methylimidazole trifluoromethanesulfonic acid Salt, 1-butyl-3-methylimidazole dinitrile salt, 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-butyl-3-methylimidazolium Chlorate, 1-butyl-3-methylimidazole dihydrogen phosphate, 1-butyl-3-methylimidazole hydrogen sulfate, 1-butyl-3-methylimidazole nitrate, 1-butyl -3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole iodide salt, 1-butyl-3-methylimidazole Chlorine salt, 1-butyl-3-methylimidazole bromide, 1-propyl-3-methylimidazole iodide salt, 1-propyl-3-methylimidazole tetrafluoroborate, 1-propyl- 3-methylimidazole bromide, 1-propyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole p-toluenesulfonate Acid salt, 1-ethyl-3 -Methylimidazole thiocyanate, 1-ethyl-3-methylimidazole trifluoroacetate, 1-ethyl-3-methylimidazole trifluoromethanesulfonate, 1-ethyl-3-methyl Imidazole dinitrile amine salt, 1-ethyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-ethyl-3-methylimidazole perchlorate, 1-ethyl-3 -Methylimidazole hydrogensulfate, 1-ethyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole iodide, 1 -Ethyl-3-methylimidazole bromide, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole tetrafluoroborate;

The pyridine salt ionic liquid includes N-octylpyridine bromide, N-hexylpyridine bis(trifluoromethanesulfonyl)imide salt, N-hexylpyridine hexafluorophosphate, and N-hexylpyridine tetrafluoroborate , N-hexylpyridine bromide, N-butylpyridine bis(trifluoromethanesulfonyl)imide salt, N-butylpyridine hexafluorophosphate, N-butylpyridine tetrafluoroborate, N-butyl Pyridine bromide, N-ethylpyridine bis(trifluoromethanesulfonyl)imide salt, N-ethylpyridine hexafluorophosphate, N-ethylpyridine tetrafluoroborate, N-ethylpyridine bromide;

The quaternary ammonium salt type ionic liquid includes tributylmethylammonium bis(trifluoromethanesulfonyl)imide salt, tributylmethylammonium chloride, N-methoxyethyl-N-methyldiethylammonium tetrafluoro Borate

The quaternary phosphonium salt ionic liquid tributylhexylphosphine bis(trifluoromethanesulfonyl) imide salt, tributylhexyl phosphonium bromide, tetrabutylphosphine bis(trifluoromethanesulfonyl) imide salt, Butyl phosphine bromide, tributyl ethyl phosphine bis(trifluoromethanesulfonyl) imide salt, tributyl ethyl phosphine bromide;

The pyrrolidine salt ionic liquid includes N-butyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imide salt and N-butyl-N-methylpyrrolidine bromide;

The piperidine salt ionic liquid includes N-butyl-N-methylpiperidine bis(trifluoromethanesulfonyl)imide salt and N-butyl-N-methylpiperidine bromide;

The functionalized ionic liquid includes guanidine hydrochloride, guanidine carbonate, tetramethylguanidine lactate, tetramethylguanidine trifluoromethanesulfonate, tetramethylguanidine bisulfate, tetramethylguanidine hydrochloride, 1- Carboxyethyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole hydrogensulfate, 1-carboxyethyl-3-methylimidazole bromide, 1-carboxyethyl-3-methylimidazole chloride salt, 1-carboxymethyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt , 1-carboxymethyl-3-methylimidazole nitrate, 1-carboxymethyl-3-methylimidazole hydrogensulfate, 1-carboxymethyl-3-methylimidazole bromide, 1-carboxymethyl- 3-Methylimidazole chloride salt, 1-ethylacetyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-ethylacetyl-3-methylimidazole hexafluorophosphate, 1 -Ethylacetate-3-methylimidazole tetrafluoroborate, 1-ethylacetyl-3-methylimidazole bromide, 1-ethylacetyl-3-methylimidazole chloride, 1-benzyl 3-methylimidazole bis(trifluoromethanesulfonyl) imide salt, 1-benzyl-3-methylimidazole hexafluorophosphate, 1-benzyl-3-methylimidazole tetrafluoroborate, 1-benzyl-3-methylimidazole bromide, 1-benzyl-3-methylimidazole chloride salt, 1-ethylethyl ether-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt , 1-ethyl ethyl ether-3-methylimidazole hexafluorophosphate, 1-ethyl ethyl ether-3-methylimidazole tetrafluoroborate, 1-ethyl ethyl ether-3-methyl Imidazole bromide, 1-ethyl methyl ether-3-methylimidazole hexafluorophosphate, 1-ethyl methyl ether-3-methylimidazole tetrafluoroborate, 1-ethyl methyl ether-3 -Methylimidazole bromide, 1-vinyl-3-butylimidazole bistrifluoromethanesulfonimide salt, 1-vinyl-3-butylimidazole hexafluorophosphate, 1-vinyl-3-butane Imidazole tetrafluoroborate, 1-vinyl-3-butylimidazole bromide, 1-vinyl-3-ethylimidazole bis(trifluoromethanesulfonimide), 1-vinyl-3-ethyl Imidazole hexafluorophosphate, 1-vinyl-3-ethylimidazole tetrafluoroborate, 1-vinyl-3-ethylimidazole bromide, 1-vinyl-3-methylimidazole bis(trifluoromethane) Sulfonyl)imide salt, 1-vinyl-3-methylimidazole iodide salt, 1-allyl-3-butylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-allyl-3 -Butylimidazole hexafluorophosphate, 1-allyl-3-butylimidazole tetrafluoroborate, 1-allyl-3-butylimidazole bromide, 1-allyl-3-ethyl Imidazole bis(trifluoromethanesulfonyl)imide salt, 1-allyl-3-ethylimidazole hexafluorophosphate, 1-allyl-3-ethylimidazole tetrafluoroborate, 1-allyl 3-ethylimidazole bromide, 1-allyl-3-ethylimidazole chloride, 1-allyl-3-methylimidazole bis(trifluoromethanesulfonyl) imide salt, 1-ene Propyl-3-methylimidazole hexafluorophosphate, 1-allyl-3-methylimidazole tetrafluoroborate, 1-allyl-3-methylimidazole bromide, 1-allyl- 3-A Imidazole chloride salt, 1-cyanopropyl-3-methylimidazole bis(trifluoromethanesulfonyl) imide salt, 1-cyanopropyl-3-methylimidazole nitrate, 1-cyanopropyl-3- Methylimidazole hexafluorophosphate, 1-cyanopropyl-3-methylimidazole tetrafluoroborate, 1-cyanopropyl-3-methylimidazole chloride, 1,2-dimethyl-3-hydroxy Ethylimidazole p-toluenesulfonate, 1,2-dimethyl-3-hydroxyethylimidazole bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-hydroxyethyl Imidazole hexafluorophosphate, 1,2-dimethyl-3-hydroxyethylimidazole tetrafluoroborate, 1-hydroxyethyl-2,3-dimethylimidazole chloride, 1-hydroxyethyl-3 -Methylimidazole bisulfate, 1-hydroxyethyl-3-methylimidazole p-toluenesulfonate, 1-hydroxyethyl-3-methylimidazole dinitrile amine salt, 1-hydroxyethyl-3 -Methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-hydroxyethyl-3-methylimidazole perchlorate, 1-hydroxyethyl-3-methylimidazole nitrate, 1-hydroxyethyl 3-methylimidazole hexafluorophosphate, 1-hydroxyethyl-3-methylimidazole tetrafluoroborate, 1-hydroxyethyl-3-methylimidazole chloride, trimethylhydroxyethylammonium Bis(trifluoromethanesulfonyl)imide salt, trimethylhydroxyethylammonium hexafluorophosphate, trimethylhydroxyethylammonium tetrafluoroborate, trimethylhydroxyethylammonium chloride salt, N-sulfonic acid Acid butyl pyridine p-toluenesulfonate, N-sulfonic acid butyl pyridine triflate, N-sulfonic acid butyl pyridine hydrogen sulfate, sulfonic acid butyl pyridine lactone, N-sulfonic acid propyl pyridine P-toluenesulfonate, N-sulfonic acid propyl pyridine triflate, N-propyl sulfonic acid pyridine hydrogen sulfate, sulfonic acid propyl pyridine lactone, 1-butanesulfonic acid-3-methyl Imidazole trifluoroacetate, 1-butanesulfonic acid-3-methylimidazole trifluoromethanesulfonate, 1-butanesulfonic acid-3-methylimidazole hydrogensulfate, 1-butanesulfonic acid-3 -Methylimidazole dihydrogen phosphate, 1-butylsulfonic acid-3-methylimidazole chloride salt, 1-sulfonic acid butyl-3-methylimidazole inner salt, 1-propylsulfonic acid-3-methyl Imidazole trifluoroacetate, 1-propylsulfonic acid-3-methylimidazole trifluoromethanesulfonate, 1-propylsulfonic acid-3-methylimidazole hydrogensulfate, 1-propylsulfonic acid-3 -Methylimidazole dihydrogen phosphate, 1-propylsulfonic acid-3-methylimidazole chloride salt, 1-sulfonic acid propyl-3-methylimidazole inner salt, 1-aminopropyl-3-methylimidazole Nitrate, 1-aminopropyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-aminopropyl-3-methylimidazole hexafluorophosphate, 1-aminopropyl-3- Methylimidazole tetrafluoroborate, 1-aminopropyl-3-methylimidazole bromide, 1-aminoethyl-3-methylimidazole nitrate, 1-aminoethyl-3-methylimidazole bis( Trifluoromethanesulfonyl) imide salt, 1-aminoethyl-3-methylimidazole hexafluorophosphate, 1-aminoethyl-3-methylimidazole tetrafluoroborate, 1-aminoethyl-3 -Methylimidazole bromide;

The ferrocene organics include 1,1'-bis(dicyclohexylphosphine)-ferrocene, ferrocene acetic acid, N,N-dimethyl ferrocene methylamine, acetyl ferrocene, two Ferrocene carboxylic acid, 6-(ferrocenyl) hexyl mercaptan, 1,1′-bis(dichlorophosphorus) ferrocene, 1,1′-bis(diisopropylphosphine) ferrocene, 1, 1'-bis(diphenylphosphine)ferrocene, (S)-(-)-N,N-dimethyl-1-ferrocenylethylamine, 1,1'-bis(di-tert-butyl Phosphino)ferrocene, 1,1'-ferrocene dicarboxylic acid, (S)-(+)-N,N-dimethyl-1-(2-biphenylphosphino)ferrocene ethylamine , (R)-(-)-N,N-dimethyl-1-(2-biphenylphosphino)ferroceneethylamine, (R)-N,N-dimethyl-1-[(S )-1',2-bis(diphenylphosphino)ferrocenyl)ethylamine, 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphine)ferrocene , 1,1'-bis(di-tert-butylphosphine)ferrocene dichloropalladium, (S)-1-(diphenylphosphino)-2-[(S)-4-isopropyloxa Azolin-2-yl]ferrocene, 1,1'-diacetylferrocene, (R)-N-diphenylphosphine-N-methyl-(S)-2-(diphenylphosphine )Ferrocenyl ethylamine, (S)-N,N-dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine, 1, 1′-bis(di-cyclohexylphosphino)ferrocene palladium dichloride, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, [1,1′-bis (Diphenylphosphine)ferrocene]cobalt(II) dichloride, (S)-1-{(RP)-2-[bis(2-furyl)phosphino]ferrocenyl}ethyl dichloride (3,5-Xylyl)phosphinoferrocene carboxylic acid, N-succinimide ester;

The metal phthalocyanine compound includes copper (II) phthalocyanine, iron (II) phthalocyanine, lead phthalocyanine (II), aluminum phthalocyanine, cobalt phthalocyanine (II), dilithium phthalocyanine, and dichlorophthalocyanine Tin (IV), zinc phthalocyanine, copper perfluorophthalocyanine;

The metal acetylacetonate includes zirconium acetylacetonate, iron acetylacetonate, zinc acetylacetonate, copper acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, hafnium acetylacetonate, aluminum acetylacetonate, and rhodium acetylacetonate bis(ethylene) (I), rhodium dicarbonyl acetylacetonate, vanadium acetylacetonate, cadmium acetylacetonate, calcium acetylacetonate, vanadyl acetylacetonate, molybdenum acetylacetonate, iridium dicarbonyl acetylacetonate (I), bis(hexafluoroacetylacetone) copper ( II) Hydrate, tin acetylacetonate, bis(2,4-pentanedionate) tin(IV) dichloride, palladium(II) hexafluoroacetylacetonate, terbium(III) acetylacetonate, iridium acetylacetonate( Ⅲ), acetylacetonate platinum (II), bis (2,4-pentanedione) manganese, tris (2,4-pentanedionate) chromium (III), bis (acetylacetonate) palladium (II), double ( Acetylacetonyl) diisopropyl titanate, silver acetylacetonate, yttrium (III) acetylacetonate, lanthanum acetylacetonate, gallium acetylacetonate (III), barium acetylacetonate, ruthenium acetylacetonate, magnesium acetylacetonate, manganese acetylacetonate, Acetylacetone (norbornadiene) rhodium, acetylacetonate bis(2-phenylpyridine)iridium;

The organic metal includes two-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine) copper (II)] chloride, bromotris (triphenylphosphine) copper (I ), copper gluconate, copper tartrate (II) hydrate, copper citrate, copper pyrophosphate, copper acetate, copper thiophene-2-carboxylate, copper 8-hydroxyquinoline salt, chlorine [1,3-bis(2 ,6-Diisopropylphenyl)imidazole-2-ylidene) copper(I), disodium copper ethylenediaminetetraacetate, copper(II) dimethyldithiocarbamate, bis(2,2,6 ,6,-Tetramethyl-3,5-Heptanedioic Acid) Copper, Bis(6,6,7,7,8,8,8,-Heptafluoro-2,2-Dimethyl-3,5 -Octanedionate) copper, copper(II)-TBTA complex, 1,5-cyclooctadiene (hexafluoro-2,4-pentanedione) copper(I), dimethyldithioamino Copper formate, magnesium citrate, iron (III) diethyldithiocarbamate, disodium ethylenediaminetetraacetic acid calcium analgin (Na), disodium manganese diaminetetraacetic acid, stannous isooctanoate, triphenyl Base tin chloride, dimethyl tin dichloride, dimethyl tin oxide, trimethyl (4-pyridyl) tin, trimethyl (2-pyridyl) tin, monochlorodiethyl aluminum, bis( 2-ethylhexanoic acid) aluminum hydroxy, aluminum glycine, 2-thienyl zinc bromide;

The halogen bond compound includes 4-iodonitrobenzene, 1-fluoro-3-iodo-5-nitrobenzene, 2-nitro-3,5-difluoroiodobenzene, 4-bromo-2-fluorobenzonitrile , 4-bromo-2,3,5,6-tetrafluorobenzoic acid, 4-bromo-2,3-difluorobenzonitrile, 4 4'-dibromooctafluorobiphenyl;

The organic borides include tetrabutylammonium borohydride, 3-nitrophenylboronic acid, trimethyl borate, 3-thiopheneboronic acid, 3-furanboronic acid, 4-formylphenylboronic acid, 3-aminophenylboronic acid, 4- Mercaptophenylboronic acid, 4-(bromomethyl)phenylboronic acid, 4-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, 5-aldehyde-2-methoxyphenylboronic acid, 5-formaldehyde furan -2-boronic acid, 2-fluoro-5-bromopyridine-3-boronic acid, 2-fluoropyridine-3-boronic acid, 2,5-dichloropyridine-4-boronic acid, benzothiophene-2-boronic acid, 3-quinone Phosphoboronic acid, thiophene-2-boronic acid pinacol ester, 4-aminophenylboronic acid pinacol ester, 3-ethoxycarbonylphenylboronic acid pinacol ester, 4-methoxycarbonylphenylboronic acid pinacol ester, 3-methyl Oxyphenylboronic acid, 4-phenylether phenylboronic acid, 3,5-dimethylisoxazole-4-boronic acid pinacol ester, 6-isopropoxypyridine-3-boronic acid pinacol ester, 3 ,6-Dihydro-2H-pyran-4-boronic acid pinacol ester, pyrimidine-5-boronic acid, 5-aldehyde-2-thiophene boronic acid, 4-fluoro-3-aldehyde phenylboronic acid, 2-cyano Phenylboronic acid, 1,3-propane diester, 3,5-dicarboxyphenylboronic acid, 2-(methoxycarbonyl)phenylboronic acid, phenylboronic acid, triethyl borate, 3-fluoro-4-aldehyde benzene Boric acid, 4-carboxyphenylboronic acid, sodium tetraborate, 4-fluorophenylboronic acid, 3-iodophenylboronic acid, 2-fluorophenylboronic acid, 4-isopropoxyphenylboronic acid, 4-vinylphenylboronic acid, 4'-( 4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)acetanilide, 3-bromophenylboronic acid, N-methyldiaminoethanol ester, 2,6 -Dichloropyridine-3-boronic acid, tris(4-chlorophenyl) borate, tris(2-cyanoethyl) borate, triethanolamine borate, 4,4,5,5-tetramethyl-2- [3-(Trifluoromethoxy)phenyl]-1,3,2-dioxolane, 4-[3-(4,4,5,5-tetramethyl-1,3, 2-Dioxaborolan-2-yl)phenyl)morpholine, 4,4,5,5-tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxane Pentaborane, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxindole, 1-(tert-butoxycarbonyl)- 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole, 4-methyl-2-(4,4,5,5 -Tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene, 2-nitro-4-(4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl)aniline, 2-(4-methoxybenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 3-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene, N,N-diethyl-4-(4 ,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, 2-bromo-3-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl) Pyridine, 2-cyanophenyl boronic acid 1,3-propane diester, 2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)pyrimidine.
A passivation method, characterized in that the passivating agent according to claim 1 or 2 or 3 is deposited between the semiconductor film and the interface material in contact with it, and/or added to the raw material for preparing the semiconductor film.
The passivation method of claim 4, wherein the semiconductor film is a perovskite film of a perovskite solar cell, and the passivation agent is deposited between the perovskite film and the interface material in contact with it , And/or added to the raw materials for preparing perovskite films.
A method for preparing a semiconductor thin film, characterized in that the semiconductor thin film to be prepared is a perovskite thin film of a perovskite solar cell, which comprises the following steps:

Step 1. Add the passivator AD according to claim 1 or 2 or 3 into the solvent S and stir to obtain the passivator solution AD-S;

Step 2. Evenly coat the passivation agent solution AD-S on the surface of the prepared perovskite film layer;

Step 3. Then the substrate coated with the passivator solution AD-S is dried, and after drying, a passivation layer is obtained on the perovskite film layer;

Wherein, the solvent S in step 1 includes amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, aromatics At least one of hydrocarbon solvents.
The method for preparing a perovskite solar cell according to claim 6, wherein in step 1, the solvent S is N,N-dimethylformamide, dimethylsulfoxide, N-methyl At least one of pyrrolidone, γ-butyrolactone, 1,8-diiodooctane, N-cyclohexyl-2-pyrrolidone, chlorobenzene, and toluene.
A method for preparing a semiconductor thin film, characterized in that the semiconductor thin film to be prepared is a perovskite thin film of a perovskite solar cell, which comprises the following steps:

Step I. Add the passivator AD according to claim 1 or 2 or 3 into the solvent S and stir to obtain the passivator solution AD-S;

Step II, uniformly coat the passivator solution AD-S on the surface of the hole transport layer or electron transport layer that has been prepared;

Step III: Then, the substrate coated with the passivator solution AD-S is dried, and after drying, a passivation layer is obtained on the hole transport layer or the electron transport layer.
A method for preparing a semiconductor thin film, characterized in that the semiconductor thin film to be prepared is a perovskite thin film of a perovskite solar cell, which comprises the following steps:

Step 1. Add the passivator AD according to claim 1 or 2 or 3 into the precursor solution PS for preparing the perovskite film layer to obtain the perovskite precursor solution AD-PS containing the passivator AD ；

Step 2: The perovskite precursor solution AD-PS is subjected to the preparation of the conventional perovskite film layer to obtain the perovskite film layer containing the passivator.
The method for preparing a perovskite solar cell according to claim 9, wherein in step 1, the ratio of adding the passivation agent AD to the precursor solution PS for preparing the perovskite film is: passivation The molar ratio of the chemical agent AD to the total halogen of the precursor solution PS is 1:100000~1:1.