Perovskite thin film layer and preparation method therefor, and perovskite silicon stacked solar cell and preparation method therefor

Abstract

Disclosed in the present application are a perovskite thin film layer (4) and a preparation method therefor, and a perovskite silicon stacked solar cell and a preparation method therefor. The perovskite thin film layer (4) comprises a perovskite buried modification layer (41) stacked on the surface of a nickel oxide hole transport layer (3) in the perovskite solar cell as well as a perovskite light absorption layer (42) stacked on the surface of the perovskite buried modification layer (41), wherein the perovskite buried modification layer (41) is doped with hydrazine and / or hydrazine derivatives.

Description

Perovskite thin film layer and preparation method thereof, perovskite silicon tandem solar cell and preparation method thereof

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on July 26, 2023, with application number 202310928947.8 and application name “Perovskite thin film layer and preparation method thereof, perovskite silicon tandem solar cell and preparation method thereof”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application relates to the field of solar cells, and in particular to a perovskite thin film layer and a preparation method thereof, a perovskite silicon tandem solar cell and a preparation method thereof. Background Art

[0003] Perovskite solar cells are currently receiving unprecedented attention due to their high efficiency and simple preparation methods. Nickel oxide is a very suitable material for the hole transport layer in perovskite solar cells, with advantages such as excellent chemical stability, high carrier mobility, and low-cost large-scale manufacturing. However, when nickel oxide is used as the hole transport layer in perovskite solar cells, the interface between the perovskite film and the nickel oxide hole transport layer in the perovskite solar cell contains a large number of defects, which accelerates the degradation of the perovskite film and ultimately affects the stability of the perovskite film and device.

[0004] Summary of the Invention

[0005] The present invention discloses a perovskite thin film layer and its preparation method, a perovskite silicon tandem solar cell and its preparation method. The perovskite thin film layer has excellent passivation and modification effects at the interface between the perovskite thin film layer and the nickel oxide hole transport layer, has few defects, is highly stable, and is not prone to decomposition.

[0006] In order to achieve the above-mentioned objectives, in the first aspect, the present application discloses a perovskite thin film layer for use in a perovskite solar cell, comprising a perovskite buried modification layer stacked on the surface of a nickel oxide hole transport layer in the perovskite solar cell and a perovskite light absorption layer stacked on the surface of the perovskite buried modification layer, wherein the perovskite buried modification layer is doped with hydrazine and / or a hydrazine derivative.

[0007] As an optional implementation manner, in an embodiment of the present application, the thickness of the perovskite buried modification layer is 10 nm to 20 nm.

[0008] As an optional implementation manner, in an embodiment of the present application, the thickness of the perovskite buried modification layer is 10 nm to 20 nm.

[0009] The thickness of the perovskite light-absorbing layer is 450 nm to 550 nm.

[0010] As an optional implementation manner, in an embodiment of the present application, the molar ratio of hydrazine and / or hydrazine derivative doping in the perovskite buried modification layer is 10% to 15%.

[0011] As an optional embodiment, in the examples of the present application, the hydrazine derivative contains one or more functional groups selected from the group consisting of phenyl, carbonyl and amino groups.

[0012] As an optional embodiment, in the examples of the present application, the hydrazine derivative can be phenylhydrazine, 4-chlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine hydrochloride, 2,6-difluorophenylhydrazine, 4-iodophenylhydrazine, benzylhydrazine dihydrochloride, 2,4-dichlorophenylhydrazine, 2-fluorophenylhydrazine, 2,3-dimethylphenylhydrazine hydrochloride, 2,4-dimethylphenylhydrazine hydrochloride, 4-(4-hydrazine-phenyl)-1,2,4-triazole hydrochloride, 4-chloro-o-tolylhydrazine hydrochloride, 4-methoxyphenylhydrazine hydrochloride, 5-bromo-2-methylphenylhydrazine hydrochloride, 2,6-dimethylphenylhydrazine hydrochloride, 3-(trifluoromethyl)phenylhydrazine hydrochloride, 3-chlorophenylhydrazine hydrochloride, 2-naphthylhydrazine, 2-naphthylhydrazine hydrochloride, 1-naphthylhydrazine hydrochloride, diphenylformyl Hydrazine, 4-(trifluoromethyl)quinolinecarboxylic acid hydrazide, 2-trifluoromethylquinoline-4-carboxylic acid hydrazide, 6-chloropyridine-3-carboxylic acid hydrazide, 6-fluoro-4-trifluoromethylquinoline-2-carboxylic acid hydrazide, 2-pyridinecarboxylic acid hydrazide, 3-phenoxybenzohydrazide, o-ethoxybenzohydrazide, 4-benzyloxybenzohydrazide, 3-trifluoromethylbenzohydrazide, 2,5-dimethoxybenzohydrazide 2,6-difluorobenzohydrazide, acetic acid hydrazide, methoxyacetic acid hydrazide, N-acetylphenylhydrazide, 1,2-diacetylhydrazine, 4-chloro-2-methylphenoxyacetic acid hydrazide, adipic acid dihydrazide, maleic acid hydrazide, maleic acid hydrazide, 4-maleimidobutyric acid hydrazide, p-dibenzoic acid dihydrazide, biphenylhydrazine, sebacic acid dihydrazide, 2-thiophenecarboxylic acid hydrazide, palmitic acid hydrazide, isophthalic acid dihydrazide, etc.

[0013] In a second aspect, the present application further discloses a method for preparing a perovskite thin film layer as in the first aspect:

[0014] Preparation of the perovskite buried modification layer: dissolving hydrazine and / or hydrazine derivatives in a perovskite precursor solution, using the nickel oxide hole transport layer in the perovskite solar cell as a substrate, depositing the perovskite precursor solution doped with hydrazine and / or hydrazine derivatives on the surface of the nickel oxide hole transport layer, and annealing to obtain the perovskite buried modification layer;

[0015] The perovskite light-absorbing layer is prepared by using the perovskite buried modification layer as a substrate, preparing a metal halide skeleton layer on the perovskite buried modification layer, spin-coating a halide cation solution on the metal halide skeleton layer, and annealing to obtain the perovskite light-absorbing layer.

[0016] As an optional implementation manner, in the embodiment of the present application, in the step of preparing the perovskite buried modification layer, the annealing temperature is 100° C. to 170° C., and the annealing time is 20 min to 40 min.

[0017] As an optional implementation, in an embodiment of the present application, in the step of preparing the perovskite light-absorbing layer, the annealing temperature is 100° C. to 170° C., and the annealing time is 20 min to 40 min.

[0018] As an optional implementation, in an embodiment of the present application, the metal halide skeleton layer includes lead iodide.

[0019] As an optional embodiment, in an example of the present application, the metal halide skeleton layer further includes cesium bromide, and the halide cations in the halide cation solution include one or more of iodomethane, bromomethylamine and chloromethylamine.

[0020] As an optional implementation manner, in an embodiment of the present application, the thickness of the metal halide skeleton layer is 350 nm to 450 nm.

[0021] In a third aspect, the present invention provides a perovskite silicon tandem solar cell:

[0022] The perovskite silicon tandem solar cell includes: a silicon base cell, a first transparent conductive film layer, a nickel oxide hole transport layer, the above-mentioned perovskite film layer, an electron transport layer, and a second transparent conductive film layer stacked in sequence. The perovskite silicon tandem solar cell also includes a positive electrode and a negative electrode. The perovskite silicon tandem solar cell also includes a positive electrode and a negative electrode. The negative electrode forms an ohmic contact with the second conductive film layer, and the positive electrode forms an ohmic contact with the silicon base cell.

[0023] As an optional implementation manner, in an embodiment of the present application, the second transparent conductive film layer is an indium zinc oxide layer.

[0024] As an optional implementation manner, in an embodiment of the present application, the thickness of the second transparent conductive film layer is 80 nm to 100 nm.

[0025] As an optional embodiment, in the embodiment of the present application, the electron transport layer is C 60 .

[0026] As an optional implementation manner, in an embodiment of the present application, the thickness of the electron transport layer is 15 nm to 20 nm.

[0027] As an optional implementation, in an embodiment of the present application, the thickness of the nickel oxide hole transport layer is 20 nm to 30 nm.

[0028] As an optional implementation, in an embodiment of the present application, the positive electrode and the negative electrode are silver.

[0029] As an optional implementation, in an embodiment of the present application, the thickness of the positive electrode is 300 nm to 350 nm.

[0030] As an optional implementation manner, in an embodiment of the present application, the thickness of the negative electrode is 300 nm to 350 nm.

[0031] As an optional implementation manner, in an embodiment of the present application, the perovskite silicon tandem solar cell further includes a buffer layer, and the buffer layer is located between the second transparent conductive film layer and the electron transport layer.

[0032] As an optional implementation, in an embodiment of the present application, the buffer layer is tin oxide.

[0033] As an optional implementation manner, in an embodiment of the present application, the thickness of the buffer layer is 20 nm to 30 nm.

[0034] In a fourth aspect, an embodiment of the present application provides a method for preparing a perovskite silicon tandem solar cell, the method for preparing a perovskite silicon tandem solar cell comprising the following steps:

[0035] Provide silicon substrate cells;

[0036] preparing a first transparent conductive film layer on the silicon substrate cell;

[0037] preparing a nickel oxide hole transport layer on the first transparent conductive film layer;

[0038] preparing the above-mentioned perovskite thin film layer on the surface of the nickel oxide hole transport layer;

[0039] preparing an electron transport layer on the surface of the perovskite thin film layer;

[0040] preparing a second transparent conductive film layer on the surface of the electron transport layer;

[0041] Post-processing is performed to obtain perovskite silicon tandem solar cells.

[0042] As an optional implementation manner, in the embodiment of the present application, the first transparent conductive film layer is prepared by physical vapor deposition.

[0043] As an optional implementation manner, in the examples of the present application, the nickel oxide hole transport layer is prepared by magnetron sputtering or physical vapor deposition.

[0044] As an optional implementation manner, in the examples of the present application, the electron transport layer is prepared by a vacuum evaporation method.

[0045] As an optional implementation manner, in the embodiment of the present application, the second transparent conductive film layer is prepared by physical vapor deposition.

[0046] As an optional embodiment, in the examples of the present application, the preparation method further includes the following steps:

[0047] A buffer layer is prepared on the electron transport layer, so that the buffer layer is located between the electron transport layer and the second transparent conductive thin film layer.

[0048] As an optional implementation, in the examples of the present application, the buffer layer is prepared by atomic layer deposition.

[0049] Compared with traditional technologies, the advantages of this application are:

[0050] A perovskite thin film layer provided in an embodiment of the present application modifies the interface between the nickel oxide hole transport layer and the perovskite light absorbing layer by introducing a perovskite buried modification layer doped with hydrazine and / or hydrazine derivatives between the nickel oxide hole transport layer and the perovskite light absorbing layer of a perovskite solar cell, while reducing stress and defects in the perovskite light absorbing layer, and significantly improving the interface stability between the nickel oxide hole transport layer and the perovskite thin film layer.

[0051] This is because the perovskite buried modification layer located between the nickel oxide hole transport layer and the perovskite light absorbing layer can not only play a physical barrier role, making the perovskite light absorbing layer less susceptible to the influence of the nickel oxide hole transport layer, but also can reduce the thermal expansion coefficient mismatch and lattice structure mismatch between the perovskite light absorbing layer and the nickel oxide hole transport layer. With the perovskite buried modification layer as the growth substrate of the perovskite light absorbing layer, the perovskite light absorbing layer is not prone to stress during the crystallization growth process. At the same time, the cations in the perovskite buried modification layer, such as MA + It is easy to migrate, and can effectively regulate the crystallinity and grain growth process of the perovskite light-absorbing layer, effectively reduce the stress and defect density in the growth of the perovskite light-absorbing layer, and improve the crystallization quality of the perovskite light-absorbing layer, thereby improving the overall quality of the perovskite film layer.

[0052] Furthermore, the perovskite buried modification layer doped with hydrazine and / or hydrazine derivatives is stacked above the nickel oxide hole transport layer. On the one hand, this can reduce the high-valent nickel ions on the surface of the nickel oxide hole transport layer, reducing the deprotonation of cationic amines in the perovskite buried modification layer by the high-valent nickel ions. On the other hand, each nitrogen atom in the hydrazine and / or hydrazine derivative contains a lone pair of electrons, which enables the hydrazine and / or hydrazine derivatives in the perovskite buried modification layer to coordinate with lead atoms at the interface between the nickel oxide hole transport layer and the perovskite thin film layer to form a complex, thereby inhibiting carrier recombination at the interface between the nickel oxide hole transport layer and the perovskite thin film layer, thereby passivating the interface defects between the nickel oxide hole transport layer and the perovskite thin film layer. Furthermore, hydrazine and / or hydrazine derivatives have better reducibility, and iodine ions in the perovskite buried modification layer are not easily oxidized to form elemental iodine, thereby effectively inhibiting the formation of elemental iodine in the perovskite buried modification layer. Perovskite decomposition is not likely to occur at the interface between the perovskite thin film layer and the nickel oxide hole transport layer, and the interface stability between the perovskite thin film layer and the nickel oxide hole transport layer is greatly enhanced.

[0053] Therefore, after adding hydrazine and / or hydrazine derivatives, the passivation and modification effects at the interface between the perovskite thin film layer and the nickel oxide hole transport layer are better, the defect density is low, and the stability is improved, which is beneficial to improving the hole extraction efficiency and energy conversion efficiency of perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0055] FIG1 is a schematic diagram of the stacked structure of the perovskite silicon tandem solar cell disclosed in Application Example 1 of this application.

[0056] FIG2 is an SEM image of the perovskite thin film layer disclosed in Example 1 of the present application.

[0057] FIG3 is a SEM image of the perovskite thin film layer disclosed in Comparative Example 1 of the present application.

[0058] FIG4 is an IV curve diagram of the perovskite silicon tandem solar cell disclosed in Application Example 1 and Comparative Application Example 1 of the present application.

[0059] Figure numerals: 1. Silicon base cell; 2. First transparent conductive film layer; 3. Nickel oxide hole transport layer; 4. Perovskite film layer; 41. Perovskite buried modification layer; 42. Perovskite light absorption layer; 5. Electron transport layer; 6. Buffer layer; 7. Second transparent conductive film layer; 8. Positive electrode; 9. Negative electrode. DETAILED DESCRIPTION

[0060] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0061] The terms "first," "second," etc., are primarily used to distinguish different devices, elements, or components (which may or may not be the same in type and configuration) and are not intended to indicate or imply the relative importance or quantity of the devices, elements, or components indicated. Unless otherwise specified, "plurality" means two or more.

[0062] Nickel oxide is a very suitable nickel oxide hole transport layer with excellent chemical stability, high carrier mobility and low-cost large-scale manufacturing advantages. It is an important component of perovskite solar cells. However, there are usually a large number of high-valent nickel ions on the surface of nickel oxide prepared by magnetron sputtering. High-valent nickel ions also serve as Proton acceptors and Lewis electron acceptors deprotonate the cationic amines in the perovskite and oxidize the iodide ions, eventually causing the perovskite to decompose at the interface of the perovskite film layer and the nickel oxide hole transport layer, forming a PbI-rich 2-x Br x The interface barrier and hysteresis effect affect the stability at the interface. At the same time, the thermal expansion coefficients of nickel oxide and perovskite are mismatched, resulting in tensile stress at the interface between the perovskite film layer and the nickel oxide hole transport layer. At the same time, the uneven distribution of halogens in the perovskite film layer will lead to large residual stress in the perovskite film layer. After the annealing of the perovskite film layer is completed, the tensile stress generated by the contraction of the perovskite film crystal structure will reduce the activation energy of ion migration, thereby accelerating the degradation of the perovskite, and ultimately affecting the stability of the perovskite film layer and the device. Although the above problems can usually be alleviated by appropriately reducing stress through precise adjustment of the annealing process, precise control of the annealing process will significantly increase the difficulty of manufacturing.

[0063] Based on the above problems, the present application provides a perovskite thin film layer and a preparation method thereof, a perovskite silicon tandem solar cell and a preparation method thereof.

[0064] In a first aspect, an embodiment of the present application provides a perovskite thin film layer 4 .

[0065] The perovskite thin film layer 4 is used for a perovskite solar cell, and includes a perovskite buried modification layer 41 stacked on the surface of a nickel oxide hole transport layer 3 in the perovskite solar cell, and a perovskite light absorption layer 42 stacked on the surface of the perovskite buried modification layer 41, wherein the perovskite buried modification layer 41 is doped with hydrazine and / or a hydrazine derivative.

[0066] By introducing a perovskite buried modification layer 41 doped with hydrazine and / or hydrazine derivatives between the nickel oxide hole transport layer 3 and the perovskite light absorption layer 42 of the perovskite solar cell, the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4 is modified, and at the same time, the stress and defects in the perovskite light absorption layer 42 are reduced, and the interface stability between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4 is significantly improved.

[0067] This is because the perovskite buried modification layer 41 located between the nickel oxide hole transport layer 3 and the perovskite light absorbing layer 42 can not only play a physical barrier role, so that the perovskite light absorbing layer 42 is not easily affected by the nickel oxide hole transport layer 3, but also can reduce the thermal expansion coefficient mismatch and lattice structure mismatch between the perovskite light absorbing layer 42 and the nickel oxide hole transport layer 3. With the perovskite buried modification layer 41 as the growth substrate of the perovskite light absorbing layer 42, the perovskite light absorbing layer 42 is not prone to stress during the crystallization growth process. At the same time, the cations such as MA in the perovskite buried modification layer 41 are not easily affected by the nickel oxide hole transport layer 3. + It is easy to migrate, can effectively regulate the crystallinity and grain growth process of the perovskite light absorbing layer 42, effectively reduce the stress and defect density existing in the growth of the perovskite light absorbing layer 42, improve the crystallization quality of the perovskite light absorbing layer 42, and thus improve the overall quality of the perovskite thin film layer 4.

[0068] Furthermore, the perovskite buried modification layer 41 doped with hydrazine and / or hydrazine derivatives is stacked on top of the nickel oxide hole transport layer 3. On the one hand, it can reduce the high-valent nickel ions on the surface of the nickel oxide hole transport layer 3, reducing the deprotonation of cationic amines in the perovskite buried modification layer 41 by the high-valent nickel ions. On the other hand, each N atom in the hydrazine and / or hydrazine derivative contains a lone pair of electrons, so that the hydrazine and / or hydrazine derivative in the perovskite buried modification layer 41 can coordinate with the lead atoms at the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4 to form a complex, thereby inhibiting carrier recombination at the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4, thereby passivating the interface defects between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4. Furthermore, hydrazine and / or hydrazine derivatives have better reducibility, and the iodine ions in the perovskite buried modification layer 41 are not easily oxidized to form elemental iodine, thereby effectively inhibiting the formation of elemental iodine in the perovskite buried modification layer 41. Perovskite decomposition is not likely to occur at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3, and the interface stability between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3 is greatly enhanced.

[0069] Therefore, after adding hydrazine and / or hydrazine derivatives, the passivation and modification effects at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3 are better, the defect density of the perovskite thin film layer 4 is reduced, and the stability is improved, which is beneficial to improving the hole extraction rate and energy conversion efficiency of the perovskite solar cell.

[0070] It should be noted that low-valent nickel refers to nickel elements with low valence and weak oxidizing properties, which are difficult to oxidize the perovskite thin film layer 4, thereby not damaging the structure of the perovskite thin film layer 4, such as divalent nickel. High-valent nickel refers to nickel elements with high valence and strong oxidizing properties, such as trivalent nickel and tetravalent nickel, which are easy to oxidize the perovskite thin film layer 4 and easily damage the structure of the perovskite thin film layer 4.

[0071] In some embodiments, the thickness of the buried perovskite modification layer 41 is 10 nm to 20 nm, and / or the thickness of the perovskite light absorption layer 42 is 450 nm to 550 nm.

[0072] The buried perovskite modification layer 41 at this thickness has a better effect on passivating the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4, and the buried perovskite modification layer 41 has a better effect on regulating the growth of the perovskite light absorbing layer 42. If the buried perovskite modification layer 41 is too thin, the interface modification effect between the nickel oxide hole transport layer 3 and the perovskite light absorbing layer 42 is poor, which can easily lead to contact between the nickel oxide hole transport layer 3 and the perovskite light absorbing layer 42, and the high-valent nickel ions deprotonate the cations in the perovskite light absorbing layer 42, affecting the interface stability. If the buried perovskite modification layer 41 is too thick, it can easily lead to the entire perovskite thin film layer 4 not being able to maintain its shape on the pyramid-structured silicon substrate battery 1, affecting the open circuit voltage and fill factor of the battery device. For example, the thickness of the perovskite buried modification layer 41 is 30 nm, 35 nm, 40 nm, 45 nm, and 50 nm, and the thickness of the perovskite light absorption layer 42 is 450 nm, 470 nm, 490 nm, 505 nm, 520 nm, 535 nm, and 550 nm, which is not specifically limited in this embodiment.

[0073] In some embodiments, in the perovskite buried modification layer 41 , the molar ratio of hydrazine and / or hydrazine derivative doping in the perovskite buried modification layer 41 is 10% to 15%.

[0074] The above-mentioned content of hydrazine and / or hydrazine derivatives has a good interface passivation effect on the nickel oxide hole transport layer 3 and the buried perovskite modification layer 41, and is conducive to obtaining a perovskite buried modification layer 41 with good uniformity and low defect state density. On the basis of this perovskite buried modification layer 41, it is easy to obtain a perovskite light absorption layer 42 with low stress defects and high crystal quality. If the content of hydrazine and / or hydrazine derivatives is too low, hydrazine and / or hydrazine derivatives will not be able to fully coordinate with the lead atoms in the perovskite thin film layer 4, resulting in poor passivation effect on the interface between the buried perovskite modification layer 41 and the nickel oxide hole transport layer 3, and poor effect on improving the interface stability between the buried perovskite modification layer 41 and the nickel oxide hole transport layer 3. If the content of hydrazine and / or hydrazine derivatives is too high, it is easy to destroy the lattice of the perovskite buried modification layer 41, making it difficult for the perovskite buried modification layer 41 to form a stable perovskite crystal phase, thereby affecting the crystal orientation of the perovskite light absorbing layer 42 above the perovskite buried modification layer 41, thereby reducing the overall quality of the perovskite thin film layer 4.

[0075] In some embodiments, the hydrazine derivative introduces one or more functional groups selected from the group consisting of phenyl, carbonyl, and amino groups.

[0076] The phenyl, carbonyl and amino groups introduced by hydrazine derivatives can react with Pb 2+ The ions work together to form a stable coordination, passivating the uncoordinated Pb 0At the same time, the amino groups can form hydrogen bonds with the halogen atoms on the surface of the perovskite light-absorbing layer 42, thereby pinning the halogen atoms with lower migration activation energy, reducing ion migration, and improving the stability of the perovskite light-absorbing layer 42. For example, the hydrazine derivative can be phenylhydrazine, 4-chlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine hydrochloride, 2,6-difluorophenylhydrazine, 4-iodophenylhydrazine, benzylhydrazine dihydrochloride, 2,4-dichlorophenylhydrazine, 2-fluorophenylhydrazine, 2,3-dimethylphenylhydrazine hydrochloride, 2,4-dimethylphenylhydrazine hydrochloride, 4-(4-hydrazinophenyl)-1,2,4-triazole hydrochloride, 4-chloro-o-tolylhydrazine hydrochloride, 4-methoxyphenylhydrazine hydrochloride, 5-bromo-2-methylphenylhydrazine hydrochloride, 2,6-dimethylphenylhydrazine hydrochloride, 3-(trifluoromethyl)phenylhydrazine hydrochloride, 3-chlorophenylhydrazine hydrochloride, 2-naphthylhydrazine, 2-naphthylhydrazine hydrochloride, 1-naphthylhydrazine hydrochloride, diphenylcarboxylic acid hydrazide, 4-(trifluoromethyl)quinolinecarboxylic acid hydrazide, 2 -trifluoromethylquinoline-4-carboxylic acid hydrazide, 6-chloropyridine-3-carboxylic acid hydrazide, 6-fluoro-4-trifluoromethylquinoline-2-carboxylic acid hydrazide, 2-pyridinecarboxylic acid hydrazide, 3-phenoxybenzohydrazide, o-ethoxybenzohydrazide, 4-benzyloxybenzohydrazide, 3-trifluoromethylbenzohydrazide, 2,5-dimethoxybenzohydrazide 2,6-difluorobenzohydrazide, acetic acid hydrazide, methoxyacetic acid hydrazide, N-acetylphenylhydrazide, 1,2-diacetylhydrazine, 4-chloro-2-methylphenoxyacetic acid hydrazide, adipic acid dihydrazide, maleic acid hydrazide, maleic acid hydrazide, 4-maleimidobutyric acid hydrazide, p-dibenzoic acid dihydrazide, biphenylhydrazine, sebacic acid dihydrazide, 2-thiophenecarboxylic acid hydrazide, palmitic acid hydrazide, isophthalic acid hydrazide, etc., which are not specifically limited in the embodiments of the present application.

[0077] In a second aspect, the embodiments of the present application further disclose a method for preparing the perovskite thin film layer 4 as in the first aspect.

[0078] The method for preparing the perovskite thin film layer 4 comprises the following steps:

[0079] Preparation of a buried perovskite modification layer 41: dissolving hydrazine and / or a hydrazine derivative in a perovskite precursor solution, using the nickel oxide hole transport layer 3 in the perovskite solar cell as a substrate, depositing the perovskite precursor solution doped with hydrazine and / or a hydrazine derivative on the surface of the nickel oxide hole transport layer 3, and annealing to obtain the buried perovskite modification layer 41;

[0080] Preparation of perovskite light absorbing layer 42: Using the above-mentioned perovskite buried modification layer 41 as a substrate, a halide metal skeleton layer is prepared on the above-mentioned perovskite buried modification layer 41, a halide cation solution is spin-coated on the halide metal skeleton layer, and the perovskite light absorbing layer 42 is obtained after annealing.

[0081] In the present application, a perovskite light absorbing layer 42 is prepared based on a buried modification layer 41 of a perovskite doped with hydrazine and / or a hydrazine derivative. The prepared perovskite light absorbing layer 42 has low stress and high quality. During the annealing process, there is no need to precisely control the annealing process to obtain a high-quality perovskite thin film layer 4 with good repeatability. Therefore, the quality control of the perovskite thin film layer 4 is easier and the process difficulty is greatly reduced.

[0082] The above-mentioned co-evaporation method for preparing the metal halide skeleton layer and the halide cation solution can react quickly, which is conducive to preparing a perovskite light-absorbing layer 42 with good density and relatively uniform thickness. Using the perovskite buried modification layer 41 as the substrate is conducive to promoting the reaction between the above-mentioned metal halide skeleton layer and the halide cation solution, thereby reducing the halide metal residue.

[0083] In some embodiments, the annealing temperature for preparing the buried perovskite modification layer 41 is 100°C to 170°C, and the annealing time is 20 minutes to 40 minutes. The annealing temperature for preparing the perovskite light absorption layer 42 is 100°C to 170°C, and the annealing time is 20 minutes to 40 minutes. When the preparation of the buried perovskite modification layer 41 and the preparation of the perovskite light absorption layer 42 are performed within the above-mentioned annealing process conditions, both the buried perovskite modification layer 41 and the perovskite light absorption layer 42 can be obtained with low tensile stress and defect density.

[0084] In some embodiments, the metal halide skeleton layer includes lead iodide.

[0085] Lead ions are one of the raw materials frequently used in the preparation of perovskite materials, but unreacted residual lead iodide can easily cause defects in the perovskite thin film layer 4 and undermine the stability of the interface between the perovskite light-absorbing layer 42 and the nickel oxide hole transport layer 3. Each nitrogen atom in hydrazine and / or a hydrazine derivative contains a lone pair of electrons, which can coordinate with the lead atoms of lead iodide at the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4 to form a complex, inhibiting carrier recombination at the interface between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4, thereby passivating the interface defects between the nickel oxide hole transport layer 3 and the perovskite thin film layer 4.

[0086] The iodide ions in the lead iodide are easily oxidized to elemental iodine by the high-valent nickel ions in the nickel oxide hole transport layer 3, causing defects at the interface between the perovskite light absorption layer 42 and the nickel oxide hole transport layer 3. Due to the good reducibility of hydrazine and / or hydrazine derivatives, the iodide ions in the perovskite buried modification layer 41 are not easily oxidized to form elemental iodine, thereby effectively suppressing the formation of elemental iodine in the perovskite buried modification layer 41. The interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3 is not prone to perovskite decomposition, and the interface stability between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3 is greatly enhanced.

[0087] In some embodiments, the metal halide skeleton layer further comprises cesium bromide, and the halogenated cations in the halogenated cation solution comprise one or more of iodomethane, bromomethylamine, and chloromethylamine.

[0088] In some embodiments, the thickness of the metal halide skeleton layer is 350 nm to 450 nm. A metal halide skeleton layer of this thickness is more effective as a skeleton for preparing the perovskite light absorbing layer 42, and is conducive to a thicker and more uniform perovskite light absorbing layer 42.

[0089] In a third aspect, the present invention provides a perovskite silicon tandem solar cell:

[0090] 1 , the perovskite silicon tandem solar cell comprises: a silicon base cell 1, a first transparent conductive film layer 2, a nickel oxide hole transport layer 3, the above-mentioned perovskite film layer 4, an electron transport layer 5, and a second transparent conductive film layer 7 stacked in sequence. The perovskite silicon tandem solar cell also comprises a positive electrode 8 and a negative electrode 9. The negative electrode 9 forms an ohmic contact with the second conductive film layer, and the positive electrode 8 forms an ohmic contact with the silicon base cell 1.

[0091] The velvet surface of the silicon-based battery 1 is pyramid-shaped, and the velvet surface of the above-mentioned perovskite thin film layer 4 has a better shape retention effect. The perovskite thin film layer 4 of the above-mentioned thickness has fewer defects at the interface with the nickel oxide hole transport layer 3, and has better stability. The crystallization quality of the perovskite thin film layer 4 is high, which is beneficial to improving the photoelectric conversion efficiency and thus improving the device efficiency.

[0092] In some embodiments, the first transparent conductive film layer 2 and the second transparent conductive film layer 7 are indium zinc oxide, and have a thickness of 80 nm to 100 nm. For example, the thickness of the first transparent conductive film layer 2 is 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc. The electron transport layer 5 is C 60 , with a thickness of 15nm to 20nm. Exemplarily, the thickness of the electron transport layer 5 is 15nm, 17nm, 19nm, 20nm, etc. The nickel oxide hole transport layer 3 is nickel oxide, with a thickness of 20nm to 30nm. Exemplarily, the thickness of the nickel oxide hole transport layer 3 is 20nm, 23nm, 25nm, 27nm, 30nm, etc. The positive electrode 8 and the negative electrode 9 are silver. The thickness of the positive electrode 8 is 300nm to 350nm. Exemplarily, the thickness of the positive electrode 8 is 300nm, 315nm, 325nm, 335nm, 350nm, etc. The thickness of the negative electrode 9 is 300nm to 350nm. Exemplarily, the thickness of the negative electrode 9 is 300nm, 315nm, 325nm, 335nm, 350nm. This embodiment does not specifically limit this.

[0093] In some embodiments, the perovskite silicon tandem solar cell further includes a buffer layer 6, which is located between the transparent conductive film layer and the electron transport layer 5. The buffer layer 6 is tin oxide and has a thickness of 20 nm to 30 nm. Exemplarily, the thickness of the buffer layer 6 is 20 nm, 22 nm, 25 nm, 28 nm, or 30 nm, which is not specifically limited in this embodiment.

[0094] In a fourth aspect, an embodiment of the present application provides a method for preparing a perovskite silicon tandem solar cell as described in the third aspect, wherein the method for preparing a perovskite silicon tandem solar cell comprises the following steps:

[0095] Providing a silicon substrate cell 1;

[0096] A first transparent conductive film layer 2 is prepared on a silicon substrate cell 1;

[0097] A nickel oxide hole transport layer 3 is formed on the first transparent conductive film layer 2;

[0098] The perovskite thin film layer 4 is prepared on the surface of the nickel oxide hole transport layer 3;

[0099] An electron transport layer 5 is prepared on the surface of the perovskite thin film layer 4;

[0100] A second transparent conductive film layer 7 is formed on the surface of the electron transport layer 5;

[0101] Post-processing is performed to obtain perovskite silicon tandem solar cells.

[0102] In some embodiments, the first transparent conductive film layer 2 is prepared on the silicon substrate cell 1 by physical vapor deposition; and / or,

[0103] A nickel oxide hole transport layer 3 is prepared on the first transparent conductive film layer 2 by magnetron sputtering or physical vapor deposition; and / or,

[0104] Prepare a perovskite thin film layer 4 on the surface of the nickel oxide hole transport layer 3; and / or,

[0105] preparing an electron transport layer 5 on the perovskite thin film layer 4 by vacuum evaporation; and / or,

[0106] The second transparent conductive thin film layer 7 is prepared on the electron transport layer 5 by using a physical vapor deposition method.

[0107] In some embodiments, the buffer layer 6 is prepared on the electron transport layer 5 by atomic layer deposition, so that the buffer layer 6 is located between the electron transport layer 5 and the second transparent conductive thin film layer 7 .

[0108] The technical solution of the present application will be further described below in conjunction with more specific embodiments and drawings.

[0109] Example 1

[0110] The first embodiment of the present application provides a perovskite thin film layer 4, including a perovskite buried modification layer 41 stacked on the surface of the nickel oxide hole transport layer 3 of the perovskite solar cell and a perovskite light absorption layer 42 stacked on the surface of the perovskite buried modification layer 41.

[0111] Specifically, the preparation method of the perovskite thin film layer 4 includes the following steps:

[0112] Dissolve hydrazine in a perovskite precursor solution, and use the nickel oxide hole transport layer 3 in the perovskite solar cell as a substrate. Spin-coat the hydrazine-doped perovskite precursor solution on the surface of the nickel oxide hole transport layer 3 at a rotation speed of 5000 rpm. Anneal at 130° C. for 30 min to obtain a perovskite buried modification layer 41 with a thickness of 15 nm. The hydrazine doping ratio in the perovskite buried modification layer 41 is 12.5%.

[0113] With the above-mentioned perovskite buried modification layer 41 as the substrate, a mixed thin film layer of lead iodide and cesium bromide with a thickness of 350 nm was prepared by co-evaporation method, and the evaporation rate ratio of lead iodide and cesium bromide was 10:1. A mixed solution of iodomethane, bromomethylamine and chloromethylamine was coated on the mixed thin film layer of lead iodide and cesium bromide, with the concentration of iodomethane being 85 mg / mL, the concentration of bromomethylamine being 12 mg / mL, and the concentration of chloromethylamine being 5 mg / mL. The mixture was annealed at 130°C for 30 minutes to obtain a perovskite light-absorbing layer 42 with a thickness of 450 nm.

[0114] Example 2

[0115] Example 2 of the present application provides a perovskite thin film layer 4. Compared with Example 1, 2,5-dichlorophenylhydrazine is used to replace hydrazine in an equal molar amount and added to the perovskite precursor solution, and the rest is consistent with Example 1.

[0116] Example 3

[0117] Example 2 of the present application provides a perovskite thin film layer 4. Compared with Example 1, diphenylformamide hydrazide is added to the perovskite precursor solution in an equal molar amount to replace hydrazine, and the rest is consistent with Example 1.

[0118] Example 4

[0119] The fourth embodiment of the present application provides a perovskite thin film layer 4. Compared with the first embodiment, the molar ratio of hydrazine in the perovskite buried modification layer 41 is 5%, and the rest is consistent with the first embodiment.

[0120] Example 5

[0121] The fifth embodiment of the present application provides a perovskite thin film layer 4. Compared with the first embodiment, the molar ratio of hydrazine in the perovskite buried modification layer 41 is 10%, and the rest is consistent with the first embodiment.

[0122] Example 6

[0123] Example 6 of the present application provides a perovskite thin film layer 4. Compared with Example 1, the molar ratio of hydrazine in the perovskite buried modification layer 41 is 15%, and the rest is consistent with Example 1.

[0124] Example 7

[0125] Example 7 of the present application provides a perovskite thin film layer 4. Compared with Example 1, the molar ratio of hydrazine in the perovskite buried modification layer 41 is 20%, and the rest is consistent with Example 1.

[0126] Example 8

[0127] Example 8 of the present application provides a perovskite thin film layer 4. Compared with Example 1, the thickness of the perovskite buried modification layer 41 is 10 nm, and the rest is consistent with Example 1.

[0128] Example 9

[0129] Example 9 of the present application provides a perovskite thin film layer 4. Compared with Example 1, the thickness of the perovskite buried modification layer 41 is 20 nm, and the rest is consistent with Example 1.

[0130] Example 10

[0131] The tenth embodiment of the present application provides a perovskite thin film layer 4. Compared with the first embodiment, the thickness of the perovskite buried modification layer 41 is 30 nm, and the rest is consistent with the first embodiment.

[0132] Comparative Example 1

[0133] Comparative Example 1 of the present application provides a perovskite thin film layer 4 . Compared with Example 1, the perovskite thin film layer 4 does not contain a perovskite buried modification layer 41 , and the rest is consistent with Example 1.

[0134] Application Example 1

[0135] This application example 1 provides a perovskite silicon tandem solar cell, comprising a heterojunction bottom cell, an indium zinc oxide first transparent conductive film layer 2, a nickel oxide hole transport layer 3, a perovskite film layer 4 of the embodiment 1, and an electron transport layer 5C. 60 , indium zinc oxide second transparent conductive film layer 7, the perovskite silicon stack solar cell also includes a silver positive electrode 8 and a silver negative electrode 9, the silver negative electrode 9 forms an ohmic contact with the indium zinc oxide second transparent conductive film layer 7, and the silver positive electrode 8 forms an ohmic contact with the heterojunction bottom cell.

[0136] The preparation method of the perovskite silicon tandem solar cell comprises the following steps:

[0137] Provide heterojunction bottom cells;

[0138] A first transparent conductive thin film layer 2 of indium zinc oxide with a thickness of 90 nm is prepared on the heterojunction bottom cell by physical vapor deposition;

[0139] A nickel oxide hole transport layer 3 with a thickness of 25 nm is prepared on the indium zinc oxide first transparent conductive film layer 2 by magnetron sputtering or physical vapor deposition;

[0140] The perovskite thin film layer 4 of Example 1 is prepared on the surface of the nickel oxide hole transport layer 3;

[0141] The electron transport layer 5C with a thickness of 17.5 nm was prepared on the perovskite thin film layer 4 of Example 1 by vacuum evaporation. 60 ,

[0142] In the electron transport layer 5C 60 A second transparent conductive film layer 7 of indium zinc oxide with a thickness of 90 nm is prepared by physical vapor deposition;

[0143] A silver negative electrode 9 with a thickness of 325 nm was prepared on the indium zinc oxide second transparent conductive film layer 7 by vacuum evaporation. A silver positive electrode 8 with a thickness of 325 nm was prepared on the heterojunction bottom cell by vacuum evaporation.

[0144] Application Example 2

[0145] Application Example 2 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 1 is replaced by the perovskite thin film layer 4 of Example 2.

[0146] Application Example 3

[0147] Application Example 3 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 3 is used to replace the perovskite thin film layer 4 of Example 1.

[0148] Application Example 4

[0149] Application Example 4 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 4 is used to replace the perovskite thin film layer 4 of Example 1.

[0150] Application Example 5

[0151] Application Example 5 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 5 is used to replace the perovskite thin film layer 4 of Example 1.

[0152] Application Example 6

[0153] Application Example 6 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 6 is used to replace the perovskite thin film layer 4 of Example 1.

[0154] Application Example 7

[0155] Application Example 7 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 7 is used to replace the perovskite thin film layer 4 of Example 1.

[0156] Application Example 8

[0157] Application Example 8 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 8 is used to replace the perovskite thin film layer 4 of Example 1.

[0158] Application Example 9

[0159] Application Example 9 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 9 is used to replace the perovskite thin film layer 4 of Example 1.

[0160] Application Example 10

[0161] Application Example 10 of the present application provides a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Example 1 is replaced by the perovskite thin film layer 4 of Example 1.

[0162] Application Comparative Example 1

[0163] The present application uses Comparative Example 1 to provide a perovskite silicon tandem solar cell. Compared with Application Example 1, the perovskite thin film layer 4 of Comparative Example 1 is used to replace the perovskite thin film layer 4 of Example 1.

[0164] Experiment 1

[0165] The perovskite thin film layer 4 of Example 1 and Comparative Example 1 was used as the experimental object. After the perovskite thin film layer 4 of the experimental object was prepared, the experimental object was placed in a nitrogen cabinet for 72 hours, and the morphology of the perovskite thin film layer 4 of the above experimental object was scanned by SEM. The test results are shown in Figures 2 and 3.

[0166] It should be noted that in Figures 2 and 3, the circled portion represents the bottom of the perovskite thin film layer 4. Decomposition of the perovskite thin film layer 4 leaves lead iodide, a wide-bandgap semiconductor with poor conductivity. Therefore, the circled portion appears relatively bright, while the remaining phase is lead iodide.

[0167] As can be seen from Figures 2 and 3, the thickness of the perovskite thin film layer 4 of Example 1 was tested to be 442.2nm~448.1nm, and the thickness of the perovskite thin film layer 4 of Comparative Example 1 was tested to be 435.2nm~497.4nm. The thickness range of the perovskite thin film layer 4 of Example 1 is narrow, and it can be observed from Figure 2 that the overall perovskite thin film layer 4 is relatively uniform, and there is no obvious lead iodide residue at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3, proving that a perovskite buried modification layer 41 modified by hydrazine doping is introduced between the perovskite light absorbing layer 42 and the nickel oxide hole transport layer 3. Even after being placed for a period of time, there is no decomposition phenomenon at the interface of the perovskite thin film layer 4, and the stability is good. In Figure 3, the thickness range of the perovskite film layer 4 of Comparative Example 1 is relatively wide, and it can be observed from Figure 3 that the perovskite film layer 4 is uneven, and there is a clear and bright lead iodide at the interface between the perovskite film layer 4 and the nickel oxide hole transport layer 3, proving that without introducing the perovskite buried modification layer 41, the perovskite light absorbing layer 42 is directly in contact with the nickel oxide hole transport layer 3. After 72 hours of placement, a relatively bright lead iodide phase can be observed, proving that the interface of the perovskite film layer 4 has decomposition and poor stability. It can be seen that compared with Comparative Example 1, adding a hydrazine-doped perovskite buried modification layer 41 between the nickel oxide hole transport layer 3 and the perovskite light absorbing layer 42 can significantly improve the stability of the interface between the perovskite film layer 4 and the nickel oxide hole transport layer 3.

[0168] Experiment 2

[0169] The performance tests of open circuit voltage, short circuit current density, fill factor and energy conversion efficiency were carried out using the halm test sorting equipment. The halm machine is a device that simulates sunlight and is equipped with electronic loads, data acquisition and computing equipment to test the electrical performance of photovoltaic devices (including perovskite silicon stacked solar cells). The silicon wafer of the solar cell tested was 1.07cm 2 , the calibration light intensity is 1000±50W / m 2 The experimental test results are as follows, where PCE represents the energy conversion efficiency (%), Voc represents the open circuit voltage (V), and Jsc represents the short circuit current density (mA / cm -2 , FF represents fill factor, the unit is %. The test results are shown in Table 1, and the IV curves of Application Example 1 and Application Comparative Example 1 are shown in Figure 4.

[0170] Table 1

[0171] Combining Table 1 and Figure 4, it can be seen that compared with the application comparison example 1, the short-circuit current of application example 1 is increased by 1.04%, the open-circuit voltage is increased by 1.17%, the fill factor is increased by 5.80%, and the energy conversion efficiency is increased by 8.14%. It is proved that the introduction of the hydrazine-doped perovskite buried modification layer 41 between the perovskite light absorption layer 42 and the nickel oxide hole transport layer 3 is beneficial to modify and passivate the defects at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3, reduce carrier recombination, and thus the hole mobility and conversion efficiency of the perovskite stacked solar cell.

[0172] The short-circuit current, open-circuit voltage, fill factor and energy conversion efficiency of Application Examples 2 and 3 are also significantly improved compared with Comparative Example 1, proving that Application Examples 2 and 3 respectively use 2,5-dichlorophenylhydrazine and diphenylformamide as doping components of the perovskite buried modification layer 41, which is also beneficial to modifying and passivating the defects at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3, thereby improving the electrical performance of the perovskite solar tandem cell.

[0173] In Application Examples 1, 4, 5, 6, and 7, the doping ratio of hydrazine in the perovskite buried modification layer 41 is different. Among them, the short-circuit current, open-circuit voltage, fill factor, and energy conversion efficiency of Application Examples 4 and 7 are significantly lower than those of Application Examples 1, 5, and 6. This proves that the perovskite buried modification layer 41 doped with a specific ratio of hydrazine has the best effect on modifying and passivating the defects of the perovskite thin film layer 4 and improving the electrical properties of the perovskite thin film layer 4. However, if the ratio of doped hydrazine is too high or too low, the defect passivation effect of the perovskite thin film layer 4 will deteriorate, and the electrical performance of the perovskite thin film layer 4 will be reduced.

[0174] The thickness of the buried perovskite modification layer 41 in Application Examples 1, 8, 9 and 10 is different. The short-circuit current, open-circuit voltage, fill factor and energy conversion efficiency measured for the perovskite solar tandem cell in Application Example 10 are significantly lower than those in Application Examples 1, 8 and 9, proving that the buried perovskite modification layer 41 in a specific thickness range is better at modifying and passivating defects at the interface between the perovskite thin film layer 4 and the nickel oxide hole transport layer 3. If the buried perovskite modification layer 41 is too thick or too thin, the passivation effect of the buried perovskite modification layer 41 will decrease, and the electrical performance of the perovskite thin film layer 4 will decrease.

[0175] The above is a detailed introduction to the perovskite thin film layer and its preparation method, perovskite silicon tandem solar cell and its preparation method disclosed in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the perovskite thin film layer and its preparation method, perovskite silicon tandem solar cell and its preparation method and its core idea of ​​the present application: At the same time, for general technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A perovskite thin film layer, characterized in that: Used in perovskite solar cells, it comprises a perovskite buried modification layer stacked on the surface of a nickel oxide hole transport layer in the perovskite solar cell and a perovskite light absorption layer stacked on the surface of the perovskite buried modification layer, wherein the perovskite buried modification layer is doped with hydrazine and / or a hydrazine derivative.

2. The perovskite thin film layer according to claim 1, characterized in that The thickness of the perovskite buried modification layer is 10nm to 20nm.

3. The perovskite thin film layer according to claim 2, characterized in that: The thickness of the perovskite light-absorbing layer is 450 nm to 550 nm.

4. The perovskite thin film layer according to claim 1, characterized in that In the perovskite buried modification layer, the molar proportion of hydrazine and / or hydrazine derivatives is 10% to 15%.

5. The perovskite thin film layer according to claim 1, characterized in that: The hydrazine derivative contains one or more functional groups selected from the group consisting of phenyl, carbonyl and amino.

6. The perovskite thin film layer according to claim 5, characterized in that: The hydrazine derivatives include phenylhydrazine, 4-chlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine hydrochloride, 2,6-difluorophenylhydrazine, 4-iodophenylhydrazine, benzylhydrazine dihydrochloride, 2,4-dichlorophenylhydrazine, 2-fluorophenylhydrazine, 2,3-dimethylphenylhydrazine hydrochloride, 2,4-dimethylphenylhydrazine hydrochloride, 4-(4-hydrazinophenyl)-1,2,4-triazole hydrochloride, 4-chloro-o-tolylhydrazine hydrochloride, 4-methoxyphenylhydrazine hydrochloride, 5-bromo-2-methylphenylhydrazine hydrochloride, 2,6-dimethylphenylhydrazine hydrochloride, 3-(trifluoromethyl)phenylhydrazine hydrochloride, 3-chlorophenylhydrazine hydrochloride, 2-naphthylhydrazine, 2-naphthylhydrazine hydrochloride, 1-naphthylhydrazine hydrochloride, diphenylformylhydrazine, 4-(trifluoromethyl)quinolineformylhydrazine , 2-trifluoromethylquinoline-4-carboxylic acid hydrazide, 6-chloropyridine-3-carboxylic acid hydrazide, 6-fluoro-4-trifluoromethylquinoline-2-carboxylic acid hydrazide, 2-pyridinecarboxylic acid hydrazide, 3-phenoxybenzohydrazide, o-ethoxybenzohydrazide, 4-benzyloxybenzohydrazide, 3-trifluoromethylbenzohydrazide, 2,5-dimethoxybenzohydrazide 2,6-difluorobenzohydrazide, acetic acid hydrazide, methoxyacetic acid hydrazide, N-acetylphenylhydrazide, 1,2-diacetylhydrazine, 4-chloro-2-methylphenoxyacetic acid hydrazide, adipic acid dihydrazide, maleic acid hydrazide, maleic acid hydrazide, 4-maleimidobutyric acid hydrazide, p-dibenzoic acid dihydrazide, biphenylhydrazine, sebacic acid dihydrazide, 2-thiophenecarboxylic acid hydrazide, palmitic acid hydrazide, isophthalic acid dihydrazide, one or more thereof.

7. A method for preparing a perovskite thin film layer according to any one of claims 1 to 6, characterized in that: The method for preparing the perovskite thin film layer comprises the following steps: Preparation of the perovskite buried modification layer: dissolving hydrazine and / or hydrazine derivatives in a perovskite precursor solution, using the nickel oxide hole transport layer in the perovskite solar cell as a substrate, depositing the perovskite precursor solution doped with hydrazine and / or hydrazine derivatives on the surface of the nickel oxide hole transport layer, and annealing to obtain the perovskite buried modification layer; The perovskite light-absorbing layer is prepared by using the perovskite buried modification layer as a substrate, preparing a metal halide skeleton layer on the perovskite buried modification layer, spin-coating a halide cation solution on the metal halide skeleton layer, and annealing to obtain the perovskite light-absorbing layer.

8. The method for preparing a perovskite thin film layer according to claim 7, characterized in that: In the step of preparing the perovskite buried modification layer, the annealing temperature is 100° C. to 170° C., and the annealing time is 20 min to 40 min.

9. The method for preparing a perovskite thin film layer according to claim 7, wherein: In the step of preparing the perovskite light-absorbing layer, the annealing temperature is 100° C. to 170° C., and the annealing time is 20 min to 40 min.

10. The method for preparing a perovskite thin film layer according to claim 7, characterized in that: The metal halide skeleton layer includes lead iodide.

11. The method for preparing a perovskite thin film layer according to claim 10, characterized in that: The metal halide skeleton layer further comprises cesium bromide, and the halogenated cations in the halogenated cation solution comprise one or more of iodomethane, bromomethylamine and chloromethylamine.

12. The method for preparing a perovskite thin film layer according to claim 7, wherein: The thickness of the metal halide skeleton layer is 350nm to 450nm.

13. A perovskite silicon tandem solar cell, characterized in that: The invention comprises a silicon substrate cell, a first transparent conductive film layer, a nickel oxide hole transport layer, a perovskite film layer according to any one of claims 1 to 6 or a perovskite film layer prepared by the preparation method according to any one of claims 7 to 12, an electron transport layer, and a second transparent conductive film layer stacked in sequence. The perovskite silicon stacked solar cell further comprises a positive electrode and a negative electrode, wherein the negative electrode forms an ohmic contact with the second conductive film layer, and the positive electrode forms an ohmic contact with the silicon substrate cell.

14. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The second transparent conductive film layer is an indium zinc oxide layer.

15. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The thickness of the second transparent conductive film layer is 80 nm to 100 nm.

16. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The electron transport layer is C 60 .

17. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The thickness of the electron transport layer is 15 nm to 20 nm.

18. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The thickness of the nickel oxide hole transport layer is 20 nm to 30 nm.

19. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The positive electrode and the negative electrode are silver.

20. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The thickness of the positive electrode is 300 nm to 350 nm.

21. The perovskite silicon tandem solar cell according to claim 13, characterized in that: The thickness of the negative electrode is 300 nm to 350 nm.

22. The perovskite silicon tandem solar cell according to any one of claims 13 to 21, characterized in that: The perovskite silicon tandem solar cell further includes a buffer layer, which is located between the second transparent conductive film layer and the electron transport layer.

23. The perovskite silicon tandem solar cell according to claim 22, characterized in that: The buffer layer is tin oxide.

24. The perovskite silicon tandem solar cell according to claim 22, characterized in that: The thickness of the buffer layer is 20 nm to 30 nm.

25. A method for preparing a perovskite silicon tandem solar cell, characterized in that: The preparation method of the perovskite silicon tandem solar cell comprises the following steps: Provide silicon substrate cells; preparing a first transparent conductive film layer on the silicon substrate cell; preparing a nickel oxide hole transport layer on the first transparent conductive film layer; preparing the perovskite thin film layer on the surface of the nickel oxide hole transport layer; preparing an electron transport layer on the surface of the perovskite thin film layer; preparing a second transparent conductive film layer on the surface of the electron transport layer; Post-processing is performed to obtain the perovskite silicon tandem solar cell as described in any one of claims 13-24.

26. The method for preparing a perovskite silicon tandem solar cell according to claim 25, characterized in that: The first transparent conductive film layer is prepared by physical vapor deposition.

27. The method for preparing a perovskite silicon tandem solar cell according to claim 25, characterized in that: The nickel oxide hole transport layer is prepared by magnetron sputtering or physical vapor deposition.

28. The method for preparing a perovskite silicon tandem solar cell according to claim 25, wherein: The electron transport layer is prepared by vacuum evaporation method.

29. The method for preparing a perovskite silicon tandem solar cell according to claim 25, wherein: The second transparent conductive film layer is prepared by physical vapor deposition.

30. The method for preparing a perovskite silicon tandem solar cell according to any one of claims 25 to 29, characterized in that: The preparation method further comprises the following steps: A buffer layer is prepared on the electron transport layer, so that the buffer layer is located between the electron transport layer and the second transparent conductive thin film layer.

31. The method for preparing a perovskite silicon tandem solar cell according to claim 30, wherein: The buffer layer is prepared by atomic layer deposition.

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