CN114597311A - Perovskite thin film, perovskite solar cell and preparation method thereof - Google Patents

Perovskite thin film, perovskite solar cell and preparation method thereof Download PDF

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CN114597311A
CN114597311A CN202210214886.4A CN202210214886A CN114597311A CN 114597311 A CN114597311 A CN 114597311A CN 202210214886 A CN202210214886 A CN 202210214886A CN 114597311 A CN114597311 A CN 114597311A
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perovskite
thin film
precursor
perovskite thin
layer
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朱桂
安扬
袁晨辰
陈加坡
陈伟中
田清勇
范斌
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Kunshan Gcl Photoelectric Materials Co ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a perovskite thin film, a perovskite solar cell and a preparation method thereof. The preparation method of the perovskite thin film comprises the following steps: providing a perovskite precursor solution, wherein the perovskite precursor solution comprises a perovskite precursor, a solvent and a cross-linking agent; coating the perovskite precursor solution on a substrate, and removing at least part of the solvent to form a perovskite thin film precursor; preheating the perovskite thin film precursor to 80-120 ℃; and heating the preheated perovskite thin film precursor to 300-400 ℃ for annealing for 5-15s to form the perovskite thin film on the substrate. The perovskite thin film prepared by the invention effectively improves the crystallinity of perovskite and reduces the crystal boundary, thereby improving the efficiency and stability of the perovskite solar cell; and the preparation method can effectively shorten the preparation time of the perovskite thin film and greatly improve the production efficiency.

Description

Perovskite thin film, perovskite solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite thin film, a perovskite solar cell and a preparation method thereof.
Background
In recent years, with the continuous and intensive research, the perovskite battery has been developed rapidly, and the efficiency is increased from the first 3.8% to more than 25%, so that the perovskite battery is known as "new hope in the photovoltaic field".
The crystallinity of perovskite is a key factor influencing the efficiency of a device, the poor crystallinity of perovskite and the too small grain size of perovskite can cause the generation of relatively more grain boundary interfaces, thereby causing a plurality of defects, such as dislocation, impurity defects and vacancy defects formed by chemical bond fracture, and influencing the efficiency and stability of the perovskite solar cell. Therefore, the method improves the crystallinity of the perovskite crystal and reduces the grain boundary, and is an effective strategy for improving the efficiency and stability of the battery.
The common perovskite annealing temperature is generally between 100-200 ℃, the perovskite crystal grains obtained by preparation are small, the crystallinity is poor, and excessive crystal boundaries are generated, so that a plurality of defects are caused, and the efficiency and the stability of the solar cell are influenced. If a conventional annealing mode is used in production, more preparation time is consumed, and the production efficiency is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a perovskite thin film, a perovskite solar cell and a preparation method thereof, which can improve the crystallinity of perovskite and reduce grain boundaries, thereby improving the efficiency and stability of the perovskite solar cell, effectively shortening the preparation time of the perovskite thin film and improving the production efficiency.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a perovskite thin film, comprising:
providing a perovskite precursor solution, wherein the perovskite precursor solution comprises a perovskite precursor, a solvent and a cross-linking agent;
coating the perovskite precursor solution on a substrate, and removing at least part of the solvent to form a perovskite thin film precursor;
preheating the perovskite thin film precursor to 80-120 ℃;
and heating the preheated perovskite thin film precursor to 300-400 ℃ for annealing for 5-15s, thereby forming the perovskite thin film on the substrate.
In a second aspect, the invention further provides a perovskite thin film prepared by the preparation method.
In a third aspect, the invention further provides a perovskite solar cell, which at least comprises a hole transport layer, a perovskite layer and an electron transport layer which are stacked, wherein the perovskite layer comprises the perovskite thin film.
In a fourth aspect, the present invention further provides a method for preparing the above perovskite solar cell, including:
providing a conductive substrate;
a step of forming a first transfer layer on the surface of the conductive substrate;
forming a perovskite thin film on the surface of the first transmission layer by using the preparation method of the perovskite thin film to serve as a perovskite layer;
a step of forming a second transmission layer on the surface of the perovskite layer; and the number of the first and second groups,
and constructing a conductive electrode on the surface of the second transmission layer, wherein the conductive characteristics of the first transmission layer and the second transmission layer are opposite.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
1. the preparation method of the perovskite thin film and the perovskite thin film effectively improve the crystallinity of perovskite and reduce crystal boundary, thereby improving the efficiency and stability of the perovskite solar cell.
2. The preparation method of the perovskite thin film provided by the invention can effectively shorten the preparation time of the perovskite thin film and greatly improve the production efficiency.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the detailed drawings.
Drawings
FIG. 1 is a surface electron microscope image of a perovskite thin film prepared in a typical embodiment provided by the present invention;
FIG. 2 is a surface electron microscope image of a perovskite thin film prepared in a typical comparative example provided by the present invention;
FIG. 3 is a plot of the current-voltage characteristics of perovskite thin films prepared in examples and comparative examples provided by the present invention;
fig. 4 is a graph of the efficiency of different perovskite thin film batteries prepared according to examples of the present invention and comparative examples, which was traced over time after being stored in a nitrogen glove box for thirty days.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment of the invention provides a preparation method of a perovskite thin film, which comprises the following steps:
providing a perovskite precursor solution, wherein the perovskite precursor solution comprises a perovskite precursor, a solvent and a cross-linking agent.
And coating the perovskite precursor solution on a substrate, and removing at least part of the solvent to form the perovskite thin film precursor.
Preheating the perovskite thin film precursor to 80-120 ℃.
And heating the preheated perovskite thin film precursor to the temperature of 300-400 ℃ for annealing for 5-15 seconds, thereby forming the perovskite thin film on the substrate.
The thermal annealing plays an important role in the growth of perovskite crystals, and through long-time research and practice, the inventor of the invention finds that with the increase of the annealing temperature, the prepared perovskite crystal grains are larger, but the excessive temperature can cause the 'escape' of organic components in the perovskite thin film, so that the components are deviated, and the battery efficiency is influenced.
In some embodiments, the crosslinking agent may include one or a combination of two or more of a triacrylate-based crosslinking agent, a polyolefin crosslinking agent, and a silane crosslinking agent.
In some embodiments, the crosslinking agent may preferably include one or a combination of two of trimethylolpropane triacrylate, polyethylene.
In the present invention, cross-linking refers to a cross-linked network structure formed by chemical bonds or physical interactions, wherein the cross-linking method may include physical cross-linking and chemical cross-linking, and the chemical cross-linking may be divided into silane cross-linking and peroxide, so that, for example, common polyethylene and silane have the same cross-linking effect.
In some embodiments, the moles of cross-linking agent in the perovskite precursor solution are between 0.1 and 0.3% of the moles of perovskite precursor.
In some embodiments, the perovskite precursor may include any one or a combination of two or more of a methylamine perovskite precursor, a methylamine formamidine mixed perovskite precursor, and a ternary mixed perovskite precursor.
In some embodiments, the concentration of the perovskite precursor in the perovskite precursor solution may be in the range of 1.2 to 1.5 mol/L.
In some embodiments, the method of making may comprise: and removing at least part of the solvent in the perovskite precursor solution by adopting a vacuum pumping and/or anti-solvent method to form the perovskite thin film precursor.
In some typical application cases, the preparation method of a perovskite thin film can be implemented by adopting the following technical scheme:
the first step is as follows: preparing perovskite precursor solution with a certain concentration, adopting N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone as a solvent, and adding an additive with a crosslinking effect, such as trimethylolpropane triacrylate.
The second step is that: spin-coating or coating a perovskite solution on a substrate, removing most of solvent by adopting a vacuum pumping mode to obtain a slightly dried perovskite thin film, then adopting a two-step annealing method, firstly heating the perovskite thin film on a 100 ℃ hot platform to completely crystallize the perovskite to obtain a black alpha-phase thin film, then annealing the perovskite thin film at a higher temperature of about 300-400 ℃ within a few seconds to a dozen seconds to remove all the solvent to obtain the perovskite thin film with larger grains.
The perovskite thin film with larger grains is prepared by the process method, the grain boundary is effectively reduced, the efficiency and the stability of the solar cell are improved, and in addition, the production efficiency can be effectively improved when the process method is applied to production.
The embodiment of the invention also provides the perovskite thin film prepared by the preparation method of any perovskite thin film, and the average size of crystal grains in the perovskite thin film is preferably 600-1000 nm.
The embodiment of the invention also provides a perovskite solar cell, which at least comprises a hole transport layer, a perovskite layer and an electron transport layer which are sequentially stacked, wherein the perovskite layer comprises the perovskite thin film.
In some embodiments, the hole transport layer may include a Spiro-OMeTAD (2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group)]-9, 9' -Spiro-IIFluorene), PEDOT: PSS, P3Any one or a combination of two or more of HT, PTAA or PCDTBT.
The embodiment of the invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
a conductive substrate is provided.
And forming a first transmission layer on the surface of the conductive substrate.
And forming a perovskite thin film on the surface of the first transmission layer by using any one of the above perovskite thin film preparation methods as a perovskite layer.
And forming a second transmission layer on the surface of the perovskite layer.
And constructing a conductive electrode on the surface of the second transmission layer, wherein the conductive characteristics of the first transmission layer and the second transmission layer are opposite.
The first transport layer may be an electron transport layer, for example, in which case the second transport layer may be a hole transport layer, or may be inverted, the first transport layer being a hole transport layer and the second transport layer being an electron transport layer.
In some typical application cases, the perovskite solar cell device can be a forward structure device or an inverted structure device. The structure is as follows: a conductive substrate/hole or electron transport layer/perovskite layer/electron or hole transport layer/electrode having a conductive property opposite to that of the above hole or electron transport layer, which are sequentially stacked, wherein the materials and thicknesses of the respective layers may preferably be: the conductive substrate is one of FTO conductive glass, ITO conductive glass, FTO conductive plastic and ITO conductive plastic, wherein the thickness of the FTO conductive glass is about 500nm, and the thickness of the ITO conductive glass is about 300-400 nm; the thickness of the buffer layer is 10-20 nm; the perovskite layer is preferably MAPbI3 (the structural formula of MA is CH3NH3+) with the thickness of 300-1000 nm; the hole transport layer is Spiro-OMeTAD (2, 2 ', 7, 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 ' -spirobifluorene), PEDOT: any one of PSS, P3HT, PTAA or PCDTBT with the thickness of 300-600 nm; the electrode is made of any one of Ag, Al, Au or TCO, and has a thickness of about 100-300 nm.
The method for preparing each layer may preferably be: the conductive substrate is prepared by a physical vapor deposition method, an evaporation method or a sputtering method; the electron transport layer and the hole transport layer are prepared by any one of methods such as spin coating, spray coating or blade coating; the perovskite layer is prepared by the preparation method of the perovskite film, wherein a vacuum pumping preparation method or an anti-solvent method is adopted to remove the solvent; the conductive electrode can be prepared by a vacuum evaporation method or a vacuum sputtering method, can be a metal electrode, and can also be a transparent conductive oxide film or TCO electrode.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The embodiment provides a preparation method of a perovskite thin film, which comprises the following steps:
the first step is as follows: preparing perovskite precursor MAPbI with concentration of 1.3mol/L3The method comprises the following steps of (1) doping trimethylolpropane triacrylate in a certain proportion, wherein the concentration of the trimethylolpropane triacrylate is 0.2% of the molar concentration of a perovskite precursor, and N, N-dimethylformamide and N-methylpyrrolidone in a volume ratio of 9: 1 are adopted as solvents;
the second step: the method comprises the steps of coating a perovskite solution on a substrate in a spinning mode, removing most of solvent by adopting a vacuum air exhaust mode to obtain a semi-crystalline perovskite film, placing the semi-crystalline perovskite film on a hot table, heating to 100 ℃ to enable the semi-crystalline perovskite film to be converted into a black alpha-phase perovskite film precursor, removing most of solvent in the preheating step, avoiding the phenomenon that the residual solvent is subjected to bumping to enable the film to form holes due to direct ultrahigh-temperature heating, and then placing the perovskite film precursor on a heating table at 400 ℃ for annealing for 5s to obtain the completely-crystallized perovskite film.
The surface electron microscope image of the perovskite thin film is shown in fig. 1.
Example 2
This example provides a method of preparing a perovskite thin film, the embodiment being substantially the same as example 1 except that:
in the perovskite precursor solution, the perovskite precursor is a mixture of methyl ammonium iodide, formamidine hydroiodide, cesium iodide and lead iodide in a molar ratio of 0.05: 0.85: 0.1: 1.
Example 3
This example provides a method of preparing a perovskite thin film, the embodiment being substantially the same as example 1 except that:
in the perovskite precursor solution, the cross-linking agent is polyethylene accounting for 0.2 mol% of the perovskite precursor.
Example 4
This example provides a method of preparing a perovskite thin film, the embodiment being substantially the same as example 1 except that:
preheating a semi-crystalline perovskite thin film to 80 ℃;
and (3) annealing the perovskite film precursor for 15s in a heating table at 300 ℃ to obtain the completely crystallized perovskite film.
Example 5
This example provides a method of preparing a perovskite thin film, the embodiment being substantially the same as example 1 except that:
preheating a semi-crystalline perovskite thin film to 120 ℃;
and (3) annealing the perovskite film precursor for 10s in a heating table at 350 ℃ to obtain the completely crystallized perovskite film. .
Example 6
This example provides a method of preparing a perovskite thin film, the embodiment being substantially the same as example 1 except that:
the crosslinking agent used is a silane crosslinking agent.
Comparative example 1
The comparative example provides a method for preparing a perovskite thin film, comprising the steps of:
the first step is as follows: preparing an undoped perovskite precursor solution: mixing methyl ammonium iodide and lead iodide in equal molar ratio to prepare perovskite precursor MAPbI3The first preparation of example 1 was carried out using N, N-dimethylformamide and N-methylpyrrolidone as solvents in a volume ratio of 9: 1Step one, perovskite precursor solution with equal concentration;
the second step is that: spin-coating the perovskite solution on a substrate, removing most of the solvent by vacuum pumping to obtain a semi-crystalline perovskite film, and annealing the perovskite film on a heating table at 100 ℃ for 30min to obtain the completely-crystalline perovskite film.
The surface electron microscope image of the perovskite thin film prepared in this comparative example is shown in fig. 2.
Comparative example 2
The comparative example provides a method for preparing a perovskite thin film, comprising the steps of:
the first step is as follows: preparing perovskite precursor solution with the same concentration and the same type as those in the embodiment 1, doping the perovskite precursor solution with the same compound as that in the embodiment 1, adopting N, N-dimethylformamide and N-methylpyrrolidone as solvents, wherein the volume ratio of the solvents is 9: 1
The second step is that: spin-coating the perovskite solution on a substrate, removing most of the solvent by vacuum pumping to obtain a semi-crystalline perovskite film, and annealing the perovskite film on a heating table at 100 ℃ for 30min to obtain the completely-crystalline perovskite film.
Comparative example 3
The comparative example provides a method for preparing a perovskite thin film, comprising the steps of:
the first step is as follows: preparing undoped perovskite precursor solution, and mixing methyl ammonium iodide and lead iodide to prepare perovskite precursor MAPbI3Preparing a perovskite precursor solution with the same concentration as that in the first step in the embodiment 1 by using N, N-dimethylformamide and N-methylpyrrolidone as solvents and the volume ratio of the solvents is 9: 1;
the second step is that: spin-coating the perovskite solution on a substrate, removing most of solvent by vacuum pumping to obtain a semi-crystalline perovskite thin film, placing the semi-crystalline perovskite thin film on a heating table, heating to 100 ℃ to convert the semi-crystalline perovskite thin film into a black alpha-phase perovskite thin film precursor, and then placing the perovskite thin film precursor on a heating table at 400 ℃ for annealing for 5s to obtain the completely-crystallized perovskite thin film.
The cell performance test of the solar cell formed by the perovskite thin films prepared in the above example 1 and comparative examples 1 to 3 is performed, and the test results are shown in the following table:
Figure BDA0003532123550000071
the voltammetry characteristic curves of the perovskite thin films prepared in the above example 1 and comparative examples 1 to 3 are shown in fig. 3, and the curves show that the open-circuit voltage, the short-circuit current, the fill factor and the final efficiency of the perovskite thin film provided by the embodiment of the invention are all significantly improved, which shows that the defects in the perovskite are significantly reduced, and the device performance is significantly optimized.
The cell efficiency of the perovskite thin-film solar cells prepared in example 1 and comparative examples 1 to 3 is shown in the graph of fig. 4, in which the stability of the perovskite thin-film solar cells prepared in example is significantly stronger than that of the perovskite thin-film solar cells prepared in example. To facilitate understanding of the technical effects of the present invention, the final result data of the above stability test are shown in the following table:
sample (I) Normalized efficiency after 30 days
Example 1 95.6％
Comparative example 1 85.1％
Comparative example 2 93.4％
Comparative example 3 91.0％
。
Based on the detection result, the perovskite thin film prepared by the preparation method of the perovskite thin film provided by the invention has the advantages that the grain size is obviously larger than that of the perovskite thin film prepared by the prior art, the crystallization performance is excellent, the efficiency and the stability of the perovskite solar cell are improved, and the efficiency of the prepared perovskite solar cell is obviously superior to that of the prior art; in addition, the annealing time of the preparation method of the perovskite thin film is obviously shortened, and the production efficiency can be greatly improved.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A method for preparing a perovskite thin film, comprising:
providing a perovskite precursor solution, wherein the perovskite precursor solution comprises a perovskite precursor, a solvent and a cross-linking agent;
coating the perovskite precursor solution on a substrate, and removing at least part of the solvent to form a perovskite thin film precursor;
preheating the perovskite thin film precursor to 80-120 ℃;
and heating the preheated perovskite thin film precursor to 300-400 ℃ for 5-15s of annealing treatment, thereby forming the perovskite thin film on the substrate.
2. The method according to claim 1, wherein the crosslinking agent comprises one or a combination of two or more of a triacrylate-based crosslinking agent, a polyolefin crosslinking agent, and a silane crosslinking agent;
preferably, the crosslinking agent comprises one or two of trimethylolpropane triacrylate and polyethylene.
3. The production method according to claim 2, wherein the number of moles of the crosslinking agent in the perovskite precursor solution is 0.1 to 0.3% of the number of moles of the perovskite precursor.
4. The production method according to claim 1, wherein the perovskite precursor includes any one or a combination of two or more of a methylamine perovskite precursor, a methylamine formamidine mixed perovskite precursor, and a ternary mixed perovskite precursor.
5. The production method according to claim 4, wherein the concentration of the perovskite precursor in the perovskite precursor solution is 1.2 to 1.5 mol/L.
6. The method of claim 1, comprising: and removing at least part of the solvent in the perovskite precursor solution by adopting a vacuum pumping and/or anti-solvent method to form the perovskite thin film precursor.
7. The perovskite thin film obtained by the production method as set forth in any one of claims 1 to 6, wherein the average size of crystal grains in the perovskite thin film is 600-1000 nm.
8. A perovskite solar cell comprising at least a hole transport layer, a perovskite layer and an electron transport layer which are stacked, wherein the perovskite layer comprises the perovskite thin film according to claim 7.
9. The perovskite solar cell of claim 8, wherein the hole transport layer comprises a mixture of Spiro-OMeTAD, PEDOT: PSS, P3Any one or more of HT, PTAA or PCDTBTA combination of two or more thereof.
10. The method of fabricating a perovskite solar cell as defined in any one of claims 8 to 9, comprising:
providing a conductive substrate;
a step of forming a first transfer layer on the surface of the conductive substrate;
a step of forming a perovskite thin film on the surface of the first transport layer as a perovskite layer by the production method according to any one of claims 1 to 6;
a step of forming a second transmission layer on the surface of the perovskite layer; and the number of the first and second groups,
and constructing a conductive electrode on the surface of the second transmission layer, wherein the conductive characteristics of the first transmission layer and the second transmission layer are opposite.
CN202210214886.4A 2022-03-04 2022-03-04 Perovskite thin film, perovskite solar cell and preparation method thereof Pending CN114597311A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360307A (en) * 2022-10-17 2022-11-18 中国华能集团清洁能源技术研究院有限公司 Preparation method of perovskite thin film
CN115498110A (en) * 2022-11-17 2022-12-20 无锡众能光储科技有限公司 Perovskite solar cell with composite structure and preparation method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360307A (en) * 2022-10-17 2022-11-18 中国华能集团清洁能源技术研究院有限公司 Preparation method of perovskite thin film
CN115360307B (en) * 2022-10-17 2023-01-24 中国华能集团清洁能源技术研究院有限公司 Preparation method of perovskite thin film
CN115498110A (en) * 2022-11-17 2022-12-20 无锡众能光储科技有限公司 Perovskite solar cell with composite structure and preparation method

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