Method for manufacturing a perovskite film

Abstract

The present application provides a method for producing a perovskite film, a perovskite film, a solar cell, and a solar cell device. The method includes the steps of: (1) providing a target material containing lead, a halogen, and one or more alkali metals; (2) sputtering the target material to obtain a film, the process gas being a rare gas, optionally argon gas; (3) subjecting the obtained film to a chemical bath treatment, the chemical bath being a solution of AX, where A is selected from one or more of formamidine and methylamine, and X is a halogen; and (4) sputtering the obtained film using metal tin to obtain a perovskite film, the process gas being a rare gas, optionally a mixture of argon gas and a halogen gas. The method has excellent film formation quality and high process controllability.

Description

Technical Field

[0001] This application relates to the technical field of solar cells, and particularly to a method for manufacturing a perovskite film and related perovskite films, solar cells, and solar cell devices.

Background Art

[0002] Perovskite film solar cells have become a hot spot in the research of next-generation solar cells because they have advantages such as a low electron-hole pair recombination rate and a wide range of strong light absorption. Currently, the manufacturing methods of perovskite films mainly include solution chemistry methods, spin coating methods, and vapor deposition methods. Among them, the solution chemistry method has a low manufacturing cost, a relatively simple process, and is the mainstream method for manufacturing high-quality film layers in the laboratory. However, such a method has low process stability, low reproducibility, and is disadvantageous for large-scale production. The coating method is the mainstream method for manufacturing large-area perovskite films, but its film formation is single, the influence of solution materials is large, and it cannot be flexibly controlled, and it is also difficult to ensure the uniformity of coating. The vapor deposition method in the prior art has high requirements for equipment, is difficult to control the relative ratio of precursors, has a high difficulty in manufacturing high-quality film layers, and has serious waste of raw materials. Therefore, it is very meaningful to provide a new method for manufacturing perovskite films with excellent film formation quality and high process controllability.

Summary of the Invention

Problems to be Solved by the Invention

[0003] This application is made in view of the above problems, and its purpose is to provide a method for manufacturing a perovskite film. The film formation of the perovskite film obtained by the method is uniform, and each process parameter of the method can be flexibly controlled, and the perovskite film can be adapted to various solar cell systems by adjusting the manufacturing parameters.

Means for Solving the Problems

[0004] To achieve the above object, the present application provides a method for manufacturing a perovskite film, a related perovskite film, a solar cell, and a solar cell device.

[0005] A first aspect of the present application provides a method for manufacturing a perovskite film, the method comprising: (1) providing a target material containing lead, a halogen, and one or more alkali metals as elements; (2) performing sputtering using the target material in step (1) to obtain a film, wherein the process gas is a noble gas, optionally argon gas; (3) treating the film obtained in step (2) in a chemical bath, wherein the chemical bath is a solution of AX, A is selected from one or more of formamidine and methylamine, and X is a halogen; (4) performing sputtering on the film obtained in step (3) using metallic tin to obtain a perovskite film, wherein the process gas is a noble gas, optionally a mixture of argon gas and halogen gas; and including.

[0006] The method of the present application allows adjustment of each parameter within a wide range, and the process stability and controllability are significantly improved compared to the prior art.

[0007] In any embodiment, optionally, based on the total molar number of each element in the target material, the target material in step (1) contains 10 - 40% alkali metal, 10 - 40% lead, and 50 - 90% halogen, and the sum thereof is 100%. When the molar content of each element is within the above range, the conversion efficiency of the corresponding solar cell is increased.

[0008] In any embodiment, optionally, the halogen in step (1) is one or more of chlorine, bromine, or iodine, and the alkali metal is one or more of potassium, rubidium, or cesium.

[0009] In any embodiment, optionally, the concentration of the solution of AX in step (3) is 10 - 100 mg / ml, and optionally 20 - 70 mg / ml. Thereby, the film-forming uniformity of the perovskite film can be further improved, thereby improving the conversion efficiency of the corresponding battery.

[0010] In any embodiment, optionally, the temperature of the chemical bath treatment in step (3) is 40 - 120 °C, and optionally 50 - 80 °C. Thereby, the properties of the obtained perovskite film can be further improved, thereby improving the conversion efficiency of the corresponding battery.

[0011] In any embodiment, optionally, the volume ratio of the noble gas, optionally argon gas, to the halogen gas in step (4) is 10:1 - 5:1. By using a mixture of a noble gas and a halogen gas as the process gas, the properties of the obtained perovskite film can be further improved, thereby improving the conversion efficiency of the corresponding battery.

[0012] In any embodiment, optionally, the halogen gas in step (4) contains one or more of iodine vapor, bromine vapor, or chlorine vapor.

[0013] In any embodiment, optionally, step (4) is carried out at a temperature of 50 - 250 °C, and optionally 100 - 200 °C.

[0014] The second aspect of the present application provides a perovskite film, which can be manufactured by the method described in the first aspect of the present application.

[0015] In any embodiment, optionally, the thickness of the perovskite film is from 200 to 500 nm, optionally from 400 to 500 nm, and further optionally from 450 to 470 nm.

[0016] In any embodiment, optionally, the band gap of the perovskite layer of the perovskite film is from 1.2 to 1.6 eV, optionally from 1.4 to 1.5 eV.

[0017] The third aspect of the present application provides a solar cell, which comprises a transparent conductive electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a back electrode, and these components are sequentially arranged from bottom to top in this order. The positions of the hole transport layer and the electron transport layer are interchangeable, and the perovskite layer is a perovskite film manufactured by the method described in the first aspect of the present application or a perovskite film described in the second aspect of the present application.

[0018] In any embodiment, optionally, the transparent conductive electrode is selected from one or more of indium tin oxide and fluorine-doped tin dioxide.

[0019] In any embodiment, optionally, the hole transport layer is poly(3,4-ethylenedioxythiophene), poly(styrene sulfonate) (PEDOT:PSS), poly(triarylamine) (PTAA), CuSCN, NiO x 、CuI、MoO x selected from one or more of them.

[0020] In any embodiment, optionally, the electron transport layer is selected from one or more of 2,2’,7,7’-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9’-spirobifluorene (spiro-OMeTAD), WO3, polyethyleneimine ethoxylate (PEIE), polyethyleneimine (PEI), ZnO, TiO2, [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM), SnO2, or fluorine-doped SnO2.

[0021] In any embodiment, optionally, the back electrode is selected from one or more of indium tin oxide, tungsten-doped indium oxide, aluminum-doped zinc oxide (AZO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg.

[0022] The fourth aspect of the present application provides a solar cell device, which includes the solar cell described in the third aspect of the present application.

[0023] Since the solar cell and the solar cell device of the present application include the perovskite film obtained by the manufacturing method of the present application, they have the same advantages as the manufacturing method of the present application.

Brief Description of the Drawings

[0024]

Figure 1

Modes for Carrying Out the Invention

[0025] Hereinafter, embodiments of a method for manufacturing a perovskite film of the present application, related perovskite films, solar cells, and solar cell devices will be described in detail with appropriate reference to the drawings. However, detailed descriptions that are not necessary may be omitted. For example, detailed descriptions of well-known matters and duplicate descriptions of actually identical structures may be omitted. This is to avoid the following description from becoming unnecessarily long and to enable those skilled in the art to easily understand. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and do not limit the theme described in the claims.

[0026] The "range" disclosed in the present application is limited in the form of a lower limit and an upper limit, and a given range is limited by selecting one lower limit and one upper limit, and the selected lower limit and upper limit define the boundary of a specific range. The range thus limited may or may not include the end values, and any combination is possible, that is, any lower limit can be combined with any upper limit to form a range. For example, when ranges of 60 to 120 and 80 to 110 are described for a specific parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also conceivable. Note that if the minimum range values are described as 1 and 2, and the maximum range values are described as 3, 4, and 5, all of the ranges of 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are conceivable. In the present application, unless otherwise specified, the numerical range of "a to b" represents a shortened expression of any real number combination of a to b, where both a and b are real numbers. For example, the numerical range of "0 to 5" means that all real numbers between "0 to 5" are listed in this specification, and "0 to 5" is only a shortened expression of the combination of these numerical values. Also, when a certain parameter is expressed as an integer ≧ 2, it corresponds to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0027] Unless otherwise specified, all embodiments and alternative embodiments of the present application can be combined with each other to form a new technical solution.

[0028] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0029] Unless otherwise specified, all steps of this application may be performed in order or randomly, and preferably, they are performed in order. For example, the fact that the method includes steps (a) and (b) means that the method may include steps (a) and (b) performed in order, or steps (b) and (a) performed in order. For example, the fact that the method mentioned above may further include step (c) means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or steps (a), (c), and (b), or steps (c), (a), and (b), etc.

[0030] Unless otherwise specified, the terms "comprising" and "including" mentioned in this application represent an open type and may also be a closed type. For example, the "comprising" and "including" may further include or contain other components not listed, or may include or contain only the listed components.

[0031] The terms "above" and "below" used in this application include that number. For example, "one or more" means one or more, and "one or more of A and B" means "A", "B", or "A and B".

[0032] Unless otherwise specified, in this application, the term "or" is inclusive. For example, the term "A or B" represents "A, B, or both A and B". More specifically, any of the conditions that A is true (or exists) and B is false (or does not exist), that A is false (or does not exist) but B is true (or exists), and that both A and B are true (or exist) satisfy "A or B".

[0033] The inventors of the present application have found the following from actual work. In a solar cell employing a perovskite film, in order to improve the conversion efficiency of the solar cell, parameters such as the width of the band gap of the perovskite film required for different solar cells are not the same. However, the manufacturing method of the perovskite film in the prior art has low controllability of process conditions and is difficult to adapt to the demands under different working conditions. In actual production, such drawbacks not only lead to an increase in the manufacturing cost of the perovskite film, but also there is a possibility that the quality of the obtained product is low, and further cause a decrease in the conversion efficiency of the solar cell. For example, the manufacturing of perovskite film by solution chemistry method not only uses toxic solvents, but also is difficult to control the uniformity of large-area film formation, and the actual application in the perovskite solar cell industry is greatly limited.

[0034] As a result of intensive research, the inventors have discovered a new method for manufacturing perovskite film, and the process stability and controllability of the manufacturing method have been significantly improved compared with the prior art. In addition, the inventors further optimize the treatment steps and corresponding process parameters, significantly improve the uniformity of the obtained film layer, improve the properties of the film layer, and enable the solar cell including the obtained film layer to have higher conversion efficiency.

[0035] [Manufacturing Method of Perovskite Film] The first aspect of the present application provides a manufacturing method of perovskite film, and this method includes: (1) providing a target material containing lead, halogen and one or more alkali metals which are elements; (2) performing sputtering using the target material in step (1) to obtain a film, wherein the process gas is a noble gas, optionally argon gas; (3) chemically bath treating the film obtained in step (2), wherein the chemical bath is a solution of AX, A is selected from one or more of formamidine and methylamine, and X is halogen. (4) Using metallic tin, performing sputtering on the film obtained in step (3) to obtain a perovskite film, wherein the process gas is a noble gas, optionally a mixture of argon gas and a halogen gas.

[0036] The manufacturing method of the perovskite film allows adjustment of each process parameter within a wide range by organically combining various processing steps, and the process stability and controllability are significantly improved compared to the prior art.

[0037] In addition, the inventors have found the following through further research. By adjusting each process parameter of the manufacturing method, the uniformity of the obtained film can be further improved, the film-forming quality can be improved, and thus the solar cell including the obtained film layer can have a higher conversion efficiency.

[0038] In some embodiments, optionally, based on the total molar number of each element in the target material, the target material in step (1) contains 10 - 40% of an alkali metal, 10 - 40% of lead, and 50 - 90% of a halogen, and the sum thereof is 100%.

[0039] Although the mechanism has not yet been elucidated, the inventors have found in their research that when the content of the elements, particularly the alkali metal and lead, is within the above range, the film formation of the perovskite film manufactured by the method described in the present application using the target material is more uniform, and the conversion efficiency of the finally manufactured solar cell is also higher.

[0040] In some embodiments, optionally, the halogen in step (1) is one or more of chlorine, bromine, or iodine, and the alkali metal is one or more of potassium, rubidium, or cesium.

[0041] In this application, initial sputtering is performed in step (2) to obtain a film layer. It should be noted that this application has no special requirements for the equipment used to perform the sputtering step, and it may be equipment commonly used in the art. For example, step (2) may be performed in a magnetron sputtering device. When performing sputtering on the target material, generally a certain substrate can be used, and the film formed on the surface of the substrate becomes the film described in step (2) of this application. In this specification, there are no particular restrictions on the selection of the substrate. For example, the substrate may be a substrate commonly used in the art, such as ceramics, glass, tin dioxide, doped tin dioxide, etc.

[0042] The method described in this application has no special requirements for the temperature at which step (2) is performed. For example, it may be performed at room temperature. However, those skilled in the art will understand that the temperature should not be too low so that the sputtering rate is not too small.

[0043] In some embodiments, optionally, in step (2), a noble gas, optionally argon gas, is used as the process gas. The presence of the process gas is beneficial to improving the uniformity of the obtained perovskite film.

[0044] In some embodiments, optionally, the flow rate of the process gas in step (2) is 100 - 500 sccm, optionally 150 - 300 sccm.

[0045] In some embodiments, optionally, when step (2) is performed in a magnetron sputtering device, the power of the corresponding magnetron sputtering device is 100 W - 20 kW, optionally 500 W - 5 kW.

[0046] In some embodiments, optionally, when step (2) is performed, the pressure in the chamber of the device is 0 - 200 Pa, excluding 0 Pa.

[0047] In some embodiments, optionally, the thickness of the sputtering in step (2) is 10 to 300 nm.

[0048] In the method described in this application, by chemically bath treating the film layer obtained in step (2), organic ions such as methylamine ions (CH3NH3 + , MA + ) or formamidine ions (FA + ) can be introduced, thereby improving the film layer quality and further enhancing the conversion efficiency of the corresponding solar cell.

[0049] In some embodiments, optionally, the concentration of the solution of AX in step (3) is 10 to 100 mg / ml, and optionally 20 to 70 mg / ml.

[0050] When the concentration of the solution of AX is lower than the above range, the improvement of the film layer performance by chemical bath treatment is not significant, and the conversion efficiency of the corresponding solar cell is low. If the concentration of the solution of AX is too high, the introduction of methylamine ions or formamidine ions may be excessive, which will instead damage the film layer quality. Optionally, when the concentration of the solution of AX is 10 to 100 mg / ml, and optionally 20 to 70 mg / ml, a more preferable effect of improving the film layer quality can be obtained.

[0051] In some embodiments, optionally, the solvent in the solution of AX is a solvent commonly used in the art, such as aromatic compounds like xylene, toluene or alkyl naphthalene, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons like chlorobenzene, vinyl chloride or methylene dichloride, alcohols like butanol, isopropanol or ethylene glycol and their ethers and esters, ketones like acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, and strong polar solvents like dimethylformamide, dimethyl sulfoxide and water. Optionally, the solvent is one or more of isopropanol or chlorobenzene.

[0052] In some embodiments, optionally, the temperature of the chemical bath treatment in step (3) is 40 to 120 °C, and optionally 50 to 80 °C.

[0053] An appropriate chemical bath treatment temperature is advantageous for promoting the penetration and migration of dopant ions into the film layer and improving the film layer quality. If the temperature of the chemical bath treatment is too low, for example, lower than room temperature, the progress of the chemical bath treatment will be very slow. When the temperature of the chemical bath treatment is higher than 150 °C, it may cause the deterioration of the film layer, degrade the properties of the film layer, and furthermore, the conversion efficiency of the solar cell will be significantly reduced.

[0054] The method described in this application further includes step (4) of performing post-treatment on the chemically bath-treated film. Different from step (2), the sputtering treatment in step (4) can improve the defects in the film layer quality caused by inappropriate operations that may occur in the aforementioned treatment steps, while the film layer quality can be further improved by introducing metals such as tin and halogens, thereby enabling the perovskite film produced to have a uniform film thickness and excellent film formation quality, and further improving the conversion efficiency of the corresponding solar cell.

[0055] In some embodiments, optionally, the volume ratio of the noble gas, optionally argon gas, to the halogen gas in step (4) is 10:1 to 5:1.

[0056] In the present application, the noble gas, optionally argon gas, serves a protective function to avoid damage to equipment or safety accidents caused by high temperatures. On the other hand, it may be used for impacts to generate ions, such as impacts on the target material or halogen gas, and thereby dope the obtained film layer to improve the film layer quality. Optionally, in the present application, when the total amount of the noble gas, optionally argon gas, and the mixed gas of the halogen gas is constant, adjusting the volume ratio between the two is advantageous for improving the film layer quality. In particular, when the volume ratio of the noble gas, optionally argon gas, to the halogen gas is 10:1 to 5:1, the improvement effect on the film layer quality is more significant.

[0057] In some embodiments, optionally, the halogen gas in step (4) includes one or more of iodine vapor, bromine vapor, and chlorine vapor.

[0058] In some embodiments, optionally, the halogen gas in step (4) is a mixture of bromine vapor and iodine vapor, and the volume ratio of bromine vapor to iodine vapor is 1:3 to 3:1.

[0059] In some embodiments, optionally, the flow rate of the process gas in step (4) is 100 to 500 sccm, and optionally 150 to 300 sccm.

[0060] In some embodiments, optionally, step (4) is carried out at a temperature of 50 to 250 °C, and optionally 100 to 200 °C.

[0061] When performing step (4) within the above temperature range, the corresponding sputtering reaction rate is high, which is beneficial for improving equipment efficiency. On the other hand, high temperature helps to accelerate the annealing process for the entire film layer by accelerating the movement of ions. Note that the appropriate operating temperature also helps to avoid the occurrence of condensation and the deterioration of film layer performance, thereby avoiding the deterioration of the conversion efficiency of the solar cell.

[0062] In some embodiments, optionally, when performing step (4) in a magnetron sputtering device, the power of the corresponding magnetron sputtering device is 600W - 5kW.

[0063] In some embodiments, optionally, when performing step (4), the pressure in the chamber of the device is 0 - 200 Pa, excluding 0 Pa.

[0064] In some embodiments, optionally, the thickness of the sputtering in step (4) is 120 - 200 nm, and optionally 150 - 170 nm.

[0065] [Perovskite Film] The second aspect of this application provides a perovskite film, which can be manufactured by the method described in the first aspect of this application.

[0066] In some embodiments, optionally, the thickness of the perovskite film is 200 - 500 nm, optionally 400 - 500 nm, and further optionally 450 - 470 nm.

[0067] It should be noted that in this application, the "thickness of the perovskite film" refers to the thickness corresponding to the film obtained after performing all of steps (1) - (4).

[0068] In some embodiments, optionally, the band gap of the perovskite layer of the perovskite film is 1.2 to 1.6 eV, and optionally 1.4 to 1.5 eV.

[0069] [Solar cell] The third aspect of the present application provides a solar cell, which includes a transparent conductive electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a back electrode, and these components are sequentially arranged from bottom to top in this order. The positions of the hole transport layer and the electron transport layer are interchangeable, and the perovskite layer is a perovskite film manufactured by the method described in the first aspect of the present application or a perovskite film described in the second aspect of the present application.

[0070] In some embodiments, optionally, the transparent conductive electrode is selected from one or more of indium tin oxide and fluorine-doped tin dioxide.

[0071] In some embodiments, optionally, the hole transport layer is poly(3,4-ethylenedioxythiophene), poly(styrenesulfonate) (PEDOT:PSS), poly(triarylamine) (PTAA), CuSCN, NiO x , CuI, MoO x selected from one or more of these.

[0072] In some embodiments, optionally, the electron transport layer is 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD), WO3, polyethyleneimine ethoxylate (PEIE), polyethyleneimine (PEI), ZnO, TiO2, [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM), SnO2 or fluorine-doped SnO2 selected from one or more of these.

[0073] In some embodiments, optionally, the back electrode is selected from one or more of indium tin oxide, tungsten-doped indium oxide, aluminum-doped zinc oxide (AZO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg.

[0074] In some embodiments, optionally, the solar cell described in the present application may be manufactured by a method generally used in the art. For example, a transparent conductive electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a back electrode layer may be sequentially laminated, wound and pressed, and the positions of the hole transport layer and the electron transport layer are interchangeable.

[0075] [Solar cell device] Perovskite films have very wide applications in functional materials, especially in the field of optoelectronics. Exemplarily, the present application has studied the application of perovskite films manufactured by the method described in the present application in the field of solar cells. It should be understood that the examples according to the present application are only for explaining the uses of the perovskite films obtained by the manufacturing method of the present application, and as will be understood by those skilled in the art, the uses of the perovskite films are not limited to the exemplified uses.

[0076] The fourth aspect of the present application provides a solar cell device, which includes one or more of the perovskite films manufactured by the method described in the first aspect of the present application, the perovskite films of the second aspect of the present application, or the solar cells described in the third aspect of the present application.

[0077] Examples Hereinafter, examples of the present application will be described. The examples described below are illustrative only and are merely for interpreting the present application, and should not be construed as limitations on the present application. When specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature of the relevant technical field or the product instruction manual are followed. For reagents or instruments used, those for which the manufacturer is not specified are all common products that can be purchased commercially.

[0078] The sources of the raw materials used in the examples are as shown in the following table.

[0079]

Table 1

[0080] Example 1-1 Manufacture of perovskite film (1) Take a set of fluorine-doped tin dioxide (FTO, with a fluorine doping amount of 10% based on the weight of tin dioxide) conductive glass with specifications of 1.5 cm × 1.5 cm × 2.2 mm, and use a laser marking machine to etch and remove a part of the FTO (the unetched area is a square area extending 0.5 cm from the center of the 1.5 cm × 1.5 cm surface of the FTO to each of the four sides). After etching, the FTO conductive glass sheet is washed several times successively with acetone and isopropanol, and finally immersed in deionized water and subjected to ultrasonic treatment for 10 minutes. After the foreign matters and dirt on the glass surface are removed, the obtained material is dried to obtain a substrate.

[0081] (2) Sputtering was performed on the substrate obtained in step (1) using target material 1 in a magnetron sputtering apparatus. A high-frequency power supply was employed, the power was 3 kW, the pressure in the magnetron sputtering apparatus chamber was 0.3 Pa, the process gas was argon gas, the argon gas flow rate was 500 sccm, the coating time (i.e., the sputtering treatment time) was 10 minutes, and the thickness of the obtained film layer was 200 nm.

[0082] (3) Transfer the film layer obtained in step (2) into a 100 ml isopropanol solution of formamidine iodide for chemical bath treatment. The concentration of the solution is 60 mg / ml, the bath treatment temperature is 50 °C, the treatment time is 20 minutes, and then it is dried to remove the solvent.

[0083] (4) Sputtering was performed on the film layer obtained in step (3) in a magnetron sputtering apparatus. A metal tin target material was adopted. The process gas is a mixed gas of argon gas, iodine vapor and bromine vapor with a volume ratio of 20:1:1. The flow rate of argon gas in the process gas is 200 sccm, and the flow rates of iodine vapor and bromine vapor are both 10 sccm. A high-frequency power supply was adopted, the power is 2 kw, the temperature in the magnetron sputtering apparatus chamber is 100 °C, the chamber pressure is 0.3 Pa, and the coating time (i.e., the sputtering treatment time) is 40 minutes. The increased film thickness after sputtering treatment in this step is 150 nm.

[0084] Through the above steps, the perovskite film of the present application was obtained.

[0085] Manufacture of Perovskite Solar Cells (1) Take a set of fluorine-doped tin dioxide (FTO, based on the weight of tin dioxide, fluorine doping amount 10%) conductive glass with specifications of 1.5 cm × 1.5 cm × 2.2 mm, and use a laser marking machine to etch and remove a part of the FTO (the unetched area is a square area extending 0.5 cm from the center of the FTO to each of the four sides). After etching, the FTO conductive glass sheet is washed several times with acetone and isopropanol in sequence, and finally immersed in deionized water for ultrasonic treatment for 10 minutes. After the foreign matter and dirt on the glass surface are removed, the obtained material is used as the substrate.

[0086] (2) The FTO conductive glass sheet obtained in step (1) is dried in a blower dryer to remove moisture, and then transferred to a magnetron sputtering device to sputter coat nickel oxide. A high-frequency power supply is adopted, the power is 1.5 kW, the temperature inside the magnetron sputtering device chamber is 50 °C, the chamber pressure is 0.2 Pa, the argon gas flow rate is 300 sccm, the oxygen gas flow rate is 50 sccm, the coating time is 5 minutes, and the thickness of the obtained film layer is 30 nm.

[0087] (3) Using the FTO conductive glass sputter-coated with nickel oxide obtained in step (2) as a substrate, the perovskite film described in this application is manufactured on the substrate, and the manufacturing process is the same as the manufacturing process of the perovskite film described above.

[0088] (4) The sheet sputtered with the perovskite film obtained in step (3) is placed in a vacuum coating machine, and 20 g of C60 (fullerene C60) and 20 g of BCP powder (2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline) are respectively placed in the magnetron sputtering device. First, C60 is vapor-deposited at a rate of 0.05 Å / s until 5 nm, and then at a rate of 0.1 Å / s until 30 nm. Then BCP is vapor-deposited at a rate of 0.05 Å / s until 2 nm, and then at a rate of 0.1 Å / s until 8 nm.

[0089] (5) The sheet obtained in step (4) is placed in an evaporation machine, and one layer of Ag electrode is evaporated, and the thickness of the Ag electrode is 50 nm.

[0090] Through the above steps, the perovskite solar cell described in this application is obtained.

[0091] Test method for related parameters Bandgap test of perovskite film The light transmittance and absorption spectrum of the film were measured using a Shimadzu UV-3600 spectrophotometer. A 5 cm × 5 cm × 2.2 mm white glass coated with a perovskite film layer was selected and placed in the test window. The light transmission and absorption formula from 300 to 1100 nm was selected from the software for testing to obtain the light transmittance and absorption spectrum of the perovskite film layer. Furthermore, the bandgap value of the perovskite film was obtained by converting the Tauc curve to the intersection of the tangent line and the energy axis.

[0092] Efficiency Test of Perovskite Solar Cells Based on the efficiency test method of standard IEC61215:2016, the IVS-KA6000 of Guangyan Technology Co., Ltd. was adopted to test the efficiency of the assembly.

[0093] Examples 1-2 to 1-5 In the process of manufacturing the perovskite film, except that the concentrations of the isopropanol solution of formamidinium iodide are 10 mg / ml, 20 mg / ml, 70 mg / ml, and 100 mg / ml respectively, the other conditions of Examples 1-2 to 1-5 are the same as those of Example 1-1.

[0094] Examples 1-6 to 1-9 In the process of manufacturing the perovskite film, except that the temperatures of the chemical bath treatment are 40 °C, 80 °C, 100 °C, and 120 °C respectively, the other conditions of Examples 1-6 to 1-9 are the same as those of Example 1-1.

[0095] Comparative Example 1 In the process of manufacturing the perovskite film, except that the concentration of the isopropanol solution of formamidinium iodide is 5 mg / ml, the other conditions of Comparative Example 1 are the same as those of Example 1-1.

[0096] Comparative Examples 2-3 In the process of manufacturing the perovskite film, except that the temperatures of the chemical bath treatment are 150 °C and 170 °C respectively, the other conditions of Comparative Examples 2-3 are the same as those of Example 1-1.

[0097] Comparative Example 4 In the process of manufacturing the perovskite film, other conditions of Comparative Example 4 are the same as those of Example 1-1, except that chemical bath treatment is not performed.

[0098] [Table 2]

[0099] As can be seen from Table I, by subjecting the obtained perovskite film to chemical bath treatment, the conversion efficiency of the solar cell can be effectively improved. However, if the concentration of AX is too low or the chemical bath treatment temperature is too high, the increase in chemical bath treatment may instead deteriorate the performance of the perovskite film and cause a decrease in the conversion efficiency of the solar cell.

[0100] Examples 2-1 to 2-5 In the process of manufacturing the perovskite film, other conditions of Examples 2-1 to 2-5 are the same as those of Example 1-1, except that the volume ratios of argon gas, iodine vapor, and bromine vapor in the post-treatment process of step (4) are 20:1:1, 10:1:1, 20:0.5:0.5, 20:1.5:0.5, and 10:0:1, respectively.

[0101] Comparative Examples 5-6 In the process of manufacturing the perovskite film, other conditions of Comparative Examples 5-6 are the same as those of Example 1-1, except that the volume ratios of argon gas, iodine vapor, and bromine vapor in the post-treatment process of step (4) are 0:0:0 and 1:0:0, respectively.

[0102] [Table 3]

[0103] As can be seen from Table II, in the post-treatment process of step (4), when argon gas and halogen gas coexist, the performance of the perovskite film can be effectively improved, and the efficiency of the solar cell can be enhanced. In particular, when the volume ratio of argon gas to halogen gas is 10:1 to 5:1, the conversion efficiency of the solar cell can be further improved.

[0104] Examples 3-1 to 3-4 In the process of manufacturing the perovskite film, except that the sputtering temperatures in the post-treatment process of step (4) are 50°C, 150°C, 200°C, and 250°C respectively, the other conditions of Examples 3-1 to 3-4 are the same as those of Example 1-1.

[0105] Comparative Examples 7-8 In the process of manufacturing the perovskite film, except that the sputtering temperatures during the post-treatment process of step (4) are 30°C and 300°C respectively, the other conditions of Comparative Examples 7-8 are the same as those of Example 1-1.

[0106]

Table 4

[0107] As can be seen from Table III, when the sputtering temperature in the post-treatment process of step (4) is 50 to 250°C, it is beneficial to the improvement of the performance of the perovskite film, thereby enhancing the efficiency of the solar cell. In particular, when the sputtering temperature is 100 to 200°C, the improvement effect on the efficiency of the solar cell is more significant.

[0108] It should be noted that this application is not limited to the above embodiments. The above embodiments are examples, and embodiments that have substantially the same configuration as the technical idea within the scope of the technical solution of this application and exhibit the same effects are all included within the technical scope of this application. In addition, within the scope not departing from the spirit of this application, various modifications that those skilled in the art can conceive of with respect to the embodiments, and other forms constructed by combining some components in the embodiments are also included within the scope of this application.

Explanation of Reference Numerals

[0109] 1. Back electrode, 2. Hole transport layer, 3. Perovskite layer, 4. Electron transport layer, 5. Transparent conductive electrode, 6. Glass

Claims

1. A method for manufacturing a perovskite film, comprising: (1) providing a target material containing lead, a halogen, and one or more alkali metals as elements; (2) performing sputtering using the target material in step (1) to obtain a film, wherein the process gas is a noble gas; (3) treating the film obtained in step (2) in a chemical bath, wherein the chemical bath is a solution of AX, A is selected from one or more of formamidine and methylamine, and X is a halogen; (4) performing sputtering on the film obtained in step (3) using metallic tin to obtain a perovskite film, wherein the process gas is a noble gas. A method for manufacturing a perovskite film, comprising the above steps.

2. The method according to claim 1, wherein the noble gas in step (2) is argon gas.

3. Based on the total number of moles of each element in the target material, the target material in step (1) contains 10-40% alkali metal, 10-40% lead, and 50-80% halogen, and the sum thereof is 100%. The method according to claim 1.

4. The method according to any one of claims 1 to 3, wherein the halogen in step (1) is one or more of chlorine, bromine, or iodine, and the alkali metal is one or more of potassium, rubidium, or cesium.

5. The method according to any one of claims 1 to 4, wherein the concentration of the AX solution in step (3) is 10-100 mg / ml.

6. The method according to claim 5, wherein the concentration of the AX solution in step (3) is 20-70 mg / ml.

7. The method according to any one of claims 1 to 6, wherein the temperature of the chemical bath treatment in step (3) is 40°C to 120°C.

8. The method according to claim 7, wherein the temperature of the chemical bath treatment in step (3) is 50°C to 80°C.

9. The method according to any one of claims 1 to 8, wherein the noble gas in step (4) is a mixture of argon gas and halogen gas, and the volume ratio of argon gas to halogen gas is 10:1 to 5:

1.

10. The method according to claim 9, wherein the halogen gas in the step (4) contains one or more of iodine vapor, bromine vapor, and chlorine vapor.

11. The method according to any one of claims 1 to 10, wherein the step (4) is performed at a temperature of 50 to 250 °C.

12. The step (4) is performed at a temperature of 100 to 200 °C, the method according to claim 11.

13. The method according to any one of claims 1 to 12, wherein the thickness of the perovskite film is 200 to 500 nm.

14. The method according to claim 13, wherein the thickness of the perovskite film is 400 to 500 nm.

15. The method according to claim 14, wherein the thickness of the perovskite film is 450 to 470 nm.

16. The method according to any one of claims 1 to 15, wherein the band gap of the perovskite layer of the perovskite film is 1.2 to 1.6 eV.

17. The method according to claim 16, wherein the band gap of the perovskite layer of the perovskite film is 1.4 to 1.5 eV.

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