Perovskite solar cells, their manufacturing method, and power consumption devices

Abstract

The present application relates to a perovskite solar cell, a preparation method thereof, and a power consumption device. The perovskite solar cell includes a transparent electrode, a first functional layer, a perovskite layer, a second functional layer, and a second electrode layer arranged in a stacked manner, the perovskite layer including a three-dimensional perovskite layer and a two-dimensional perovskite layer arranged in a stacked manner, the surface of the three-dimensional perovskite layer contacting the first functional layer is a first surface, the remaining surfaces constitute second surfaces, and the two-dimensional perovskite layer covers the entire second surface.

Description

[Technical Field]

[0001] (cross reference) This application references patent application number PCT / CN2022 / 123787, filed on October 8, 2022, entitled "Perovskite solar cell, manufacturing method thereof, and power consumption device," which is incorporated herein by reference in its entirety.

[0002] (Technical field) The present application relates to the field of solar cell technology, and in particular to perovskite solar cells, methods for manufacturing the same, and power consumption devices. [Background technology]

[0003] Perovskite solar cells are solar cells that use perovskite-type organic metal halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and are also called new concept solar cells.

[0004] 3D-2D hybrid perovskite solar cells are perovskite solar cells that contain 2D perovskite and 3D perovskite structures stacked on the light-absorbing layer. They combine the advantages of the excellent stability of 2D perovskite and the excellent efficiency of 3D perovskite, and have therefore become one of the hotspot directions of current research. Summary of the Invention

[0005] The present application has been made in view of the above-mentioned problems, and its object is to provide a perovskite solar cell, a method for manufacturing the same, and a power consuming device.

[0006] According to a first aspect of the present application, there is provided a perovskite solar cell, the perovskite solar cell comprising a transparent electrode, a first functional layer, a perovskite layer, a second functional layer and a second electrode layer arranged in a stacked manner, the perovskite layer comprising a three-dimensional perovskite layer and a two-dimensional perovskite layer arranged in a stacked manner, the surface of the three-dimensional perovskite layer in contact with the first functional layer being a first surface and the remaining surfaces constituting second surfaces, and the two-dimensional perovskite layer covering the entire second surface.

[0007] The two-dimensional perovskite layer in the perovskite solar cell covers all surfaces (second surfaces) except for the surface (first surface) in contact with the first functional layer, effectively reducing the formation of defects, reducing the sites for decomposition of oxygen, water, etc., and improving device stability.

[0008] In some embodiments, the two-dimensional perovskite layer is a continuous structure.

[0009] In some embodiments, the general structural formula of the active material in the three-dimensional perovskite layer is ABX3 or A2CDX6, and the general structural formula of the active material in the two-dimensional perovskite layer is A'BX3 or A'2CDX6;

[0010] A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions;

[0011] Here, the ionic radius of at least one monovalent cation among the A′ ions is larger than the ionic radius of the monovalent cation among the A ions.

[0012] In some embodiments, the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer is (0.2-10):100. When the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer is within the above range, the thickness of the two-dimensional perovskite layer can sufficiently cover the second surface of the three-dimensional perovskite layer, improving device stability, while keeping the proportion of secondary perovskite within an appropriate range, thereby improving device efficiency.

[0013] In some embodiments, the thickness of the two-dimensional perovskite layer is 1 to 50 nm, as determined from the surface roughness of the three-dimensional perovskite. If the thickness of the two-dimensional perovskite layer is within this range, complete coverage of the second surface of the three-dimensional perovskite layer can be achieved, while improving device efficiency.

[0014] In some embodiments, the thickness of the three-dimensional perovskite layer is 300 to 2000 nm. When the thickness of the three-dimensional perovskite layer is within the above range, the device current can be set within an appropriate range, the carrier transport ability can be increased, and the device efficiency can be improved.

[0015] In some embodiments, the A' ions include organic amine ions, which can further improve the uniformity of the two-dimensional perovskite layer.

[0016] In some embodiments, the A' ion has the following structural feature: (R)N + , each R independently comprises H, at least one R substituted or unsubstituted C1-C20 alkyl, C1-C20 alkenyl, C3-C10 cycloalkyl, R0C(O)-, R0C(O)O-, R0S(O)2-, thiol, sulfonic acid group, phosphate group, or C6-C10 aryl, where each R independently comprises H, C1-C10 alkyl, C6-C10 aryl, halogen-substituted C6-C10 aryl, C1-C5 alkyl-substituted C6-C10 aryl, halogen, C3-C10 cycloalkyl, or boronic acid group.

[0017] In some embodiments, the A ion is an organic amine ion, Li + , Na + , K. + , Rb + and Cs + and optionally, the A ions include one or more of an organic amine ion and Cs + Contains one or more of the following:

[0018] In some embodiments, the B ions are Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , and Ni 2+ Furthermore, the B ion contains one or more of Pb 2+ and Sn 2+ Contains one or two of the following:

[0019] In some embodiments, the C ion is Cs + , Ag + , K. + , and Ru + Contains one or more of the following:

[0020] In some embodiments, the D ion is Bi 3+ , Ni 3+ , Fe 3+ , and Cu 3+ Contains one or more of the following:

[0021] In some embodiments, the X ion is F - , Cl - , Br - and I - Furthermore, the X ion may be Cl - , Br and I - Furthermore, the X ion may be one or more of Br - and I -Contains one or two of the following:

[0022] In some embodiments, the active material of the three-dimensional perovskite layer is CH3NH3PbI3 (abbreviated as MAPbI3), CH(NH2)2PbI3 (abbreviated as FAPbI3), FA 0.83 Cs 0.17 It contains one or more of PbI3 (abbreviated as CsFA), CsPbI3, CsPbI2Br and CsPbIBr2.

[0023] In some embodiments, the active material of the two-dimensional perovskite layer comprises one or more of (PEA)2PbI3, (PBA)2PbI3, (OAm)2PbI3, (mF-PEA)2PbI3, and (PD)2PbI3.

[0024] According to a second aspect of the present application, there is provided a method for manufacturing a perovskite solar cell, the method comprising:

[0025] preparing a first functional layer on the surface of a transparent electrode;

[0026] preparing a perovskite layer on a surface of the first functional layer, the perovskite layer comprising a three-dimensional perovskite layer and a two-dimensional perovskite layer disposed in a stacked manner, the surface of the three-dimensional perovskite layer in contact with the first functional layer being a first surface, and each remaining surface being a second surface, the two-dimensional perovskite layer covering the entire second surface;

[0027] preparing a second functional layer on the surface of the perovskite layer;

[0028] and preparing a second electrode layer on the surface of the second functional layer.

[0029] In some embodiments, the method for producing the perovskite layer comprises:

[0030] preparing a three-dimensional perovskite matrix layer on the surface of the first functional layer, wherein the active material of the three-dimensional perovskite matrix layer has a general structural formula of ABX3 or A2CDX6;

[0031] solvent-treating a surface of the three-dimensional perovskite matrix layer corresponding to the second surface with a mixed solvent;

[0032] reacting the solvent-treated three-dimensional perovskite matrix layer with a compound that provides A' ions to produce the two-dimensional perovskite layer, wherein the general structural formula of the active material in the two-dimensional perovskite layer is A'BX3 or A'2CDX6;

[0033] A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions;

[0034] Here, the ionic radius of at least one monovalent cation among the A′ ions is larger than the ionic radius of the monovalent cation among the A ions.

[0035] The method for producing the perovskite layer involves first dissolving and removing A ions from the surface of the three-dimensional perovskite matrix layer using a mixed solvent, and then reacting the exposed BX3 or CDX6 with a compound that supplies A' ions. The ionic radius of the A' ions is larger than that of the A ions. The introduction of A' ions effectively promotes the formation of two-dimensional perovskite, while simultaneously completely and continuously covering the entire second surface of the three-dimensional perovskite.

[0036] At the same time, even if two-dimensional perovskite layers can be produced using conventional methods, the prepared two-dimensional perovskite layers still have problems such as poor uniformity, relatively poor batch-to-batch reproducibility, and inability to control thickness. The above-mentioned perovskite layer production method can promote the production of two-dimensional perovskite layers, effectively improve the uniformity of the two-dimensional perovskite layer, and by controlling the type, proportion, treatment time, etc. of the mixed solvent, the amount of dissolved three-dimensional perovskite can be relatively controlled, and the thickness of the two-dimensional perovskite layer can be controlled, for example, the two-dimensional perovskite can be only a shallow surface layer, while the main body remains three-dimensional perovskite, and the reproducibility between production batches and the degree of completion are high.

[0037] The method for producing the perovskite layer described above does not adversely affect device performance during the preparation process, and can maintain stability in device performance.

[0038] In some embodiments, the mixed solvent comprises a combination of a first solvent, a second solvent, and a third solvent.

[0039] Specifically, the first solvent includes one or more of the solvents used to prepare the precursor solution of the three-dimensional perovskite matrix layer, and optionally includes one or more of amine-based, sulfone-based, sulfoxide-based, ester-based, and ketone-based solvents, and further optionally includes one or more of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and γ-butyrolactone (GLB).

[0040] Specifically, the second solvent includes a solvent that can dissolve A ions but cannot dissolve BX2, or the second solvent includes a solvent that can dissolve A ions but cannot dissolve CDX4, and optionally the second solvent includes one or more of alcohol-based, nitrile-based, and ketone-based solvents, and further optionally the second solvent includes one or more of isopropanol (IPA), ethanol, methanol, acetone, and acetonitrile.

[0041] Specifically, the third solvent includes one or more anti-solvents for preparing the three-dimensional perovskite matrix layer, and optionally includes one or more of aromatic hydrocarbon, ether, and ester solvents; and optionally includes one or more of chlorobenzene (CB), anisole, diethyl ether, and ethyl acetate.

[0042] In some embodiments, the first solvent accounts for 0.01% to 1% by volume of the third solvent.

[0043] The amount of the first solvent is within the above range, which makes it easy to form a continuous two-dimensional perovskite film, improves device stability, and does not excessively increase the amount of three-dimensional perovskite dissolved, thereby improving device efficiency.

[0044] In some embodiments, the second solvent is present in an amount of 0.01% to 10% by volume of the third solvent, which allows for the formation of a continuous two-dimensional perovskite film while avoiding excessive thickness of the two-dimensional perovskite layer, thereby improving device efficiency.

[0045] In some embodiments, the volume ratio of the first solvent to the second solvent is (0.1~1):1. By controlling this volume ratio, the three-dimensional perovskite mother layer can be dissolved relatively well, which is beneficial for the formation of a continuous two-dimensional perovskite film. It improves the device stability, while reducing the decrease in the overall thickness of the device. For example, some non-reactive BX2 or CDX4 present inside is dissolved, reducing the overall thickness of the device and optimizing the device efficiency.

[0046] In some embodiments, the solvent treatment time is 1 min to 60 min. The solvent treatment time has a corresponding relationship with the usage amounts of the first solvent and the second solvent added. When the usage amounts of the first solvent and the second solvent are large, the required time is short, preventing excessive loss of A-site cations and forming a relatively thick two-dimensional perovskite layer. When the usage amounts of the first solvent and the second solvent are small, the required time is long, preventing the inability to form a continuous two-dimensional perovskite film layer.

[0047] In some embodiments, the temperature of the mixed solvent used for solvent treatment is 20°C to 30°C.

[0048] In some embodiments, the usage amount of the first solvent is X μL, and the thickness of the two-dimensional perovskite layer is Y nm, where X and Y satisfy 0.05 < X / Y < 5. By controlling the X / Y ratio, the time length to reach the desired thickness of the two-dimensional perovskite layer can be shortened, which is beneficial for the optimization of the interface layer and the improvement of the fill factor. At the same time, it improves the uniformity and complete coverage of the two-dimensional perovskite.

[0049] In some embodiments, the conditions for reacting the solvent-treated three-dimensional perovskite mother layer with the compound supplying A' ions include performing annealing treatment under the condition that the temperature is 50°C to 150°C. Optionally, the annealing treatment time is 20 min to 40 min.

[0050] In some embodiments, the A' ion compound includes one or more of the following compounds: CH3CH2CH2CH2CH2CH2CH2NH2, CH3CH2CH2CH2CONH2, CH3CH2CH2CH2COONH2, phenethylamine, benzylamine, amphetamine, fluorophenylethylamine, fluorophenethylamine iodide (F-PEAI), phenylamine boronate, oleylamine, octylammonium bromide, N,N-bis(2-chloroethyl)-p-toluenesulfonamide, and cyclopentanecarboxamide, and salts thereof.

[0051] According to a third aspect of the present application, there is provided a power consuming device, the power consuming device comprising at least one of the perovskite solar cell according to the first aspect and a perovskite solar cell produced by the production method according to the second aspect. [Brief explanation of the drawings]

[0052] [Figure 1] FIG. 1 is a schematic diagram of the preparation process of the perovskite layer in a perovskite solar cell according to one embodiment of the present application.

[0053] [Figure 2] 1 is a schematic diagram of a solar cell powered power consuming device according to one embodiment of the present application; DETAILED DESCRIPTION OF THE INVENTION

[0054] The perovskite solar cell, its manufacturing method, and power consumption device of the present application will be described in more detail below in conjunction with specific embodiments. The present invention may be embodied in many different forms and is not limited to the embodiments set forth herein. Rather, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0055] The details of one or more embodiments of the application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the application will become apparent from the description, drawings, and claims.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used to describe the present invention herein are for the purpose of describing particular embodiments only and are not intended to be limiting of the present invention.

[0057] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of the end values, and are arbitrarily combinable; i.e., any lower limit can be combined with any upper limit to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also contemplated. Furthermore, if 1 and 2 are listed as minimum range values ​​and 3, 4, and 5 are listed as maximum range values, the ranges 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all contemplated. In this application, unless otherwise specified, a numerical range "a to b" represents a shorthand notation for any combination of real numbers a to b, where a and b are both real numbers. For example, the numerical range "0-5" represents a list of all real numbers between "0-5" in this specification, and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0058] Unless otherwise stated, all embodiments and optional embodiments in the present application can be combined with each other to form a new technical solution.

[0059] Unless otherwise stated, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0060] Unless otherwise specified, all steps in this application may be performed in order or randomly, and are preferably performed in order. For example, when the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed in order, or steps (b) and (a) performed in order. For example, when the method mentioned above may further include step (c), it means that step (c) may be added to the method in any order, and for example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.

[0061] Unless otherwise specified, the terms "comprise" and "include" used in this application may be open-ended or closed-ended. For example, the terms "comprise" and "include" may indicate that other components not listed may be further included or included, or that only the listed components may be included or included.

[0062] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) but B is true (or exists), or when both A and B are true (or exist).

[0063] In this application, the term "aryl" refers to an aromatic hydrocarbon group derived by removing a hydrogen atom from an aromatic ring compound, and may be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. In the case of a polycyclic ring, at least one ring is an aromatic ring system. For example, "C6-C10 aryl" refers to an aryl containing 6 to 10 carbon atoms, and each occurrence may be, independently of each other, a C6 aryl, a C7 aryl, a C8 aryl, a C9 aryl, or a C10 aryl.

[0064] In this application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing primary (straight-chain), secondary, tertiary, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, such as "C1-C20 alkyl," mean alkyl containing 1 to 10 carbon atoms, and each occurrence may, independently of each other, be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C12 alkyl, C15 alkyl, or C20 alkyl.Suitable examples are methyl (Me, -CH), ethyl (Et, -CHCH), 1-propyl (n-Pr, n-propyl, -CHCHCH), 2-propyl (i-Pr, i-propyl, -CH(CH)), 1-butyl (n-Bu, n-butyl, -CHCHCHCHCH), 2-methyl-1-propyl (i-Bu, i-butyl, -CHCH(CH)), 2-butyl (s-Bu, s-butyl, -CH(CH)CH CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2 CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3 ), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3) and octyl (-(CH2)7CH3).

[0065] As used herein, the term "cycloalkyl" refers to a non-aromatic hydrocarbon containing ring carbon atoms, and may be a monocycloalkyl, spirocycloalkyl, or bridged cycloalkyl. Phrases containing this term, such as "C3-C10 cycloalkyl," refer to a cycloalkyl containing 3 to 10 carbon atoms, and each occurrence may, independently of the others, be C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl, C9 cycloalkyl, or C10 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Furthermore, "cycloalkyl" may contain one or more double bonds; representative examples of cycloalkyls containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutadienyl.

[0066] In this application, the term "three-dimensional perovskite" refers to a perovskite with a three-dimensional crystal structure comprising a BX6 octahedral framework with A cations occupying apex positions.

[0067] In this application, the term "two-dimensional perovskite" refers to a perovskite in which the BX6 octahedral framework is separated by large volumes of A-position cations, e.g., A' ions, forming a special layered structure with alternating organic and inorganic layers.

[0068] Specifically, "3D perovskite" and "2D perovskite" can be distinguished by the position of the XRD peak. Generally, the XRD peaks of 3D perovskite are mainly expressed in multiple crystal orientations such as (001), (010), and (111), with the main peak position appearing between 13 and 15. However, the XRD peaks of 2D perovskite are mainly expressed in a single crystal orientation such as (0x0)x=2 / 4 / 6 / 8, with no clear main peak and the possibility of peaks appearing below 10.

[0069] Traditionally, 3D-2D hybrid perovskite solar cells have been fabricated primarily by reducing the dimensionality of 3D perovskites. For example, thermal injection synthesis can be used to efficiently prepare quasi-2D perovskites by adjusting and controlling the kinetics of colloidal synthesis on metal ion surfaces. Other methods involve incorporating organic ligands into the absorber layer of a perovskite cell to reduce the 3D perovskite framework to a 2D structure, forming a perovskite absorber layer structure consisting of one inorganic perovskite layer and two organic ligand layers. Other methods involve gradient annealing to obtain perovskite films with a 2D / 3D planar heterojunction structure, with a 2D bottom layer and a 3D top layer. However, the focus of these methods is the lack of process control during the perovskite layer preparation process, making it difficult to enhance the production of 2D perovskites for industrial applications.

[0070] Another method involves treating the surface of a 3D perovskite film with saturated n-butylammonium vapor to rapidly form a thin 2D perovskite layer on the surface. This method is simple, has good process controllability, is inexpensive, and is suitable for large-area industrial applications. Although this method overcomes the problem of uncontrollable processes to some extent, it does not ensure the formation of 2D perovskite, and even if 2D perovskite is formed, it is difficult to form a continuous 2D perovskite layer structure. In particular, the probability of forming 2D perovskite around 3D perovskite is relatively low, making it impossible to achieve complete coverage of the 3D perovskite.

[0071] The present application provides a perovskite solar cell comprising a transparent electrode, a first functional layer, a perovskite layer, a second functional layer and a second electrode layer arranged in a stacked manner, wherein the perovskite layer comprises a three-dimensional perovskite layer and a two-dimensional perovskite layer arranged in a stacked manner, wherein a surface of the three-dimensional perovskite layer in contact with the first functional layer is a first surface and each remaining surface constitutes a second surface, and the two-dimensional perovskite layer covers the entire second surface.

[0072] The two-dimensional perovskite layer in the perovskite solar cell covers all surfaces (second surfaces) except for the surface (first surface) in contact with the first functional layer, effectively reducing the formation of defects, reducing the sites for decomposition of oxygen, water, etc., and improving device stability.

[0073] Furthermore, the two-dimensional perovskite layer has good uniformity and high film layer quality, which can effectively reduce the interface contact electrical resistance between layers and improve the device fill factor.

[0074] Furthermore, the two-dimensional perovskite layer covers the second surface and is in contact with the first functional layer, covering the three-dimensional perovskite layer.

[0075] In some embodiments, the two-dimensional perovskite layer is a continuous structure, thus forming a continuous and uninterrupted layer structure, completely covering the second surface.

[0076] In some embodiments, the general structural formula of the active material in the three-dimensional perovskite layer is ABX3 or A2CDX6, and the general structural formula of the active material in the two-dimensional perovskite layer is A'BX3 or A'2CDX6;

[0077] A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions;

[0078] Here, the ionic radius of at least one monovalent cation among the A′ ions is larger than the ionic radius of the monovalent cation among the A ions.

[0079] As an example, the ionic radius may be calculated from first principles based on density functional theory (DET).

[0080] In some embodiments, the A' ions include organic amine ions. In this way, the uniformity of the two-dimensional perovskite layer can be further improved. Specifically, the A' ions have the following structural features: (R)N + , each R independently includes H, at least one R substituted or unsubstituted C1-C20 alkyl, C1-C20 alkenyl, C3-C10 cycloalkyl, R0C(O)—, R0C(O)O—, R0S(O)2—, thiol, sulfonic acid group, phosphate group, or C6-C10 aryl, where each R independently includes H, C1-C10 alkyl, C6-C10 aryl, halogen-substituted C6-C10 aryl, C1-C5 alkyl-substituted C6-C10 aryl, halogen, C3-C10 cycloalkyl, or boronic acid group.

[0081] In some embodiments, the A' ions include one or more of phenylethylamine (PEA) ions, fluorophenylethylamine (mF-PEA) ions, phenylboronic acid amine (PBA) ions, and oleylamine (OAm) ions. As can be appreciated, the "m" in "mF-PEA" refers to the meta positions of F and PEA on the benzene ring.

[0082] In some embodiments, the A ion is an organic amine ion, Li + , Na + , K. + , Rb + and Cs + and optionally, the A ions include one or more of an organic amine ion and Cs + Contains one or more of the following:

[0083] In some embodiments, the B ions are Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , and Ni2+ Furthermore, the B ion contains one or more of Pb 2+ and Sn 2+ Contains one or two of the following:

[0084] In some embodiments, the C ion is Cs + , Ag + , K. + , and Ru + Contains one or more of the following:

[0085] In some embodiments, the D ion is Bi 3+ , Ni 3+ , Fe 3+ , and Cu 3+ Contains one or more of the following:

[0086] In some embodiments, the X ion is F - , Cl - , Br - and I - Furthermore, the X ion may be Cl - , Br and I - Furthermore, the X ion may be one or more of Br - and I - Contains one or two of the following:

[0087] In some embodiments, the active material of the three-dimensional perovskite layer is CH3NH3PbI3 (abbreviated as MAPbI3), CH(NH2)2PbI3 (abbreviated as FAPbI3), FA 0.83 Cs 0.17 It contains one or more of PbI3 (abbreviated as CsFA), CsPbI3, CsPbI2Br and CsPbIBr2.

[0088] In some embodiments, the active material of the two-dimensional perovskite layer comprises one or more of (PEA)2PbI3, (PBA)2PbI3, (OAm)2PbI3, (mF-PEA)2PbI3, and (PD)2PbI3.

[0089] In some embodiments, the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer is (0.2-10):100. When the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer is within the above range, the thickness of the two-dimensional perovskite layer can sufficiently cover the second surface of the three-dimensional perovskite layer, improving device stability, while keeping the proportion of secondary perovskite within an appropriate range, thereby improving device efficiency. Specifically, the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer includes, but is not limited to, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1:100, 1.5:100, 1.6:100, 1.7:100, 2:100, 2.2:100, 2.4:100, 2.5:100, 2.7:100, 4:100, 5:100, 5.6:100, 6:100, 7:100, 8:100, 9:100, 10:100, or a range consisting of any two of the above values.

[0090] In some embodiments, the thickness of the two-dimensional perovskite layer is 1 to 50 nm, as determined from the surface roughness of the three-dimensional perovskite. A thickness of the two-dimensional perovskite layer within the above range can achieve complete coverage of the three-dimensional perovskite layer on the second surface while improving device efficiency. Specifically, the thickness of the two-dimensional perovskite layer includes, but is not limited to, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 14 nm, 16 nm, 20 nm, 23 nm, 25 nm, 28 nm, 32 nm, 35 nm, 38 nm, 40 nm, 45 nm, 50 nm, or a range consisting of any two of the foregoing values. Furthermore, the thickness of the two-dimensional perovskite layer is 2 to 32 nm.

[0091] In some embodiments, the thickness of the three-dimensional perovskite layer is 300 to 2000 nm. When the thickness of the three-dimensional perovskite layer is within the above range, the device current can be set within an appropriate range, the carrier transport ability can be increased, and the device efficiency can be improved. Specifically, the thickness of the three-dimensional perovskite layer includes, but is not limited to, 300nm, 350nm, 370nm, 380nm, 390nm, 400nm, 450nm, 480nm, 500nm, 520nm, 550nm, 580nm, 600nm, 620nm, 640nm, 650nm, 670nm, 680nm, 700nm, 750nm, 800nm, 850nm, 870nm, 890nm, 900nm, 950nm, 1000nm, 1200nm, 1400nm, 1500nm, 1600nm, 1700nm, 1900nm, 2000nm, or a range consisting of any two of the above values.

[0092] The present application provides a method for manufacturing a perovskite solar cell, the method comprising:

[0093] preparing a first functional layer on the surface of a transparent electrode;

[0094] preparing a perovskite layer on a surface of the first functional layer, the perovskite layer comprising a three-dimensional perovskite layer and a two-dimensional perovskite layer disposed in a stacked manner, the surface of the three-dimensional perovskite layer in contact with the first functional layer being a first surface, and each remaining surface being a second surface, the two-dimensional perovskite layer covering the entire second surface;

[0095] preparing a second functional layer on the surface of the perovskite layer;

[0096] and preparing a second electrode layer on the surface of the second functional layer.

[0097] In some embodiments, the two-dimensional perovskite layer is a continuous structure.

[0098] In some embodiments, the method for producing the perovskite layer comprises:

[0099] preparing a three-dimensional perovskite matrix layer on the surface of the first functional layer, wherein the active material of the three-dimensional perovskite matrix layer has a general structural formula of ABX3 or A2CDX6;

[0100] solvent-treating a surface of the three-dimensional perovskite matrix layer corresponding to the second surface with a mixed solvent;

[0101] reacting the solvent-treated three-dimensional perovskite matrix layer with a compound that provides A' ions to produce the two-dimensional perovskite layer, wherein the general structural formula of the active material in the two-dimensional perovskite layer is A'BX3 or A'2CDX6;

[0102] A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions;

[0103] Here, the ionic radius of at least one monovalent cation among the A′ ions is larger than the ionic radius of the monovalent cation among the A ions.

[0104] The method for producing the perovskite layer involves first dissolving and removing A ions from the surface of the 3D perovskite matrix using a mixed solvent, and then reacting the exposed BX3 or CDX6-providing compound. The ionic radius of the A' ions is larger than that of the A ions. The introduction of A' ions effectively promotes the formation of 2D perovskite while simultaneously completely and continuously covering the entire second surface of the 3D perovskite.

[0105] At the same time, even if two-dimensional perovskite layers can be produced using conventional methods, the prepared two-dimensional perovskite layers still have problems such as poor uniformity, relatively poor batch-to-batch reproducibility, and inability to control thickness. The above-mentioned perovskite layer production method can promote the production of two-dimensional perovskite layers, effectively improve the uniformity of the two-dimensional perovskite layer, and by controlling the type, proportion, treatment time, etc. of the mixed solvent, the amount of dissolved three-dimensional perovskite can be relatively controlled, and the thickness of the two-dimensional perovskite layer can be controlled, for example, the two-dimensional perovskite can be only a shallow surface layer, while the main body remains three-dimensional perovskite, and the reproducibility between production batches and the degree of completion are high.

[0106] The above-described method for producing a perovskite layer can improve the stability of device performance without adversely affecting device performance during the preparation process.

[0107] As can be seen, the portion of the three-dimensional perovskite matrix where the two-dimensional perovskite layer is removed still remains as the original three-dimensional perovskite layer.

[0108] Specifically, an example of the method for manufacturing the perovskite layer may be seen in FIG. 1, which shows: (a) providing a preform (including a transparent electrode 100 and a hole transport layer 200 stacked together) for preparing a three-dimensional perovskite matrix layer 300; (b) treating the surfaces of the three-dimensional perovskite matrix layer 300 other than the surface that contacts the hole transport layer with a mixed solvent to dissolve and remove the A ions in the corresponding active material, thereby obtaining a remaining material 400; (c) reacting the remaining material 400 with a compound that provides A' ions to generate a two-dimensional perovskite layer 500, at the same time, the remaining three-dimensional perovskite matrix layer is a three-dimensional perovskite layer.

[0109] In some embodiments, the mixed solvent comprises a combination of a first solvent, a second solvent, and a third solvent.

[0110] Specifically, the first solvent includes one or more of the solvents used to prepare the precursor solution of the three-dimensional perovskite matrix layer, and optionally includes one or more of amine-based, sulfone-based, sulfoxide-based, ester-based, and ketone-based solvents, and further optionally includes one or more of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and γ-butyrolactone (GLB).

[0111] Specifically, the second solvent may include a solvent capable of dissolving A ions but not BX2, or a solvent capable of dissolving A ions but not CDX4. Optionally, the second solvent may include one or more of alcohols, nitriles, and ketones. More optionally, the second solvent may include one or more of isopropanol (IPA), ethanol, methanol, acetone, and acetonitrile. Although not particularly limited, the solubility of the A ions in the second solvent is greater than 0.1 mg / mL at room temperature, and the solubility of BX2 or CDX4 in the second solvent is less than 0.05 mg / mL at room temperature.

[0112] As can be understood, BX2 and CDX4 are precursor materials for preparing the corresponding B and X, C, D and X materials in ABX3, A2CDX6, A'BX3, A'2CDX6, i.e., perovskite layers.

[0113] Specifically, the third solvent includes one or more anti-solvents for preparing the three-dimensional perovskite matrix layer, and optionally includes one or more of aromatic hydrocarbon, ether, and ester solvents; and optionally includes one or more of chlorobenzene (CB), anisole, diethyl ether, and ethyl acetate.

[0114] In some embodiments, the first solvent accounts for 0.01% to 1% by volume of the third solvent.

[0115] The amount of the first solvent is within the above range, which facilitates the formation of a continuous two-dimensional perovskite film, improves device stability, and prevents the dissolution of an excessive amount of three-dimensional perovskite, thereby improving device efficiency. Specifically, the volume percentage of the first solvent in the third solvent includes, but is not limited to, 0.01%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or a range consisting of any two of the above values.

[0116] In some embodiments, the volume percentage of the second solvent in the third solvent is 0.01% to 10%. The amount of the second solvent within this range can form a continuous two-dimensional perovskite film while preventing the two-dimensional perovskite layer from becoming too thick, further improving device efficiency. Specifically, the volume percentage of the second solvent in the third solvent can be, but is not limited to, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 5%, 8%, 9%, 10%, or a range consisting of any two of the foregoing values.

[0117] In some embodiments, the volume ratio of the first solvent to the second solvent is (0.1-1:1). Controlling this volume ratio allows for relatively good dissolution of the 3D perovskite matrix, favoring the formation of a continuous 2D perovskite film, improving device stability while minimizing the reduction in overall device thickness. For example, some of the unreacted BX2 or CDX4 present inside the matrix is ​​dissolved, reducing the overall device thickness and optimizing device efficiency. Specifically, the volume ratio of the first solvent to the second solvent may be, but is not limited to, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, or a range consisting of any two of the foregoing values.

[0118] In some embodiments, the solvent treatment time is from 1 min to 60 min. The solvent treatment time has a corresponding relationship with the usage amounts of the first solvent and the second solvent added. When the usage amounts of the first solvent and the second solvent are large, the required time is short, preventing excessive loss of A-site cations, forming a relatively thick two-dimensional perovskite layer. When the usage amounts of the first solvent and the second solvent are small, the required time is long, preventing the inability to form a continuous two-dimensional perovskite film layer. Specifically, the solvent treatment time is 1 min, 5 min, 10 min, 15 min, 20 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min or includes a range consisting of any two of the above numerical values, but is not limited thereto.

[0119] In some embodiments, the temperature of the mixed solvent used for solvent treatment is 20°C to 30°C (room temperature).

[0120] In some embodiments, the usage amount of the first solvent is X μL, and the thickness of the two-dimensional perovskite layer is Y nm, and X and Y satisfy 0.05 < X / Y < 5. By controlling the X / Y ratio, the time length to reach the desired thickness of the two-dimensional perovskite layer can be shortened, which is beneficial for the optimization of the interface layer and the improvement of the fill factor. At the same time, the uniformity and complete coverage of the two-dimensional perovskite are improved. Specifically, the X / Y ratio value is 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 1, 1.5, 2, 3, 4, 5 or includes a range consisting of any two of the above numerical values, but is not limited thereto.

[0121] In some embodiments, the conditions for reacting the solvent-treated three-dimensional perovskite mother layer with the compound supplying A' ions include performing annealing treatment under the condition that the temperature is 50°C to 150°C. Optionally, the annealing treatment time is 20 min to 40 min.

[0122] In some embodiments, the A' ion-donating compound may include one or more of the following compounds: CH3CH2CH2CH2CH2CH2CH2NH2, CH3CH2CH2CH2CONH2, CH3CH2CH2CH2COONH2, phenethylamine, benzylamine, amphetamine, fluorophenylethylamine, fluorophenethylamine iodide (F-PEAI), phenylamine boronate, oleylamine, octylammonium bromide, N,N-bis(2-chloroethyl)-p-toluenesulfonamide, and cyclopentanecarboxamide, and salts thereof. Without limitation, the salts may include halide or acid salts of the aforementioned compounds.

[0123] In addition, the technical solutions for the three-dimensional perovskite layer and the two-dimensional perovskite layer in the above manufacturing method are the same as those for the perovskite solar cell described above, and will not be further described here.

[0124] As can be understood, perovskite solar cells include formal and transformer types. For the formal type, the perovskite solar cell includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer, which are sequentially stacked on the transparent electrode. For the transformer type, the perovskite solar cell includes a transparent electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer, which are sequentially stacked on the transparent electrode.

[0125] In some embodiments, the band gap of the perovskite layer is 1.20 eV to 2.30 eV. The band gap may be measured by obtaining an ultraviolet absorption curve through an ultraviolet absorption spectrum test and then calculating the band gap using Tauc's equation.

[0126] In some embodiments, the perovskite layer has a thickness of between 400 nm and 1000 nm.

[0127] Although there is no particular limitation, the transparent electrode includes a transparent conductive glass base, and examples of the material include FTO, ITO, AZO, BZO, and IZO.

[0128] Although there is no particular limitation, the electron transport layer material is [6,6]-phenyl C 61 Butyric acid methyl ester (PC 61 BM), [6,6]-phenyl C 71 Butyric acid methyl ester (PC 71 The material may include at least one of materials such as fullerene C60 (C60), fullerene C70 (C70), tin dioxide (SnO2), zinc oxide (ZnO), and derivatives thereof, as well as materials obtained by doping or passivation thereof.

[0129] Although not particularly limited, the hole transport layer may include at least one of materials such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)ammonium] (PTAA), poly-3-hexylthiophene (P3HT), triptycene-based triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrenesulfone) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), copper iodide (CuI), copper oxide (CuO), and derivatives thereof, as well as materials obtained by doping or passivation thereof.

[0130] Although there are no particular limitations, the material of the second electrode layer may include an organic, inorganic, or mixed organic-inorganic conductive material, such as Ag, Cu, C, Au, Al, ITO, AZO, BZO, and IZO.

[0131] Specifically, the perovskite solar cell is a formal type, and the manufacturing method thereof includes the following steps:

[0132] Step 1: Etch, clean and dry the transparent electrode.

[0133] Step 2: Preparing an electron transport layer on the transparent electrode;

[0134] Step 3: preparing the perovskite layer on the electron transport layer;

[0135] Step 4: preparing a hole transport layer on the perovskite layer;

[0136] Step 5: Prepare a second electrode layer on the hole transport layer.

[0137] Specifically, the perovskite solar cell is a transformer type, and the manufacturing method thereof includes the following steps:

[0138] Step 1: Etch, clean and dry the transparent electrode.

[0139] Step 2: preparing a hole transport layer on the transparent electrode;

[0140] Step 3: preparing the perovskite layer on the electron transport layer;

[0141] Step 4: preparing an electron transport layer on the perovskite layer;

[0142] Step 5: Prepare a second electrode layer on the hole transport layer.

[0143] The present application provides a power consuming device, which includes at least one of the perovskite solar cell described above and a perovskite solar cell manufactured by the method for manufacturing a solar cell described above.

[0144] In some embodiments, the solar cell may be used as a power source for a power consuming device or as an energy storage unit for a power consuming device.

[0145] Furthermore, the power consuming devices may include, but are not limited to, mobile devices such as mobile phones, laptops, etc., electric vehicles, electric trains, ships and satellites, energy storage systems, etc.

[0146] An example power consuming device 20 is shown in Figure 2. The power consuming device 20 may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0147] Other examples of power consuming devices may include mobile phones, tablet computers, laptops, and the like. [Example]

[0148] The following examples of the present application are described. The examples described below are illustrative and are intended only to interpret the present application and should not be construed as limitations on the present application. Unless specific techniques or conditions are specified in the examples, they are carried out in accordance with the techniques or conditions described in literature in the art or in accordance with the product specifications. Unless the manufacturer of the reagents or equipment used is specified, they are all ordinary products that can be obtained commercially. Example 1

[0149] This embodiment provides a perovskite solar cell, and the manufacturing process is as follows:

[0150] (1) A 2.0cm x 2.0cm ITO conductive glass was taken, and 0.35cm of ITO was removed from each end by laser etching to expose the glass base. The etched ITO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropanol, and then the solvent was blown off the ITO conductive glass with a nitrogen gas gun to dry it, and then it was placed in an ultraviolet ozone machine for further cleaning.

[0151] (2) A 2 mg / mL poly[bis(4-phenyl)(2,4,6-trimethylphenyl)ammonium] (PTAA) organic hole-transporting layer was spin-coated onto the UV-ozone-treated ITO substrate at a rate of 5000 rpm / s, and then annealed on a hot stage at 100 °C for 10 min.

[0152] (3) A perovskite precursor solution was spin-coated onto the hole transport layer at 3000 rpm / s, annealed at 100°C for 30 min, and cooled to room temperature (20°C-30°C) to prepare a three-dimensional perovskite film on the surface of the hole transport layer. The perovskite precursor solution contained 1.2 mol / L lead iodide, 1.0 mol / L formamidine hydroiodide, and 0.2 mol / L cesium iodide in a 4:1 volume ratio of N,N-dimethylformamide and dimethyl sulfoxide. The active material of the prepared perovskite film was FA. 0.83 Cs 0.17 It is a PbI3(CsFA) system.

[0153] (4) The exposed surface of the perovskite film (the surface other than the surface in contact with the hole transport layer) was completely immersed in a mixed solvent (DMF / IPA / CB, volume ratio 1:5:1000, used amounts 2µL:10µL:2000µL, respectively) and treated at room temperature (20-30°C) for 10 min. After removal and drying with nitrogen gas, the exposed surface was spin-coated at 4000 rpm with a compound that supplies A' ions (tetrafluoroethylene ammonium iodide, CAS number: 1413269-55-2, F-PEAI) for 30 s, and then annealed at 100°C for 30 min to produce a 2D-3D perovskite. The active material of the 2D perovskite was tetrafluorophenethylammonium lead iodide ((mF-PEA)2PbI3).

[0154] (5) The electron transport layer [6,6]-phenyl C was deposited on the 2D-3D perovskite layer at 1200 rpm / s. 61 The substrate was spin-coated with polymethylbutyrate (PCBM) and annealed at 100°C for 10 min, immediately followed by spin-coating the passivation layer bathocuproine (BCP) at 5000 rpm / s.

[0155] (6) A metal electrode (Ag) was evaporated onto the passivation layer, the edges were cleaned, and the device was tested.

[0156] The perovskite solar cells according to Examples 2 to 23 were the same as those according to Example 1, with the main differences shown in Table 1. In Examples 22 and 23, the thickness of the 2D and 3D perovskite was changed by controlling the rotation speed and time for spin-coating the compound supplying A' ions.

[0157] The perovskite solar cell according to the comparative example is the same as that of Example 1, with the main difference being that the manufacturing method of the 2D-3D perovskite layer is as follows:

[0158] (1) A 2.0cm x 2.0cm ITO conductive glass was taken, and 0.35cm of ITO was removed from each end by laser etching to expose the glass base. The etched ITO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropanol, and then the solvent was blown off the ITO conductive glass with a nitrogen gas gun to dry it, and then it was placed in an ultraviolet ozone machine for further cleaning.

[0159] (2) A 2 mg / mL poly[bis(4-phenyl)(2,4,6-trimethylphenyl)ammonium] (PTAA) organic hole-transporting layer was spin-coated onto the UV-ozone-treated ITO substrate at a rate of 5000 rpm / s, and then annealed on a hot stage at 100 °C for 10 min.

[0160] (3) A perovskite precursor solution was spin-coated onto the hole transport layer at 3000 rpm / s, annealed at 100°C for 30 min, and cooled to room temperature (20°C-30°C) to prepare a three-dimensional perovskite film on the surface of the hole transport layer. The perovskite precursor solution contained 1.2 mol / L lead iodide, 1.0 mol / L formamidine hydroiodide, and 0.2 mol / L cesium iodide in a 4:1 volume ratio of N,N-dimethylformamide and dimethyl sulfoxide. The active material of the prepared perovskite film was FA. 0.83 Cs 0.17 It is a PbI3(CsFA) system.

[0161] (4) A compound that supplies A' ions at 5000 rp / s (phenylethylamine hydroiodide, CAS number: 151059-43-7, PEAI) was spin-coated onto the three-dimensional perovskite surface for 30 s, and then annealed at 100 °C for 10 min.

[0162] (5) The prepared perovskite film was spin-coated with an electron transport layer, [6,6]-phenyl C61 methyl butyrate (PCBM), at 1200 rpm / s, annealed at 100 °C for 10 min, and immediately thereafter spin-coated with a passivation layer, bathocuproine (BCP), at 5000 rpm / s.

[0163] (6) A metal electrode (Ag) was evaporated onto the passivation layer, the edges were cleaned, and the device was tested.

[0164] Test example:

[0165] (1) Perovskite thickness test

[0166] The thickness of the 2D perovskite and 3D perovskite were jointly tested by ellipsometer and step profiler, and the results are listed in Table 1.

[0167] (2) Photoelectric conversion efficiency of perovskite solar cells

[0168] Standard simulated sunlight (AM 1.5G, 100 mW / cm 2 The battery performance was tested under irradiation of 1000 kJ / cm 2 , and the IV curve was obtained. From the IV curve and the data fed back from the test equipment, the short circuit current Jsc (unit: mA / cm 2 ) was calculated. 2 ), open circuit voltage Voc (unit: V), maximum optical output current Jmpp (unit: mA), and maximum optical output voltage Vmpp (unit: V) can be obtained. The fill factor FF (unit: %) of the battery was calculated using the formula FF = Jsc × Voc / (Jmpp × Vmpp). The photoelectric conversion efficiency PCE (unit: %) of the battery was calculated using the formula PCE = Jsc × Voc × FF / Pw, where Pw represents the input power in mW.

[0169] The results are shown in Table 2.

[0170] (3) Perovskite solar cell stability test

[0171] The prepared battery device was placed in a dry room and stored in the dark at a humidity of about 5%. After 100 days, the device efficiency was retested and the ratio of the efficiency to the initial efficiency was calculated. The specific experimental results are shown in Table 2. [Table 1-1] [Table 1-2]

[0172] The thickness of the 2D perovskite in the comparative example is marked with " / ", indicating that the prepared 2D perovskite is discontinuous and the thickness parameter is difficult to obtain. [Table 2]

[0173] As can be seen, compared with the comparative example, all of Examples 1 to 23 of the present application can achieve better device stability.

[0174] Furthermore, as can be seen from the comparison between Examples 1 to 3, there is a difference in device stability when different perovskite film active materials are used as the host layer, and here, CsFA and FAPbI3 have superior stability.

[0175] As can be seen from the comparison between Examples 1, 4 to 6, there is a difference in the stability of the device when the base layer is ion-substituted with different compounds that supply A' ions, and here, the stability of the device prepared using F-PEAI and octylammonium bromide as compounds that supply A' ions is superior.

[0176] As can be seen from the comparison between Examples 1, 7 to 9, by treating the base layer with solvents in different ratios, two-dimensional perovskite with different thicknesses can be obtained. Here, the base layer is treated with solvents in a ratio of 2:10:2000, and the stability of the prepared device is excellent.

[0177] As can be seen from the comparison between Examples 1, 10, and 12, two-dimensional perovskite films with different thicknesses can be obtained by treating the base layer with different solvents. Here, the base layer was treated with a combination of DMF / IPA / CB as the solvent, and the prepared devices showed excellent stability.

[0178] As can be seen from the comparison between Examples 1, 13 to 16, different thicknesses of 2D perovskite can be obtained by solvent-treating the host layer for different times, and as the time increases, the thickness of the 2D perovskite increases accordingly, and the stability of the prepared devices is also improved to a certain extent.

[0179] As can be seen from the comparison between Examples 1, 19 to 23, as the thickness ratio of the 2D perovskite to the 3D perovskite increases, the thickness of the prepared 2D perovskite increases, and at the same time, the device stability decreases to a certain extent. Here, in Example 23, the thickness of the 3D perovskite is too thin, so the device stability also decreases to a certain extent.

[0180] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea and achieves the same effects within the scope of the technical solution of the present application is included within the technical scope of the present application. In addition, various modifications that a person skilled in the art can make to the embodiments and other forms formed by combining some of the components of the embodiments are also included within the scope of the present application, as long as they do not deviate from the spirit of the present application.

Claims

1. 1. A perovskite solar cell comprising: a transparent electrode, a first functional layer, a perovskite layer, a second functional layer, and a second electrode layer, which are stacked together; the perovskite layer comprises a three-dimensional perovskite layer and a two-dimensional perovskite layer, which are stacked together; a surface of the three-dimensional perovskite layer in contact with the first functional layer is a first surface; each of the remaining surfaces constitutes a second surface; and the two-dimensional perovskite layer covers the entire second surface.

2. 2. The perovskite solar cell according to claim 1, wherein the two-dimensional perovskite layer has a continuous structure.

3. The general structural formula of the active material in the three-dimensional perovskite layer is ABX ３ or A ２ CDX ６ and the general structural formula of the active material in the two-dimensional perovskite layer is A'BX ３ Or A' ２ CDX ６ and A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions; The perovskite solar cell according to any one of claims 1 to 2, characterized in that the ionic radius of at least one monovalent cation among the A' ions is larger than the ionic radius of the monovalent cation among the A ions.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that the thickness ratio of the two-dimensional perovskite layer to the three-dimensional perovskite layer is (0.2-10):

100.

5. 5. The perovskite solar cell of claim 1, wherein the thickness of the two-dimensional perovskite layer is 1-50 nm, and optionally the thickness of the two-dimensional perovskite layer is 2-32 nm.

6. The perovskite solar cell according to any one of claims 1 to 5, wherein the three-dimensional perovskite layer has a thickness of 300 to 2000 nm.

7. The A' ion comprises an organic amine ion, and optionally the A' ion has the structural feature shown below: (R) ４ N ＋ , R are each independently H, at least one R ０ Substituted or unsubstituted C1-C20 alkyl, C1-C20 alkenyl, C3-C10 cycloalkyl, R ０ C(O)-, R ０ C(O)O-, R ０ S (O) ２ -, thiol, sulfonic acid group, phosphate group, or C6-C10 aryl, where R ０ each independently comprise H, a C1-C10 alkyl, a C6-C10 aryl, a halogen-substituted C6-C10 aryl, a C1-C5 alkyl-substituted C6-C10 aryl, a halogen, a C3-C10 cycloalkyl, or a boronic acid group.

8. It has at least one of the following characteristics: (1) The A ion is an organic amine ion, Li ＋ , Na ＋ , K. ＋ , Rb ＋ and Cs ＋ and optionally, the A ions include one or more of organic amine ions and Cs ＋ and (2) The B ions are Pb ２＋ , Sn ２＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Zn ２＋ , Ge ２＋ , Fe ２＋ , Co ２＋ , and Ni ２＋ and optionally, the B ions include one or more of Pb ２＋ and Sn ２＋ One or two of the following are included: (3) The C ion is Cs ＋ , Ag ＋ , K. ＋ , Ru ＋ and (4) The D ion is Bi ３＋ , Ni ３＋ , Fe ３＋ and Cu ３＋ and (5) The X ion is F － , Cl － ,Br － and I － and optionally, the X ion is Cl － ,Br － and I － The perovskite solar cell according to any one of claims 3 to 7, characterized in that it contains one or more of the following:

9. The active material of the three-dimensional perovskite layer is CH ３ NH ３ PbI ３ , CH(NH ２ ) ２ PbI ３ , F.A. ０．８３ Cs ０．１７ PbI ３ , CsPbI ３ , CsPbI ２ Br and CsPbIBr ２ The perovskite solar cell according to any one of claims 1 to 8, characterized in that it contains one or more of the following:

10. The active material of the two-dimensional perovskite layer is (PEA) ２ PbI ３ , (PBA) ２ PbI ３ , (OAm) ２ PbI ３ , (mF-PEA) ２ PbI ３ and (PD) ２ PbI ３ The perovskite solar cell according to any one of claims 1 to 8, characterized in that it contains one or more of the following:

11. A method for manufacturing a perovskite solar cell, comprising: preparing a first functional layer on the surface of a transparent electrode; preparing a perovskite layer on a surface of the first functional layer, the perovskite layer comprising a three-dimensional perovskite layer and a two-dimensional perovskite layer disposed in a stacked manner, the surface of the three-dimensional perovskite layer in contact with the first functional layer being a first surface, and each remaining surface being a second surface, the two-dimensional perovskite layer covering the entire second surface; preparing a second functional layer on the surface of the perovskite layer; and preparing a second electrode layer on the surface of the second functional layer.

12. The method for producing the perovskite layer includes the steps of: A step of preparing a three-dimensional perovskite matrix layer on the surface of the first functional layer, wherein the active material of the three-dimensional perovskite matrix layer has a general structural formula of ABX ３ or A ２ CDX ６ and solvent treating a surface of the three-dimensional perovskite matrix layer corresponding to the second surface with a mixed solvent; A step of reacting the solvent-treated three-dimensional perovskite matrix layer with a compound that provides A' ions to produce the two-dimensional perovskite layer, wherein the general structural formula of the active material in the two-dimensional perovskite layer is A'BX ３ or A' ２ CDX ６ and a step in which A' ions and A ions contain one or more monovalent cations, B ions contain one or more divalent metal cations, C ions and D ions each contain one or more monovalent and trivalent metal cations, and X ions contain one or more monovalent anions; 12. The method for producing a perovskite solar cell according to claim 11, wherein the ionic radius of at least one monovalent cation among the A' ions is larger than the ionic radius of the monovalent cation among the A ions.

13. the mixed solvent comprises a combination of a first solvent, a second solvent, and a third solvent; The first solvent includes one or more of the solvents used to prepare the precursor solution of the three-dimensional perovskite matrix layer, and optionally includes one or more of amine-based, sulfone-based, sulfoxide-based, ester-based, and ketone-based solvents, and further optionally includes one or more of dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and γ-butyrolactone; The second solvent is capable of dissolving A ions and BX ２ or the second solvent is capable of dissolving A ions and CDX ４ and optionally, the second solvent comprises one or more of an alcohol-based solvent, a nitrile-based solvent, and a ketone-based solvent; and further optionally, the second solvent comprises one or more of isopropanol, ethanol, methanol, acetone, and acetonitrile; 13. The method for producing a perovskite solar cell according to claim 12, wherein the third solvent comprises one or more anti-solvents for preparing the three-dimensional perovskite host layer, and optionally the third solvent comprises one or more of an aromatic hydrocarbon-based, ether-based, and ester-based solvent, and further optionally the third solvent comprises one or more of chlorobenzene, anisole, diethyl ether, and ethyl acetate.

14. The mixed solvent has at least one of the following characteristics: (1) the first solvent has a volume percentage of 0.01% to 1% of the third solvent; (2) the second solvent has a volume percentage of 0.01% to 10% of the third solvent; (3) The method for producing a perovskite solar cell according to claim 12 or 13, characterized in that the volume ratio of the first solvent to the second solvent is (0.1 to 1):

1.

15. The solvent treatment conditions include at least one of the following characteristics: (1) The solvent treatment time is 1 minute to 60 minutes; (2) The temperature of the mixed solvent used in the solvent treatment is 20°C to 30°C; (3) The method for producing a perovskite solar cell according to any one of claims 12 to 14, characterized in that the amount of the first solvent used is X μL, the thickness of the two-dimensional perovskite layer is Y nm, and X and Y satisfy 0.05 < X / Y < 5.

16. The method for producing a perovskite solar cell according to any one of claims 12 to 15, characterized in that the conditions for reacting the solvent-treated three-dimensional perovskite base layer with the compound that supplies A' ions include performing an annealing treatment at a temperature of 50°C to 150°C, and optionally, the annealing treatment time is 20 minutes to 40 minutes.

17. The compound that supplies the A' ions is CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ NH ２ , C.H. ３ CH ２ CH ２ CH ２ CONH ２ , C.H. ３ CH ２ CH ２ CH ２ COONH ２ , phenethylamine, benzylamine, amphetamine, fluorophenylethylamine, fluorophenethylamine iodide, phenylamine boronate, oleylamine, octylammonium bromide, N,N-bis(2-chloroethyl)-p-toluenesulfonamide and cyclopentanecarboxamide compounds, and salts thereof.

18. A power consumption device comprising at least one of the perovskite solar cell according to any one of claims 1 to 10 and a perovskite solar cell manufactured by the manufacturing method according to any one of claims 11 to 17.

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