Hole transport material and preparation method thereof, perovskite solar cell and preparation method thereof

Abstract

The invention discloses a hole transport material and a preparation method thereof, and a perovskite solar cell and a preparation method thereof. The hole transport material comprises at least one of structures shown in a formula 1 or a formula 2, wherein the formula 1 # imgabs 0 # and the formula 2 # imgabs 1 # are shown in the specification, wherein X is independently selected from Se or S; r is selected from any one of hydrogen, a cyano group, an amino group, a C1-C20 straight chain or branched chain alkyl group, a C1-C20 halogen-containing alkyl group, a C1-C15 alkoxy group and a C1-C15 disubstituted alkylamino group; ar is independently selected from any one of hydrogen, C1-C20 straight-chain or branched-chain alkyl, C1-C15 alkoxy and groups shown in a formula 3; formula 3 # imgabs2 #, wherein R2 is independently selected from any one of hydrogen, C1-C20 straight-chain or branched-chain alkyl, alkoxy, phenyl, p-methoxyphenyl, p-tert-butylphenyl and carbazole; the dashed line represents a replacement position. The hole transport material provided by the invention is beneficial to improving the photoelectric conversion efficiency of the battery.

Description

Technical Field

[0001] This application belongs to the technical field of perovskite solar cells, and specifically relates to a hole transport material and a preparation method thereof, a perovskite solar cell and a preparation method thereof. Background Art

[0002] As one of the thin-film photovoltaic technologies with great application potential in the future, perovskite solar cells (PSCs) have developed rapidly in the past decade. Perovskite solar cells include inverted-structure cells (p-i-n) and normal-structure cells (n-i-p). Taking the inverted-structure cell as an example, the inverted-structure cell has the advantages of low hysteresis, simple preparation, and strong stability, and is an ideal structure for commercialized cells.

[0003] In the inverted structure, the hole transport layer (HTL) is the first functional layer to be prepared. Its main function is to achieve the extraction and transport of holes, while blocking electrons to prevent charge recombination. In addition, the HTL can also regulate the film-forming morphology of the adjacent perovskite layer or passivate the bottom surface defects of the perovskite layer. Therefore, the selection of the HTL material has a crucial impact on the performance of perovskite battery devices. Among them, nickel oxide has attracted more and more attention due to its high transmittance, ideal valence band position, excellent chemical stability, and easy preparation, and is a commonly used hole transport material in current inverted-structure perovskite solar cells. However, existing research technologies show that NiO x As the hole transport layer of the inverted perovskite battery, the photoelectric conversion efficiency of the perovskite battery needs to be further improved. Summary of the Invention

[0004] This application aims to solve at least one of the technical problems in the related technologies to some extent. To this end, an object of this application is to provide a hole transport material and a preparation method thereof, a perovskite solar cell and a preparation method thereof. This hole transport material can be used in perovskite solar cells as a modification layer of the hole transport layer, which is beneficial to achieving a better energy level matching between the perovskite light-absorbing layer and the hole transport layer, enhancing the hole extraction ability, and improving the photoelectric conversion efficiency of perovskite solar cells.

[0005] In one aspect of this application, a hole transport material is provided, including at least one of the structures shown in Formula 1 or Formula 2:

[0006]

[0007] In Formula 1 and Formula 2:

[0008] X is independently selected from Se or S;

[0009] R is independently selected from any one of hydrogen, cyano group, amino group, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, C1-C20 halogenated alkyl group, C1-C15 alkoxy group, and C1-C15 disubstituted alkylamino group;

[0010] Ar is independently selected from any one of hydrogen, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, C1-C15 alkoxy group, and the group shown in Formula 3:

[0011]

[0012] In Formula 3: R2 is independently selected from any one of hydrogen, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, alkoxy group, phenyl group, p-methoxyphenyl group, p-tert-butylphenyl group, and carbazole; the dotted line represents the substitution position.

[0013] In the present application, a thiophene derivative is connected to a pyridine derivative to form a basic A-π-A type parent nucleus structure, and functional modification is carried out on it to synthesize an organic small molecule with multiple functional sites that can synergistically modify and passivate NiO x The organic small molecule of the hole transport layer, and the addition of the organic small molecule interface modification layer is beneficial to improving NiO x The energy level matching problem between the hole transport layer and the perovskite light-absorbing layer, and the problem of poor interface contact, increases the hole extraction and transport ability of the hole transport layer, and is beneficial to improving the photoelectric conversion efficiency of the perovskite solar cell.

[0014] In some embodiments, at least one of the following is satisfied:

[0015] (a) R is independently selected from any one of hydrogen, methoxy group, dimethylamino group, cyano group, and amino group;

[0016] (b) At least one of Ar is selected from The rest are selected from hydrogen;

[0017] (c) R2 is selected from p-methoxyphenyl group.

[0018] In some embodiments, the hole transport material includes at least one of Formula I to Formula IX:

[0019]

[0020] In some embodiments, the hole transport material includes at least one of the following:

[0021]

[0022] The second aspect of the present application proposes a method for preparing a hole transport material, including:

[0023] React raw material A with raw material B to prepare a hole transporting material;

[0024] Wherein:

[0025] Raw material A includes at least one of

[0026] Raw material B includes The hole transporting material includes, at least one of

[0027] X is independently selected from Se or S;

[0028] R is independently selected from any one of hydrogen, cyano group, amino group, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, C1-C20 halogenated alkyl group, C1-C15 alkoxy group, and C1-C15 disubstituted alkylamino group.

[0029] In some embodiments, the method for preparing the hole transporting material further includes at least one of the following (1) to (3):

[0030] (1) React with trimethyltin chloride to prepare

[0031] (2) React with bis(pinacolato)diboron to prepare

[0032] (3) React 4-bromo-4',4'-dimethoxytriphenylamine with bis(pinacolato)diboron to prepare Then react with to prepare

[0033] In some embodiments, R is selected from any one of hydrogen, methoxy group, and dimethylamino group.

[0034] The third aspect of the present application provides a perovskite solar cell, which includes a hole transporting layer, and a modification layer is provided on at least one side of the hole transporting layer;

[0035] The hole transporting layer contains a second hole transporting material, and the second hole transporting material includes NiO x ;

[0036] The modification layer contains the hole transporting material proposed in the first aspect above, or contains the hole transporting material obtained by the method proposed in the second aspect above.

[0037] In some embodiments, the perovskite solar cell further includes a perovskite layer, and the modification layer is located between the hole transport layer and the perovskite layer;

[0038] The perovskite layer contains a perovskite material, and the perovskite material includes a metal halide perovskite material. The chemical general formula of the metal halide perovskite material is ABX3; wherein, A represents a monovalent cation; B represents a divalent cation; and X represents a monovalent anion.

[0039] A fourth aspect of the present application provides a method for preparing a perovskite solar cell, including:

[0040] Forming a hole transport layer on the first electrode; the hole transport layer contains a second hole transport material, and the second hole transport material includes NiO x ;

[0041] Forming a modification layer on the hole transport layer, and the modification layer includes the hole transport material proposed in the first aspect above, or includes an organic substance obtained by the method proposed in the second aspect above;

[0042] Forming a perovskite layer on the modification layer;

[0043] Forming an electron transport layer on the perovskite layer;

[0044] Forming a second electrode on the electron transport layer to obtain a perovskite solar cell.

[0045] Additional aspects and advantages of the present application will be partially given in the following description, partially become apparent from the following description, or be understood through the practice of the present application. Description of the Drawings

[0046] Figure 1 is the 1H NMR spectrum of 2,5-bis(methylstannyl)thiophene provided in Example A of the present application.

[0047] Figure 2 is the 1H NMR spectrum of TPA-Br provided in Example A of the present application.

[0048] Figure 3 is the 1H NMR spectrum of TPA-BO provided in Example A of the present application.

[0049] Figure 4 is the 1H NMR spectrum of TPA-PY provided in Example A of the present application.

[0050] Figure 5 is the 1H NMR spectrum of BOBS provided in Example A of the present application.

[0051] Figure 6 is the 1H NMR spectrum of TPA-PY-Se provided in Example 1 of the present application.

[0052] Figure 7 is the mass spectrum of TPA-PY-Se provided in Example 1 of this application.

[0053] Figure 8 is the 1H NMR spectrum of TPA-PY-S provided in Example 1 of this application.

[0054] Figure 9 is the mass spectrum of TPA-PY-S provided in Example 1 of this application.

[0055] Figure 10 is the 1H NMR spectrum of TPA-PY-BOBS provided in Example 1 of this application.

[0056] Figure 11 is the mass spectrum of TPA-PY-BOBS provided in Example 1 of this application.

[0057] Figure 12 is a schematic diagram of the device structure of a perovskite solar cell provided in an embodiment of this application; Reference numerals:

[0058] 1, transparent bottom electrode; 2, hole transport layer; 3, modification layer; 4, perovskite light-absorbing layer; 5, passivation layer; 6, electron transport layer; 7, top electrode.

[0059] Figure 13 is the J-V curve diagram comparing the cell with the modification layer using TPA-PY-S provided in Example 4 of this application with the cell provided in Comparative Example 1.

[0060] Figure 14 is the J-V curve diagram comparing the cell with the modification layer using TPA-PY-Se provided in Example 5 of this application with the cell provided in Comparative Example 1.

[0061] Figure 15 is the J-V curve diagram comparing the cell with the modification layer using TPA-PY-BOBS provided in Example 6 of this application with the cell provided in Comparative Example 1. Detailed implementation manners

[0062] The embodiments of the present application are described in detail below, which are intended to explain the present application and should not be construed as a limitation to the present application.

[0063] Nickel oxide has attracted more and more attention due to its high transmittance, ideal valence band position, excellent chemical stability and easy preparation, and is a commonly used hole transport material in current inverted perovskite solar cells. However, existing research technologies show that NiO x (refers to a mixed system of divalent and trivalent nickel oxides) as the hole transport layer of an inverted perovskite solar cell will have problems such as energy level mismatch, poor interface contact, and the need to further improve the hole transport ability. In addition, due to NiOx It is usually composed of a mixed system of divalent and trivalent nickel, which is prone to non-radiative recombination.

[0064] Therefore, in one aspect of the embodiments of the present application, the embodiments of the present application propose a hole transport material, including at least one of the structures shown in Formula 1 or Formula 2:

[0065]

[0066] In Formula 1 and Formula 2:

[0067] X is independently selected from Se or S;

[0068] R is independently selected from any one of hydrogen, cyano group, amino group, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, C1-C20 halogen-containing alkyl group, C1-C15 alkoxy group, and C1-C15 disubstituted alkylamino group;

[0069] Ar is independently selected from any one of hydrogen, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, C1-C15 alkoxy group, and the group shown in Formula 3:

[0070]

[0071] In Formula 3: R2 is independently selected from any one of hydrogen, C1-C20 straight-chain alkyl group, C1-C20 branched-chain alkyl group, alkoxy group, phenyl group, p-methoxyphenyl group, p-tert-butylphenyl group, and carbazole; the dotted line represents the substitution position.

[0072] In the embodiments of the present application, thiophene derivatives are connected to pyridine derivatives to form a basic A-π-A type parent nucleus structure, which is functionally modified to synthesize organic small molecules with multiple functional sites. These organic small molecules can be used in perovskite solar cells as x a modification layer material for the hole transport layer of NiO x to add an interface modification layer on the surface of the NiO x hole transport layer, achieving the effects of multi-functional synergistic optimization of the energy level of the NiO x hole transport layer, improving the hole transport performance, passivating interface defects, and reducing non-radiative recombination at the interface contact. When the organic small molecule is used as the interface modification layer of the NiO x hole transport layer, the conjugated π-bridge constructed by thiophene derivatives in the molecular structure of the organic small molecule makes the molecule of this structure have a higher electron cloud density, which effectively enhances the hole transport ability of the hole transport material. The lone electron pairs contained in multiple pyridine groups in the molecular structure can effectively passivate the trivalent nickel in NiO xThe problem of energy level matching between the hole transport layer and the perovskite light-absorbing layer. The S and / or Se atoms on the thiophene derivative unit in the molecular structure effectively passivate the shallow surface defects at the bottom interface during the formation of the perovskite light-absorbing layer, suppressing the non-radiative recombination problem at the interface contact. Based on the above improvements, the hole transport material provided in the embodiments of the present application is used for NiO x In the modification layer of the hole transport layer, it is beneficial to obtain a high-quality perovskite light-absorbing layer with large grain size and low defect density, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0073] In some embodiments of the present application, at least one of the following is satisfied:

[0074] (a) R is independently selected from any one of hydrogen, methoxy, dimethylamino, cyano, and amino;

[0075] (b) At least one of Ar is independently selected from The rest are selected from hydrogen;

[0076] (c) R2 is independently selected from p-methoxyphenyl.

[0077] This type of organic small molecule provided in the embodiments of the present application is used as a hole transport material in the modification layer of the NiOx hole transport layer, and has multifunctional sites that can synergistically modify and passivate NiO x The role of the hole transport layer, which is beneficial to improving NiO x The interfacial contact with the perovskite light-absorbing layer can adjust the energy level, increase the hole extraction and transport ability of the hole transport layer, and is beneficial to improving the photoelectric conversion efficiency of the perovskite solar cell.

[0078] In some embodiments of the present application, the hole transport material includes at least one of Formula I to Formula IX:

[0079]

[0080]

[0081] In the embodiments of the present application, when using NiO x As the hole transport layer of the inverted perovskite battery, at least one of the above compounds can be used as the hole transport material to modify NiO x The hole transport layer is modified to adjust the NiO x Energy level to make the hole transport layer more matched with the perovskite light-absorbing layer, enhance the hole extraction ability and optimize the interface in contact with the perovskite light-absorbing layer, which is beneficial to preparing a high-quality perovskite light-absorbing layer film and a perovskite battery device with higher photoelectric conversion efficiency.

[0082] In some embodiments of the present application, the hole transport material includes at least one of the following:

[0083]

[0084]

[0085] The three types of hole transport materials provided by the embodiments of the present application, when applied to the modification layer of the NiOx hole transport layer in a perovskite solar cell, can effectively adjust the NiO x energy level to make the hole transport layer more matched with the perovskite light-absorbing layer, enhance the hole extraction ability and optimize the interface in contact with the perovskite light-absorbing layer. The obtained perovskite solar cell exhibits excellent photoelectric conversion efficiency.

[0086] Among them, the compound provided by Formula I has a molecular formula of C 54 H 44 N4O4S and a molar mass of 844.71 g / mol. The compound provided by Formula IV has a molecular formula of C 54 H 44 N4O4Se and a molar mass of 892.65 g / mol. The compound provided by Formula VII has a molecular formula of C 62 H 48 N4O4S and a molar mass of 944.84 g / mol.

[0087] The second aspect of the embodiments of the present application proposes a method for preparing a hole transport material, including:

[0088] Reacting raw material A with raw material B to prepare a hole transport material;

[0089] Wherein:

[0090] Raw material A includes at least one of;

[0091] Raw material B includes

[0092] The hole transport material includes, at least one of;

[0093] X is independently selected from Se or S;

[0094] R is independently selected from any one of hydrogen, cyano, amino, C1-C20 straight-chain alkyl, C1-C20 branched-chain alkyl, C1-C20 halogenated alkyl, C1-C15 alkoxy, and C1-C15 disubstituted alkylamino.

[0095] Further, R is independently selected from any one of hydrogen, methoxy, and dimethylamino.

[0096] This application uses an electron-rich thiophene derivative unit as the π-bridge, which is connected to an electron-withdrawing pyridine derivative unit to form a basic A-π-A type parent nucleus structure, and synthesizes an organic small molecule with multifunctional sites. This organic small molecule can be applied to the NiO hole transport layer interface of a perovskite solar cell to improve the photoelectric conversion efficiency. x Hole transport layer interface modification improves the photoelectric conversion efficiency of perovskite solar cells.

[0097] For such thiophene-pyridine parent nucleus derivative organic small molecules with multifunctional sites, the conjugated π-bridge constructed by the thiophene derivative in the molecular structure is conducive to the overlap of the electron clouds in the molecular structure, thereby increasing the density of the electron clouds in the molecular structure. This effectively enhances the hole transport ability of the hole transport material, thus improving the photoelectric performance of the perovskite solar cell device. At the same time, the construction of the π-bridge increases the number of N atoms in the pyridine unit in the molecular structure and the exposure degree of its lone pair electrons. The lone pair electrons in the pyridine group in the molecular structure can coordinate with the trivalent nickel in NiO, adjust the smooth energy level, and make the energy levels of the NiO hole transport layer and the perovskite light-absorbing layer more matched. The S and Se atoms on the thiophene derivative unit in the molecular structure can passivate the divalent cation defects (such as Pb defects) on the perovskite light-absorbing layer. By forming bonds such as Pb-S and Pb-Se, the shallow surface defects at the bottom interface during the formation of the perovskite light-absorbing layer are effectively passivated, and the non-radiative recombination at the interface contact is inhibited. Furthermore, the photoelectric conversion efficiency of the perovskite solar cell is effectively improved. x in x The hole transport layer and the perovskite light-absorbing layer have more matching energy levels; the S and Se atoms on the thiophene derivative unit in the molecular structure can passivate the divalent cation defects (such as Pb 2+ defects) on the perovskite light-absorbing layer, forming Pb-S and Pb-Se through bonding, effectively passivating the shallow surface defects at the bottom interface during the formation of the perovskite light-absorbing layer, and inhibiting the non-radiative recombination at the interface contact. Furthermore, the photoelectric conversion efficiency of the perovskite solar cell is effectively improved.

[0098] In some embodiments of this application, the method for preparing the hole transport material further includes at least one of the following (1) to (3):

[0099] (1) React with trimethyltin chloride to prepare

[0100] (2) React with bis(pinacolato)diboron to prepare

[0101] (3) React 4-bromo-4',4'-dimethoxytriphenylamine with bis(pinacolato)diboron to prepare Then react with to prepare

[0102] In some embodiments of this application, R is independently selected from any one of hydrogen, methoxy, and dimethylamino.

[0103] In some embodiments of this application, the preparation method of the hole transport material specifically includes:

[0104] Synthesis of TPA - BO:

[0105]

[0106] Mix 4 - bromo - 4',4' - dimethoxytriphenylamine, bis(pinacolato)diboron, PdCl2dppf (dichloride [1,1' - bis(diphenylphosphino)ferrocene] palladium), potassium acetate, and a solvent (such as 1,4 - dioxane), and carry out a heating reflux reaction to prepare TPA - BO, that is

[0107] Synthesis of TPA - PY:

[0108]

[0109] Mix TPA - BO, PdCl2dppf, potassium carbonate, and a composite solvent (such as a mixed solvent prepared according to the ratio of 1,4 - dioxane: water = 5:1), and carry out a heating reflux reaction to obtain TPA - PY, that is

[0110]

[0111] Synthesis

[0112] Mix with anhydrous tetrahydrofuran, add n - butyllithium under low temperature and inert atmosphere, carry out a room - temperature stirring reaction, and then add trimethyltin chloride and mix for reaction to prepare

[0113] Synthesis

[0114]

[0115] Mix bis(pinacolato)diboron, PdCl2dppf (dichloride [1,1' - bis(diphenylphosphino)ferrocene] palladium), potassium acetate, and a solvent (such as 1,4 - dioxane), and carry out a heating reflux reaction to prepare

[0116] Synthesis of hole - transporting material

[0117]

[0118] Mix tetrakis(triphenylphosphine)palladium, copper(I) iodide, cesium fluoride, and DMF solvent, and carry out a heating reaction to prepare the hole - transporting material.

[0119] Synthesis of hole - transporting material

[0120]

[0121] Mix PdCl2dppf, potassium carbonate, and a composite solvent (such as a mixed solvent prepared according to the ratio of 1,4-dioxane:water = 5:1), and heat under reflux to obtain a hole transporting material.

[0122] In a third aspect of the embodiments of the present application, a perovskite solar cell is proposed, which includes a hole transporting layer, and a modification layer is provided on at least one side of the hole transporting layer;

[0123] The hole transporting layer contains a second hole transporting material, and the second hole transporting material includes NiO x ;

[0124] The modification layer contains the hole transporting material proposed in the first aspect above, or contains the hole transporting material obtained by the method proposed in the second aspect above.

[0125] The perovskite solar cell provided by the embodiments of the present application uses a modification layer to modify the nickel oxide hole transporting layer and improve the interfacial contact effect between the perovskite light-absorbing layer and the hole transporting layer. The material of the modification layer contains the hole transporting material proposed in the first aspect above, or contains the hole transporting material obtained by the method proposed in the second aspect above. It is an organic small molecule with a thiophene-pyridine-based core having multiple functional sites. This organic small molecule can be applied to the NiO x hole transporting layer interface modification of the perovskite battery to improve the photoelectric conversion efficiency of the battery device.

[0126] In addition, in the embodiments of the present application, for the second hole transporting material NiO x has the meaning well-known in the art. Usually, x takes values of 1 and 1.5. Correspondingly, NiO x usually refers to a mixture of Ni2O3 and NiO. Through improvement in the embodiments of the present application, the trivalent nickel can be reduced, and the ratio of Ni 2+ / Ni 3+ can be increased to improve the photoelectric conversion efficiency of the battery device.

[0127] In some embodiments of the present application, the perovskite solar cell further includes a perovskite layer, and the modification layer is located between the hole transporting layer and the perovskite layer;

[0128] The perovskite layer contains a perovskite material, and the perovskite material includes a metal halide perovskite material. The chemical general formula of the metal halide perovskite material is ABX3; wherein, A represents a monovalent cation; B represents a divalent cation; X represents a monovalent anion.

[0129] Furthermore, A includes monovalent organic cations and / or monovalent inorganic cations; as an example, A includes Rb + , C s+ , CH3NH3 + , CH3CH2NH3 + , CH3(CH2)2NH3 + , CH3(CH2)3NH3 + , HC(NH2)2 + or a combination of several of them.

[0130] Furthermore, B includes divalent inorganic cations, which can be Pb 2+ , or a combination of Pb 2+ and other divalent cations. As an example, B includes Pb 2+ , Sn 2+ , Cu 2+ , Ge 2+ or a combination of several of them.

[0131] Furthermore, X includes monovalent organic anions and / or monovalent inorganic anions; as an example, X includes Cl - , Br - , I - , SCN - , BF4 - , PF6 - or a combination of several of them.

[0132] In some embodiments of the present application, the divalent cations at least include Pb 2+ . Furthermore, the divalent cations may also include Sn 2+ , Cu 2+ , Ge 2+ or a combination of several of them.

[0133] In some embodiments of the present application, the perovskite solar cell further includes a first electrode, an electron transport layer, and a second electrode; the first electrode, the hole transport layer, the modification layer, the perovskite light absorption layer, the electron transport layer, and the second electrode are arranged in sequence.

[0134] The perovskite solar cell provided by the embodiment of the present application is a reverse perovskite solar cell. Using the organic small molecule with a thiophene-pyridine-based mother nucleus having multifunctional sites provided by the embodiment of the present application as the modification layer is beneficial to better improving the photoelectric conversion effect of the perovskite solar cell.

[0135] In some embodiments of the present application, the first electrode includes a transparent conductive substrate electrode, and the transparent conductive substrate electrode includes a substrate and a conductive layer; wherein, the substrate includes at least one of glass, steel plate, PET (polyethylene terephthalate), PI (polyimide), PEN (polyethylene naphthalate), flexible glass, and flexible steel plate; the conductive layer includes at least one of ITO (indium tin oxide), AZO (aluminum-doped zinc oxide), and FTO (fluorine-doped tin oxide).

[0136] In some embodiments of the present application, the electron transport layer includes TiO2, SnO2, ZnO, PC 61 BM, PC 71 BM, TIPD, ICBA, C 60 , one or more of BCP.

[0137] In some embodiments of the present application, the second electrode includes a metal electrode and a transparent oxide electrode;

[0138] As an example, the metal electrode includes materials with a relatively high work function, such as metals including gold, silver, copper, aluminum, etc.

[0139] As an example, the transparent oxide electrode includes one or more of ITO and IZO.

[0140] Furthermore, the preparation method of the second electrode includes one or more of evaporation, vacuum evaporation, magnetron sputtering, and multi-arc ion plating.

[0141] A fourth aspect of the embodiments of the present application provides a method for preparing a perovskite solar cell, including:

[0142] Forming a hole transport layer on the first electrode; the hole transport layer contains a second hole transport material, and the second hole transport material includes NiO x ;

[0143] Forming a modification layer on the hole transport layer, the modification layer includes the hole transport material proposed in the first aspect above, or includes an organic substance obtained by the method proposed in the second aspect above;

[0144] Forming a perovskite layer on the modification layer;

[0145] Forming an electron transport layer on the perovskite layer;

[0146] Forming a second electrode on the electron transport layer to obtain a perovskite solar cell.

[0147] The method for preparing a perovskite solar cell provided by the embodiments of the present application can form a modified layer containing a hole transport material on the surface of the nickel oxide hole transport layer, which contains the hole transport material proposed in the first aspect above, or contains the hole transport material obtained by the method proposed in the second aspect above. The organic small molecule with a thiophene-pyridine-based parent nucleus having multifunctional sites can be applied to the NiO of the perovskite cell x The interface modification of the hole transport layer improves the photoelectric conversion efficiency of the battery device.

[0148] In some embodiments of the present application,

[0149] For the step of forming a hole transport layer on the first electrode, the method adopted includes at least one of magnetron sputtering, electron beam evaporation, atomic layer deposition, sol-gel method, solution combustion method, and spray pyrolysis method;

[0150] And / or, for the step of forming a modified layer on the hole transport layer, it includes: coating a slurry containing an organic substance on the hole transport layer and obtaining the modified layer through annealing treatment; the coating method adopted includes at least one of doctor blade coating, spin coating, spraying, slot die coating, inkjet printing, and screen printing methods.

[0151] Some modified layers of the hole transport layer provided by the prior art, either have a complex preparation method or will limit the preparation method of the modified layer, and even limit the preparation method of the hole transport layer to only a specific method, which is not applicable to the commercial development and application of large-area perovskite battery technology.

[0152] In the method for preparing a perovskite solar cell provided by the embodiments of the present application, the organic small molecule with a thiophene-pyridine-based parent nucleus can be applied to a variety of methods to form a modified layer, including but not limited to at least one of doctor blade coating, spin coating, spraying, slot die coating, inkjet printing, or screen printing methods; there are also various preparation methods applicable to the hole transport layer, including but not limited to at least one of magnetron sputtering, electron beam evaporation, atomic layer deposition, sol-gel method, solution combustion method, and spray pyrolysis method.

[0153] The interface modification layer containing the organic small molecule with a thiophene-pyridine-based parent nucleus provided by the embodiments of the present application has a simple preparation process, can be prepared by a low-temperature solution method, and is easy to realize industrial large-scale production, thereby realizing the preparation of a perovskite solar cell device with high photoelectric conversion efficiency and opening up ideas for the commercialization of large-area perovskite battery technology.

[0154] In some embodiments of the present application, the specific steps for forming a modified layer on the hole transport layer include:

[0155] Dissolve a hole transporting material (i.e., an organic small molecule with a thiophene-pyridine-based parent nucleus) in a solvent to obtain a solution. Deposit the resulting solution on the surface of the hole transporting layer by any one of blade coating, spin coating, spraying, slot die coating, inkjet printing, and screen printing.

[0156] Perform annealing treatment to form an interfacial modification layer film.

[0157] Furthermore, the solution concentration is 0.1 mg / ml to 0.5 mg / ml; for example, the solution concentrations are 0.1 mg / ml, 0.2 mg / ml, 0.3 mg / ml, 0.4 mg / ml, 0.5 mg / ml, etc.

[0158] Furthermore, the method for forming the solution includes one or more of shaking, ultrasonic treatment, heating, bubbling, and magnetic stirring. For example, a homogeneous and transparent solution containing the hole transporting material can be formed by dissolving at room temperature with shaking.

[0159] Furthermore, the solvent includes one or more of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chlorobenzene, toluene, chloroform, and N-methylpyrrolidone (NMP).

[0160] Furthermore, the annealing method includes at least one of an oven and a hot stage.

[0161] Furthermore, the annealing temperature is 90 °C to 120 °C, and the annealing time is 5 min to 15 min. For example, the annealing temperatures are 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, etc. For example, the annealing times are 5 min, 7 min, 9 min, 11 min, 13 min, 15 min, etc.

[0162] In some embodiments of the present application, the method for fabricating a perovskite solar cell device includes the following steps:

[0163] Form a nickel oxide hole transporting layer on a transparent bottom electrode;

[0164] Coat a solution containing the hole transporting material on the nickel oxide hole transporting layer, and form a modification layer through annealing treatment;

[0165] Coat a perovskite precursor solution on the modification layer, and form a perovskite light-absorbing layer through annealing treatment;

[0166] Form a passivation layer on the perovskite light-absorbing layer;

[0167] Form an electron transporting layer on the perovskite light-absorbing layer;

[0168] Form a metal electrode on the electron transporting layer to obtain a perovskite solar cell.

[0169] In addition, corresponding functional layers can be set based on actual requirements. As an example, a passivation layer can be set between the perovskite light-absorbing layer and the electron transport layer, and a buffer layer can be set between the electron transport layer and the metal electrode.

[0170] The present application will be described below with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present application in any way. The reagents used in the embodiments are all from Aladdin Biochemical Technology Co., Ltd.

[0171]

Preparation of Hole Transport Material

[0172] Example A

[0173] (1) Synthesis of 2,5-bis(methylstannyl)thiophene (intermediate):

[0174]

[0175] Add 655 mg (5 mmol) of thiophene and 30 ml of anhydrous THF (tetrahydrofuran) to a 100 ml two-necked flask. Under -78 °C and nitrogen protection, add 5 ml of n-butyllithium (BuLi) (2.5 M in hexane, 12.5 mmol). After the reaction system is stirred at room temperature for 30 min, add 12 ml of trimethyltin chloride (1.0 M in THF, 12.0 mmol). Then, stir the reaction system at room temperature overnight. After the reaction is completed, pour the reaction system into 20 ml of saturated aqueous KF (potassium fluoride) solution, extract and separate with dichloromethane, then dry the organic phase with anhydrous sodium sulfate. Rotate and evaporate the organic phase solvent to obtain the crude product. Finally, recrystallize with methanol and perform vacuum filtration to obtain white crystals, which are 2,5-bis(methylstannyl)thiophene with a yield of 75%. The synthesis route is shown in Reaction Formula 1. 2,5-bis(methylstannyl)selenophene can be prepared in the same way.

[0176] 1H NMR (400 MHz, CDCl3) δ 7.39–7.36 (m, 2H), 0.37 (s, 18H). See the attached Figure 1 .

[0177] (2) Synthesis of TPA-Br:

[0178]

[0179] 5.0 g (29 mmol) of 4-bromoaniline, 20.0 g (85 mmol) of 4-iodoanisole, 1.1 g of cuprous iodide (CuI), 1.2 g of anhydrous o-phenanthroline (1,10-Phenanthroline hydrate), 13.0 g of potassium hydroxide and 150 ml of toluene were added to a 250 ml single-necked flask in a mass ratio of 1:4, and the mixture was refluxed at 125 °C for 36 h. After the reaction was completed, the reaction system was poured into deionized water, extracted and separated with dichloromethane, the organic phase was dried with anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and 8.9 g of a yellow solid was obtained after column chromatography separation, with a yield of 80%. The synthetic route is shown in Reaction Scheme 2.

[0180] 1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 8.9 Hz, 2H), 7.02 (d, J = 8.8 Hz, 4H), 6.82 (d, J = 9.0 Hz, 6H), 3.79 (s, 6H). The 1H NMR spectrum is shown in the appendix. Figure 2 。

[0181] (3) Synthesis of TPA-BO:

[0182]

[0183] 7.66 g (20 mmol) of 4-bromo-4',4'-dimethoxytriphenylamine, 6.10 g (24 mmol) of bis(pinacolato)diboron, 0.73 g of PdCl2dppf (dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, 5% equivalent), 7.85 g (4-fold equivalent) of potassium acetate and 150 ml of 1,4-dioxane were added to a 250 ml single-necked flask, and the mixture was refluxed at 80 °C for 12 h. After the reaction was completed, the reaction system was poured into deionized water, extracted and separated with dichloromethane, the organic phase was dried with anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and 7.3 g of a white solid was obtained after column chromatography separation (eluent PE:DCM = 3:1), with a yield of 84.9%. The synthetic route is shown in Reaction Scheme 3.

[0184] 1H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 8.5 Hz, 2H), 7.06 (d, J = 8.9 Hz, 4H), 6.88–6.81 (m, 6H), 3.79 (s, 6H), 1.32 (s, 12H). The 1H NMR spectrum is shown in the appendix. Figure 3 。

[0185] (4) Synthesis of TPA-PY:

[0186]

[0187] Add 4.3 g (10 mmol) of TPA-BO, 2.83 g (10 mmol, taking R as H as an example) of 3-bromo-5-iodopyridine, 0.36 g (5% equivalent) of PdCl2dppf, and 4.14 g (3 equivalents) of potassium carbonate into a 250 ml single-neck flask. Add 100 ml of 1,4-dioxane and 20 ml of deionized water as the solvent according to the ratio of 1,4-dioxane: water = 5:1. React under reflux at 80 °C for 8 h. After the reaction is completed, pour the reaction system into deionized water, extract and separate with dichloromethane. Dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation under reduced pressure. After column chromatography separation (eluent PE:EA = 5:1), a yellow-green oil is obtained. After vacuum drying and low-temperature treatment, 3.6 g of yellow-green solid is obtained with a yield of 78%. The synthetic route is shown in Reaction Formula 4.

[0188] 1H NMR (400 MHz, CDCl3) δ 8.70 (s, 1H), 8.56 (s, 1H), 7.95 (s, 1H), 7.38–7.32 (m, 2H), 7.16–7.03 (m, 4H), 7.01–6.94 (m, 2H), 6.92–6.79 (m, 4H), 3.80 (d, J = 5.8 Hz, 6H). The 1H NMR spectrum is shown in the appendix Figure 4 。

[0189] (5) Synthesis of 3,7-boronic acid ester dibenzothiophene (BOBS):

[0190]

[0191] Add 1.72 g (5 mmol) of 3,7-dibromodibenzothiophene, 3.81 g (3 eq) of bis(pinacolato)diboron, 0.36 g (5% equivalent) of PdCl2dppf, and 1.50 g (3 equivalents) of potassium acetate into a 250 ml single-neck flask. React PdCl2dppf (0.375 g) and 100 ml of 1,4-dioxane under reflux at 80 °C for 12 h. After the reaction is completed, pour the reaction system into deionized water, extract and separate with dichloromethane. Dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation under reduced pressure. After column chromatography separation, 1.81 g of white solid is obtained with a yield of about 83%. The synthetic route is shown in Reaction Formula 5.

[0192] 1H NMR (400 MHz, CDCl3) δ 8.33 (s, 2H), 8.19 (d, J = 7.9 Hz, 2H), 7.87 (d, J = 7.9 Hz, 2H), 1.38 (s, 24H). The 1H NMR spectrum is shown in the appendix Figure 5 。

[0193] Example 1

[0194] Synthesis of TPA-PY-Se:

[0195]

[0196] Add 0.412 g (1 mmol) of 2,5-bis(methylstannyl)selenophene, 1.15 g (2.5 mmol) of 4-(5-bromo-3-pyridyl)-4',4'-dimethoxytriphenylamine (TPA-PY), 116 mg (5% equivalent) of tetrakis(triphenylphosphine)palladium (Pb(PPh3)4), 30 mg (4% equivalent) of cuprous iodide (CuI), 0.604 g (2-fold equivalent) of cesium fluoride (CsF), and 50 ml of DMF (N,N-dimethylformamide) solvent into a 100 ml single-necked flask, and react at 125 °C for 12 h. After the reaction is completed, pour the reaction system into 100 ml of saturated aqueous KF solution to precipitate a brown solid. Stir the mixture overnight, then filter by suction. Dissolve the filter cake in dichloromethane, dry with anhydrous sodium sulfate, and remove the solvent by rotary evaporation under reduced pressure. After column chromatography separation (eluent EA:DCM = 1:1), 0.64 g of yellow solid powder is obtained, and the yield is 71.7%. The synthesis route is shown in Reaction Formula 6.

[0197] 1H NMR (400 MHz, CDCl3) δ 8.73 (dd, J = 9.5, 2.0 Hz, 4H), 7.94 (t, J = 2.1 Hz, 2H), 7.60 (s, 2H), 7.47–7.38 (m, 4H), 7.16–7.08 (m, 8H), 7.02 (d, J = 8.7 Hz, 4H), 6.90–6.82 (m, 8H), 3.82 (s, 12H). MALDI-TOF MS: Calcd. For C 54 H 44 N4O4Se [M / z]: 892.25; found: 892.65. The 1H NMR spectrum is shown in the appendix Figure 6 , and the mass spectrum is shown in the appendix Figure 7 .

[0198] Example 2

[0199] Synthesis of TPA-PY-S:

[0200]

[0201] Specifically, adopt the synthesis method of Example 1, and the synthesis route and raw materials are shown in Reaction Formula 7.

[0202] 1H NMR (400 MHz, CDCl3) δ 8.79 (dd, J = 12.0, 2.1 Hz, 2H), 8.72 (dd, J = 6.8, 2.1 Hz, 2H), 8.01 (t, J = 2.1 Hz, 2H), 7.46 (d, J = 2.0 Hz, 2H), 7.44 (d, J = 2.5 Hz, 4H), 7.12 (d, J = 9.0 Hz, 8H), 7.03 (d, J = 8.7 Hz, 4H), 6.87 (d, J = 9.0 Hz, 8H), 3.82 (s, 12H). MALDI-TOF MS: Calcd. For C54H44N4O4S [M / z]: 844.30; found: 844.71. 1H NMR spectrum is shown in the appendix Figure 8 , and the mass spectrum is shown in the appendix Figure 9 .

[0203] Example 3

[0204] Synthesis of TPA-PY-BOBS:

[0205]

[0206] Specifically, the method for synthesizing TPA-PY in step (4) of Example A was adopted, and the synthesis route and raw materials are as shown in Reaction Formula 8.

[0207] 1H NMR (400 MHz, CDCl3) δ 8.84 (dd, J = 12.8, 2.1 Hz, 4H), 8.30 (d, J = 8.2 Hz, 2H), 8.18–8.05 (m, 4H), 7.76 (dd, J = 8.2, 1.6 Hz, 2H), 7.52–7.44 (m, 4H), 7.18–7.08 (m, 8H), 7.04 (d, J = 8.7 Hz, 4H), 6.91–6.81 (m, 8H), 3.82 (s, 12H). MALDI-TOF MS: Calcd. For C 62 H 48 N4O4S [M / z]: 944.33; found: 944.84. 1H NMR spectrum is shown in the appendix Figure 10 , and the mass spectrum is shown in the appendix Figure 11 .

[0208]

Preparation of Perovskite Solar Cells

[0209] Example 4

[0210] (1) Preparation of a transparent bottom electrode:

[0211] The glass / ITO was ultrasonically cleaned with detergent, deionized water, absolute ethanol, acetone, and isopropanol for 5 min in sequence, then dried with a high-pressure nitrogen gun, and treated with ultraviolet / ozone for 30 min.

[0212] (2) Preparation of hole transport layer:

[0213] Magnetron sputter nickel oxide with a thickness of 20 nm on an ITO (indium tin oxide) substrate.

[0214] First, clean the magnetron sputtering instrument: clean the inner lining ring of the polished target with a sandblaster, clean the dust in the cavity with a vacuum cleaner, and finally wipe it clean with anhydrous ethanol. Fix the glass substrate on the rotatable metal substrate in the cavity with a mask, close the chamber door, and adjust the target-substrate distance to 15 cm. After the vacuum degree drops to 9×10 -6 Pa, the control program starts sputtering. The sputtering process parameters are: power supply: RF, sputtering gas: Ar, target: NiO, sputtering pressure: 45 mTorr, sputtering power: 65 W, substrate temperature: room temperature.

[0215] (3) Preparation of modification layer

[0216] Weigh TPA-PY-S and dissolve it in chlorobenzene. Oscillate until it is completely dissolved, with a concentration of 0.2 mg / ml. Spin-coat it on the nickel oxide substrate. The rotational speed of the spin coater is 3000 rpm, the acceleration is 1000 rpm, spin-coat for 30 s, heat the hot plate to 100 °C, and anneal for 10 min to form a modification layer on the upper surface of the hole transport layer.

[0217] (4) Preparation of perovskite light-absorbing layer

[0218] The perovskite light-absorbing layer is prepared by the doctor blade method. Doctor blade a perovskite precursor solution of 1.31 M FA 0.85 MA 0.1 Cs 0.05 PbI3. The height of the doctor blade is 150 μm, the moving speed of the substrate is 2 mm / s, the air knife pressure is 0.4 MPa, and then quickly move the substrate to the hot plate at 100 °C and anneal for 1 h to obtain the perovskite light-absorbing layer.

[0219] (5) Preparation of passivation layer

[0220] Weigh EDAI2 (ethyl-1,2-diammonium iodide) and dissolve it in a mixed solvent of IPA (isopropyl alcohol) and CB (CB) (IPA:CB = 2:1). The solution concentration is 1 mg / ml. Spin-coat it on the surface of the perovskite film. The rotational speed of the spin coater is 5000 rpm, spin-coat for 30 s, heat the hot plate to 100 °C, and anneal for 5 min to form a passivation layer on the upper surface of the perovskite light-absorbing layer.

[0221] (6) Preparation of electron transport layer

[0222] By thermal evaporation, sequentially deposit LiF (1 nm, ), C60 (15 nm, ), BCP (6 nm, ) to form a composite electron transport layer.

[0223] (7) Prepare the top electrode:

[0224] Under the condition of a vacuum degree of 6.5×10 -4 Pa, evaporate the metal electrode Ag (100 nm, ) on the composite electron transport layer.

[0225] The perovskite solar cell device structure prepared by the above method is as Figure 12 shown: glass / ITO / NiO x / TPA-PY-S / FA 0.85 MA 0.1 Cs 0.05 PbI3 / EDAI2 / LiF,C60,BCP / Ag, with an effective area of 9 mm 2 , and the photoelectric conversion efficiency data are shown in the appendix Figure 13 .

[0226] The test conditions for the photoelectric conversion efficiency are: spectral distribution AM1.5 G, light intensity 1000 W / m 2 , AAA solar simulator (XES-502S+ELS155 type of SAN-EI Corporation, Japan), and the I-V curve is measured with a Keithly 2400 type digital source meter.

[0227] Example 5

[0228] Example 5 adopts the preparation method of Example 4, the difference is that the method for preparing the modification layer in step (3) is different, and the preparation of the modification layer is specifically as follows:

[0229] Weigh TPA-PY-Se and dissolve it in chlorobenzene, shake until completely dissolved, with a concentration of 0.1 mg / ml, spin-coat it on the nickel oxide substrate, the rotation speed of the spin coater is 3000 rpm, the acceleration is 1000 rpm, spin-coat for 30 s, the hot stage is at 90 °C, anneal for 15 min, and form a modification layer on the upper surface of the hole transport layer.

[0230] The perovskite solar cell device structure prepared by the above method is as Figure 12 shown: glass / ITO / NiO x / TPA-PY-Se / FA 0.85 MA 0.1 Cs 0.05 PbI3 / EDAI2 / LiF,C60,BCP / Ag, with an effective area of 9 mm 2 , and the photoelectric conversion efficiency data are shown in the appendix Figure 14 , and the test conditions are the same as those in Example 4.

[0231] Example 6

[0232] Example 6 adopts the preparation method of Example 4, except that the method for preparing the modification layer in step (3) is different. The preparation of the modification layer is specifically as follows:

[0233] Weigh TPA-PY-BOBS and dissolve it in chlorobenzene. Shake until it is completely dissolved, with a concentration of 0.5 mg / ml. Spin-coat it on the nickel oxide substrate. The rotation speed of the spin coater is 3000 rpm, the acceleration is 1000 rpm, and spin-coat for 30 s. Use a hot plate at 120 °C and anneal for 5 min to form a modification layer on the upper surface of the hole transport layer.

[0234] The device structure of the perovskite solar cell prepared by the above method is as Figure 12 shown: Glass / ITO / NiO x / TPA-PY-BOBS / FA 0.85 MA 0.1 Cs 0.05 PbI3 / EDAI2 / LiF, C60, BCP / Ag, with an effective area of 9 mm 2 , and the photo - electric conversion efficiency data can be seen in the appendix Figure 15 , and the test conditions are the same as those in Example 4.

[0235] Comparative Example 1

[0236] Example 2 adopts the preparation method of Example 1, except that step (3) is not included, that is, the obtained perovskite solar cell has no modification layer.

[0237] The device structure of the perovskite solar cell prepared by the above method is: Glass / ITO / NiO x / FA 0.85 MA 0.1 Cs 0.05 PbI3 / EDAI2 / LiF, C60, BCP / Ag, with an effective area of 9 mm 2 , and the photo - electric conversion efficiency data can be seen in the appendix Figure 13 、 14 、15, and the test conditions are the same as those in Example 4.

[0238] The efficiency of the device with TPA - PY - S used in the modification layer is 19.95%; the efficiency of the device with TPA - PY - Se used in the modification layer is 19.52%; the efficiency of the device with TPA - PY - BOBS used in the modification layer is 19.50%; the efficiency of all devices is better than that of the standard device without using the modification molecule (18.78%).

[0239] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0240] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present application. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present application.

Claims

1. A hole transport material, characterized in that, Comprising at least one of the structures represented by Formula 1 or Formula 2: In Formula 1 and Formula 2: X is independently selected from Se or S; R is independently selected from any one of hydrogen, cyano, amino, C1-C20 linear alkyl, C1-C20 branched alkyl, C1-C20 haloalkyl, C1-C15 alkoxy, and C1-C15 disubstituted alkylamino; Ar is independently selected from any one of hydrogen, C1-C20 linear alkyl, C1-C20 branched alkyl, C1-C15 alkoxy, and the group represented by Formula 3: In Formula 3: R2 is independently selected from any one of hydrogen, C1-C20 linear alkyl, C1-C20 branched alkyl, alkoxy, phenyl, p-methoxyphenyl, p-tert-butylphenyl, and carbazole; the dotted line represents the substitution position.

2. The hole transporting material according to claim 1, wherein Satisfying at least one of the following: (a) R is independently selected from any one of hydrogen, methoxy, dimethylamino, cyano, and amino; (b) at least one of said Ar is taken from and the rest is taken from hydrogen; (c) R2 is selected from p-methoxyphenyl.

3. The hole transporting material according to claim 1 or 2, characterized in that, The hole transport material comprises at least one of Formula I to Formula IX:

4. The hole transporting material according to claim 1 or 2, characterized in that, The hole transport material comprises at least one of the following:

5. A method for preparing a hole transporting material, characterized in that, Comprising: Reacting raw material A with raw material B to prepare a hole transport material; Wherein: The raw material A includes at least one of; the raw material B includes The hole transport material includes, at least one of; X is independently selected from Se or S; R is independently selected from any one of hydrogen, cyano, amino, C1-C20 linear alkyl, C1-C20 branched alkyl, C1-C20 haloalkyl, C1-C15 alkoxy, and C1-C15 disubstituted alkylamino.

6. The method according to claim 5, characterized in that Further comprising at least one of the following (1) to (3): (1) React with trimethyltin chloride to prepare (2) React with bis(pinacolato)diboron to prepare (3) 4-bromo-4',4'-dimethoxytriphenylamine reacts with bis(pinacolato)diboron to prepare Then reacts with to prepare 7. The method according to claim 5, wherein R is independently selected from any one of hydrogen, methoxy, and dimethylamino.

8. A perovskite solar cell, characterized in that, Comprising a hole transport layer, and a modification layer is provided on at least one side of the hole transport layer; The hole transport layer includes a second hole transport material, and the second hole transport material includes NiO x ; The modification layer contains the hole transport material according to any one of Claims 1 to 4, or contains the hole transport material obtained by the method according to any one of Claims 5 to 7.

9. The perovskite solar cell according to claim 8, wherein, The perovskite solar cell further comprises a perovskite layer, and the modification layer is located between the hole transport layer and the perovskite layer; The perovskite layer contains a perovskite material, and the perovskite material comprises a metal halide perovskite material, and the chemical general formula of the metal halide perovskite material is ABX3; wherein, A represents a monovalent cation; B represents a divalent cation; X represents a monovalent anion.

10. A method for preparing a perovskite solar cell, characterized in that, Comprising: A hole transport layer is formed on the first electrode; the hole transport layer contains a second hole transport material, and the second hole transport material includes NiO x ; Forming a modification layer on the hole transport layer, the modification layer contains the hole transport material according to any one of Claims 1 to 4, or contains an organic substance obtained by the preparation method according to any one of Claims 5 to 7; Forming a perovskite layer on the modification layer; Forming an electron transport layer on the perovskite layer; Forming a second electrode on the electron transport layer to obtain a perovskite solar cell.

Images