Photoresponse hole transport composite layer and preparation method thereof, perovskite solar cell and electric device

Abstract

The invention relates to the technical field of solar cells, in particular to a photoresponse hole transport composite layer and a preparation method thereof, a perovskite solar cell and a power utilization device, and the photoresponse hole transport composite layer comprises a hole transport layer and a photoresponse molecular layer arranged on the hole transport layer; the hole transport layer is a self-assembled monomolecular layer, and the self-assembled monomolecular layer comprises a self-assembled monomolecular material; the photoresponse molecular layer comprises at least one of an azobenzene derivative and a spiropyrane derivative. The light response molecular layer is arranged on the surface of the hole transport layer, so that reversible adjustment of the wettability of the surface of the hole transport layer before and after deposition of the perovskite absorption layer is realized, and the problem that the hydrophilic and hydrophobic properties of the surface of the hole transport layer before and after deposition of the perovskite absorption layer are not matched is solved.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to photoresponsive hole transport composite layers and their preparation methods, perovskite solar cells, and electrical devices. Background Technology

[0002] In perovskite solar cells, the hole transport layer is crucial for device performance. To simplify the fabrication process of perovskite solar cells, functionalized substrates with pre-assembled self-assembled single-molecule (SAM) hole transport layers on transparent conductive substrates have been developed in recent years. However, these functionalized substrates face the following technical challenges: to ensure uniform spreading and film formation of the perovskite absorber solution during deposition, the functionalized substrate typically requires a certain degree of hydrophilicity. However, this hydrophilicity makes the SAM hole transport layer more susceptible to environmental moisture and oxygen during storage, transportation, and handling, severely impacting the substrate's performance and reliability, leading to decreased efficiency and stability, or even cell failure. Summary of the Invention

[0003] Based on this, the main objective of this application is to provide a photoresponsive hole transport composite layer, which solves the problem of decreased reliability of hydrophilic self-assembled monolayers due to the influence of water vapor and oxygen before the deposition of perovskite absorption layer by setting a photoresponsive molecular layer on the surface of the hole transport layer.

[0004] The first aspect of this application provides a photoresponsive hole transport composite layer, comprising a hole transport layer and a photoresponsive molecular layer disposed on the hole transport layer; the hole transport layer is a self-assembled monolayer comprising a self-assembled monomolecule material; the photoresponsive molecular layer comprises at least one of an azobenzene derivative and a spiropyran derivative.

[0005] In some embodiments, the azobenzene derivatives include at least one of 4-carboxyazobenzene, 4-aminoazobenzene, N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo)aniline, 4,4'-dihydroxyazobenzene, and azobenzene-4,4'-dicarboxylic acid.

[0006] In some embodiments, the spiropyran derivatives include at least one of 6-nitrospiropyran, 8-methoxyspiropyran, bromospiropyran, dinitrospiropyran, and carboxyspiropyran.

[0007] In some implementations, the hole transport layer has a thickness of 1 nm to 2 nm; and / or the photoresponsive molecular layer has a thickness of 1 nm to 2 nm.

[0008] In some embodiments, the self-assembled monomolecular materials include [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethoxy-9H-carbazole-9-yl)hexyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethyl-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethyl-9H-carbazole-9-yl)hexyl]phosphonic acid, [1-(3,6-dimethyl-9H-carbazole-9-yl)methyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [8-(3,6-dimethyl-9H-carbazole-9-yl)octyl]phosphate, [1-(9H-carbazole-9-yl)methyl]phosphate, (2-(9H-carbazole-9-yl)ethyl)phosphate, [3-(9H-carbazole-9-yl)propyl]phosphate, [4-(9H-carbazole-9-yl)butyl]phosphate, [6-(9H-carbazole-9-yl)hexyl]phosphate, [8-(9H-carbazole-9-yl)octyl]phosphate, [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl]phosphate, 2,3,4,5,6-pentafluorobenzyl phosphate, [2-(9H-9'-phenyl-3,3'-di-carbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-di-carbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-di-di-carbazole-9-yl)ethyl]phosphate, [Carbazole-9-yl)butyl]phosphate, [4-(diphenylamino)phenyl)ethyl]phosphate, [4-(diphenylamino)phenyl)propyl]phosphate, [4-(10H-phenthiazin-10-yl)butyl]phosphate, [2-(7H-dibenzocarbazole-7-yl)ethyl]phosphate, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphate, [3-(3,6-dibromo-9H-carbazole-9-yl)propyl]phosphate, [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphate, [6-(3,6-dibromo-9H-carbazole-9-yl)hexyl]phosphate, [1-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphate, [2-(3,6-di-tert-butyl-9H- [Carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [8-(3,6-di-tert-butyl-9H-carbazole-9-yl)octyl]phosphoric acid, [1-(3,6-diphenyl-9H-carbazole-9-yl)methyl]phosphoric acid, [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-diphenyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl ...hexyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [6-(3,6-di-tertAt least one of the following: [6-diphenyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [8-(3,6-diphenyl-9H-carbazole-9-yl)octyl]phosphoric acid, [2-(10H-phenoxazine-10-yl)ethyl]phosphoric acid, [4-(3,7-dibromo-10H-phenthiazine-10-yl)butyl]phosphoric acid, and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphoric acid.

[0009] The second aspect of this application provides a method for preparing a photoresponsive hole transport composite layer as provided in the first aspect of this application, comprising the following steps: coating a self-assembled monomolecular material solution to prepare a hole transport layer; coating at least one of an azobenzene derivative solution, a spiropyran derivative solution, and a mixed solution of an azobenzene derivative and a spiropyran derivative on the surface of the hole transport layer to form a photoresponsive molecular layer on the hole transport layer.

[0010] In some embodiments, at least one of the following conditions is met: (1) the solute concentration of the self-assembled monomolecular material solution is 0.1 mg / mL to 1 mg / mL; (2) the solute concentration of the azobenzene derivative solution is 0.1 mM to 0.8 mM; (3) the solute concentration of the spiropyran derivative solution is 0.1 mM to 0.8 mM; (4) the solute concentration of the mixed solution of the azobenzene derivative and the spiropyran derivative is 0.2 mM to 0.8 mM.

[0011] In some embodiments, the solvents for the self-assembled monomolecular material solution, the azobenzene derivative solution, the spiropyran derivative solution, and the mixed solution of azobenzene and spiropyran derivatives are each independently selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0012] The third aspect of this application provides a perovskite solar cell, including the photoresponsive hole transport composite layer provided in the first aspect of this application or the photoresponsive hole transport composite layer prepared by the preparation method provided in the second aspect of this application.

[0013] The fourth aspect of this application provides an electrical device including the perovskite solar cell provided in the third aspect of this application.

[0014] Compared with traditional technologies, this application has at least the following beneficial effects:

[0015] This application incorporates a photoresponsive molecular layer on a hole transport layer. The azobenzene derivatives and / or spiropyran derivatives in this photoresponsive molecular layer exhibit a reversible photoisomerization effect, ensuring that the self-assembled monomolecules are in a hydrophobic configuration during storage or transportation, and that the hole transport layer surface is entirely hydrophobic, thereby effectively resisting water and oxygen intrusion. When a perovskite absorber layer needs to be deposited, only a simple light irradiation treatment is required to transform the self-assembled monomolecules into a hydrophilic configuration, ensuring uniform spreading and film formation of the perovskite absorber layer solution, thereby improving battery efficiency and stability. Attached Figure Description

[0016] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings.

[0017] Figure 1 This is a schematic diagram of the structure of the photoresponsive hole transport composite layer in one embodiment of this application.

[0018] Figure 2 This is a schematic diagram of a method for preparing a photoresponsive hole transport composite layer according to an embodiment of this application.

[0019] Explanation of reference numerals in the attached figures

[0020] 1. Photoresponsive hole transport composite layer; 10. Hole transport layer; 20. Photoresponsive molecular layer. Detailed Implementation

[0021] Reference will now be made to detailed embodiments of this application, one or more of which are described below. Each example is provided for explanation and not for limitation of this application. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to this application without departing from its scope or spirit. For example, features described or illustrated as part of one embodiment may be used in another embodiment to produce further embodiments.

[0022] Therefore, this application is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents. Other objects, features, and aspects of this application are disclosed in or will be apparent from the following detailed description. It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of this application.

[0023] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0024] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0025] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0026] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0027] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0028] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0029] like Figure 1 As shown, this application provides a photoresponsive hole transport composite layer 1, including a hole transport layer 10 and a photoresponsive molecular layer 20 disposed on the hole transport layer 10; the hole transport layer 10 is a self-assembled monolayer, including a self-assembled monomolecule material; the photoresponsive molecular layer 20 includes at least one of azobenzene derivatives and spiropyran derivatives.

[0030] This application provides a photoresponsive molecular layer 20 on the hole transport layer 10. The azobenzene derivatives and / or spiropyran derivatives in the photoresponsive molecular layer 20 have a reversible photoisomerization effect, which makes the self-assembled single-molecule material in a hydrophobic configuration during storage or transportation, and the surface of the hole transport layer 10 is generally hydrophobic, thereby effectively resisting water and oxygen intrusion. When it is necessary to deposit a perovskite absorber layer, only a simple light irradiation treatment is needed to transform the self-assembled single-molecule material into a hydrophilic configuration, ensuring that the perovskite absorber layer solution is uniformly spread and formed, thereby improving the battery efficiency and stability.

[0031] In some embodiments, the photoresponsive molecular layer 20 includes spiropyran derivatives.

[0032] The photoresponsive molecular layer 20 in this application contains spiropyran derivatives. The MC-configured (colored open-ring zirconia structure) molecules within these spiropyran derivatives generate a π-π stacking effect with the aromatic rings of SAM molecules (such as Me-4PACz) through their extended conjugated structures. This stabilizes and orderly fixes the passivated molecules at the interface, increasing the anchoring ability of the interfacial bonding between the hole transport layer 10 and the photoresponsive molecular layer 20 on the surface. Simultaneously, the MC-configured molecules expose Lewis base functional groups such as carbonyl (C=O) and thiocarbonyl (C=S). During perovskite crystallization, a large amount of uncoordinated Pb exists at the perovskite / hole transport layer 10 interface. 2+ (Lewis acid) undergoes strong coordination, achieving in-situ passivation.

[0033] In some embodiments, the photoresponsive molecular layer 20 includes an azobenzene derivative.

[0034] The azobenzene derivatives described in this application exhibit no significant shift in their molecular orbital energy levels, particularly the highest occupied molecular orbital (HOMO) level, during cis-trans isomerization. Regardless of the optical isomerization state, they maintain a good match with the HOMO level of the underlying hole transport layer (SAM). This characteristic ensures that no additional energy barrier is introduced at the interface when holes are extracted from the perovskite layer towards the electrode, thereby guaranteeing low series resistance and high hole extraction efficiency, which in turn improves the device's fill factor (FF) and short-circuit current density (Jsc).

[0035] In some embodiments, the azobenzene derivatives include at least one of 4-carboxyazobenzene, 4-aminoazobenzene, N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo)aniline, 4,4'-dihydroxyazobenzene, and azobenzene-4,4'-dicarboxylic acid.

[0036] In some embodiments, the spiropyran derivatives include at least one of 6-nitrospiropyran, 8-methoxyspiropyran, bromospiropyran, dinitrospiropyran, and carboxyspiropyran.

[0037] In some embodiments, the thickness of the hole transport layer 10 is 1nm to 2nm, specifically 1nm, 1.2nm, 1.4nm, 1.6nm, 1.8nm, or 2nm.

[0038] In some embodiments, the thickness of the photoresponsive molecular layer 20 is 1 nm to 2 nm, including but not limited to 1 nm, 1.2 nm, 1.4 nm, 1.6 nm, 1.8 nm, and 2 nm. Further, the thickness of the photoresponsive molecular layer 20 is 1 nm to 1.6 nm.

[0039] In some embodiments, the self-assembled monomolecular materials include [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethoxy-9H-carbazole-9-yl)hexyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethyl-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethyl-9H-carbazole-9-yl)hexyl]phosphonic acid, [1-(3,6-dimethyl-9H-carbazole-9-yl)methyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [8-(3,6-dimethyl-9H-carbazole-9-yl)octyl]phosphate, [1-(9H-carbazole-9-yl)methyl]phosphate, (2-(9H-carbazole-9-yl)ethyl)phosphate, [3-(9H-carbazole-9-yl)propyl]phosphate, [4-(9H-carbazole-9-yl)butyl]phosphate, [6-(9H-carbazole-9-yl)hexyl]phosphate, [8-(9H-carbazole-9-yl)octyl]phosphate, [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl]phosphate, 2,3,4,5,6-pentafluorobenzyl phosphate, [2-(9H-9'-phenyl-3,3'-di-carbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-di-carbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-di-di-carbazole-9-yl)ethyl]phosphate, [Carbazole-9-yl)butyl]phosphate, [4-(diphenylamino)phenyl)ethyl]phosphate, [4-(diphenylamino)phenyl)propyl]phosphate, [4-(10H-phenthiazin-10-yl)butyl]phosphate, [2-(7H-dibenzocarbazole-7-yl)ethyl]phosphate, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphate, [3-(3,6-dibromo-9H-carbazole-9-yl)propyl]phosphate, [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphate, [6-(3,6-dibromo-9H-carbazole-9-yl)hexyl]phosphate, [1-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphate, [2-(3,6-di-tert-butyl-9H- [Carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [8-(3,6-di-tert-butyl-9H-carbazole-9-yl)octyl]phosphoric acid, [1-(3,6-diphenyl-9H-carbazole-9-yl)methyl]phosphoric acid, [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-diphenyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl ...hexyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)ethyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [6-(3,6-di-tertAt least one of the following: [6-diphenyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [8-(3,6-diphenyl-9H-carbazole-9-yl)octyl]phosphoric acid, [2-(10H-phenoxazine-10-yl)ethyl]phosphoric acid, [4-(3,7-dibromo-10H-phenthiazine-10-yl)butyl]phosphoric acid, and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphoric acid.

[0040] like Figure 2 As shown, a second aspect of this application provides a method for preparing the photoresponsive hole transport composite layer 1 as provided in the first aspect of this application, comprising the following steps:

[0041] S1. Coating a self-assembled monomolecular material solution to prepare hole transport layer 10.

[0042] S2. Coat the surface of hole transport layer 10 with at least one of azobenzene derivative solution, spiropyran derivative solution, and a mixed solution of azobenzene derivative and spiropyran derivative to form a photoresponsive molecular layer on the hole transport layer.

[0043] In some embodiments, the solute concentration of the self-assembled monomolecular material solution is 0.1 mg / mL to 1 mg / mL.

[0044] In some embodiments, the solute concentration of the azobenzene derivative solution is 0.1 mM to 0.8 mM.

[0045] In some embodiments, the solute concentration of the spiropyran derivative solution is 0.1 mM to 0.8 mM.

[0046] In some embodiments, the solute concentration of the mixed solution of azobenzene derivatives and spiropyran derivatives is 0.2 mM to 0.8 mM.

[0047] In some embodiments, the concentration of azobenzene derivatives in the mixed solution is 0.1 mM to 0.4 mM; and the concentration of spiropyran derivatives is 0.1 mM to 0.4 mM.

[0048] In some embodiments, the solvents for the self-assembled monomolecular material solution, the azobenzene derivative solution, the spiropyran derivative solution, and the mixed solution of azobenzene and spiropyran derivatives are each independently selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0049] In some embodiments, the coatings in S1 and S2 described above are each independently selected from at least one of spin coating, blade coating, slot coating, and inkjet printing.

[0050] It is understandable that S1 above refers to coating a self-assembled monomolecular material solution onto the substrate surface.

[0051] In some embodiments, the step of cleaning the substrate is also included.

[0052] In some embodiments, the cleaning process is at least one of ultrasonic cleaning or ultraviolet ozone treatment.

[0053] The third aspect of this application provides a perovskite solar cell, including the photoresponsive hole transport composite layer 1 provided in the first aspect of this application or the photoresponsive hole transport composite layer 1 prepared by the preparation method provided in the second aspect of this application.

[0054] In some embodiments, a perovskite solar cell includes a transparent conductive substrate, a photoresponsive hole transport composite layer 1, a perovskite absorber layer, an electron transport layer, a buffer layer, and a metal electrode stacked together.

[0055] In some embodiments, the transparent conductive substrate includes one or more of ITO, IZO, IWO, ICO, FTO, and AZO.

[0056] In a specific example, the transparent conductive substrate is an FTO substrate.

[0057] In some embodiments, the perovskite layer material comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion. A includes Cs + K + 、Rb + One or more of monovalent amine cations and monovalent amido cations. Non-limiting examples of monovalent amine cations include CH3NH3. + (Methylamine, MA) + ), ammonium (NH4) + Non-limiting examples of monovalent amidine cations include NH₂CH=NH₂. + (Formamidin, FA) + B includes Pb. 2+ Sn 2+ Fe 2+ Mn 2+ Ni 2+ 、Ge 2+ Co 2+ and Sb 2+ One or more of these. X includes I. - ,Br - and Cl - One or more of them.

[0058] In a specific example, the electron transport layer material includes C60 and / or PCBM (methyl methanefullerene phenyl-C61-butyrate).

[0059] In a specific example, the material of the buffer layer includes SnO2 and / or BCP (Bathocuproine, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline).

[0060] In some embodiments, the material of the metal electrode includes one or more of Cu, Al, Ag, and Au.

[0061] In some embodiments, this application also provides a method for fabricating a perovskite solar cell, comprising the following steps:

[0062] S10. Illuminate the photoresponsive hole transport composite layer 1.

[0063] S20. A perovskite absorption layer is formed on the photoresponsive molecular layer 20 in the photoresponsive hole transport composite layer 1.

[0064] S30, an electron transport layer is formed on the perovskite absorption layer.

[0065] S40. A buffer layer is formed on the electron transport layer.

[0066] S50, Form a metal electrode on the buffer layer.

[0067] In one specific embodiment, the photoresponsive hole transport composite layer 1 is illuminated with ultraviolet light of 4.3nm~400nm.

[0068] The fourth aspect of this application provides an electrical device including the perovskite solar cell provided in the third aspect of this application.

[0069] The present application will be further described below with reference to specific embodiments and comparative examples.

[0070] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0071] Example 1

[0072] Fabrication of photoresponsive hole transport composite layer 1 and perovskite solar cell:

[0073] 1) The FTO substrate was ultrasonically cleaned sequentially with deionized water, ethanol, acetone and isopropanol, with each cleaning step lasting 10 minutes. It was then dried with a nitrogen (N2) gas gun and treated with a UV-zone (ultraviolet ozone) for 20 minutes to obtain the substrate ready for use.

[0074] 2) Dissolve Me-4PACZ ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid) in anhydrous ethanol and stir to obtain a Me-4PACZ solution with a concentration of 0.5 mg / mL; use dynamic spin coating method to coat the Me-4PACZ solution onto the substrate at a coating speed of 3000 rpm for 30 s, and anneal at 100℃ for 10 min to form a hole transport layer 10 with a thickness of 1.5 nm.

[0075] 3) Dissolve 4-carboxy-azobenzene (4-CAz) in anhydrous ethanol and stir to obtain a 0.5 mM 4-carboxy-azobenzene solution. Use dynamic spin coating method to coat the 4-carboxy-azobenzene solution on the hole transport layer 10 at a coating speed of 5000 rpm for 30 s. Anneal at 70 °C for 5 min to form a photoresponsive molecular layer 20 with a thickness of 1.5 nm.

[0076] 4) The photoresponsive molecular layer was irradiated with 365nm ultraviolet light for 10 minutes. Before irradiation, the surface static water contact angle was 93.2°, indicating a hydrophobic state. After irradiation, 4-carboxyazobenzene was isomerized from trans to cis, and the surface contact angle decreased to 28.3°, indicating a hydrophilic state.

[0077] 5) Dissolve 1.6 mol of FAPbI3 perovskite solution in 1 mL of a 4:1 (v / v) mixed solvent of DMF and DMSO, and stir for 2 h to obtain a perovskite precursor solution. Using a one-step spin-coating method, spin-coat the perovskite precursor solution onto the photoresponsive molecular layer 20 after phototreatment at a coating speed of 5000 rpm for 30 s. 15 s before the end of the spin-coating deposition, rapidly add 300 μL of chlorobenzene to the perovskite precursor solution to form a perovskite wet film. Anneal at 150 °C for 15 min to form a perovskite absorption layer with a thickness of 500 nm.

[0078] 6) A C60 (fullerene) layer with a thickness of 30 nm was deposited on the perovskite absorber layer at a rate of 0.5 Å / s as an electron transport layer.

[0079] 7) A 6 nm thick BCP (Bathocuproine, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) layer was deposited on the electron transport layer at a rate of 0.5 Å / s as a buffer layer.

[0080] 8) A 110 nm silver (Ag) electrode is deposited on the buffer layer using a thermal evaporation deposition method to obtain a perovskite solar cell.

[0081] Example 2

[0082] The preparation process of this embodiment is basically the same as that of Example 1. The main difference is that in this embodiment, step 3) is: 6-nitro-spiropyran (6-nitro-BIPS) is dissolved in anhydrous ethanol and stirred to obtain a 0.5 mM 6-nitro-spiropyran solution. The 6-nitro-spiropyran solution is coated on the hole transport layer 10 at a coating speed of 5000 rpm for 30 s using a dynamic spin coating method. The coating is then annealed at 70 °C for 5 min to form a photoresponsive molecular layer 20 with a thickness of 1.5 nm.

[0083] Step 4) involves irradiating the photoresponsive molecular layer with 365nm ultraviolet light for 205 minutes. Before irradiation, the surface static water contact angle is 95.5°, indicating a hydrophobic state. After irradiation, the spiropyran molecules undergo ring-opening transformation into the MC configuration (colored ring-opening moniliform structure), and the surface contact angle decreases to 28.7°, indicating a hydrophilic state.

[0084] Example 3

[0085] The preparation process of this embodiment is basically the same as that of Embodiment 1. The main difference is that in this embodiment, the concentration of Me-4PACZ solution in step 2) is 0.8 mg / mL and the thickness of hole transport layer 10 is 2 nm.

[0086] Step 3) is as follows: Dissolve 4-aminoazobenzene in anhydrous ethanol and stir to obtain a 0.8 mM 4-aminoazobenzene solution. Use dynamic spin coating method to coat the 4-aminoazobenzene solution on the hole transport layer 10 at a coating speed of 5000 rpm for 30 s. Anneal at 70 °C for 5 min to form a photoresponsive molecular layer 20 with a thickness of 2 nm.

[0087] Step 4 involves irradiating the photoresponsive molecular layer with 365nm ultraviolet light for 20 minutes. Before irradiation, the surface static water contact angle is 86°, indicating a hydrophobic state. After irradiation, 4-aminoazobenzene isomerizes from trans to cis, and the surface contact angle decreases to 34.6°, indicating a hydrophilic state.

[0088] Example 4

[0089] The preparation process of this embodiment is basically the same as that of Embodiment 1. The main difference is that in this embodiment, the concentration of Me-4PACZ solution in step 2) is 0.5 mg / mL and the thickness of hole transport layer 10 is 1.5 nm.

[0090] Step 3) involves dissolving 8-methoxyspiropyran in anhydrous ethanol and stirring to obtain a 0.1 mM 8-methoxyspiropyran solution. The 8-methoxyspiropyran solution is then coated onto the hole transport layer 10 using a dynamic spin-coating method at a coating speed of 5000 rpm for 30 seconds. The coating is then annealed at 70°C for 5 minutes to form a photoresponsive molecular layer 20 with a thickness of 1 nm.

[0091] Step 4) involves irradiating the photoresponsive molecular layer with 365nm ultraviolet light for 20 minutes. Before irradiation, the surface static water contact angle is 93.2°, indicating a hydrophobic state. After irradiation, the spiropyran molecules undergo ring-opening transformation into the MC configuration (colored ring-opening moniliform structure), and the surface contact angle decreases to 35.3°, indicating a hydrophilic state.

[0092] Example 5

[0093] The preparation process of this embodiment is basically the same as that of Embodiment 1. The main difference is that in this embodiment, the concentration of Me-4PACZ solution in step 2) is 0.5 mg / mL and the thickness of hole transport layer 10 is 1.5 nm.

[0094] Step 3) involves dissolving 4,4'-dihydroxyazobenzene and dinitrospiropyran in anhydrous ethanol and stirring to obtain a mixed solution with a concentration of 0.8 mM (4,4'-dihydroxyazobenzene has a concentration of 0.4 mM and dinitrospiropyran has a concentration of 0.4 mM). The mixed solution is then coated onto the hole transport layer 10 using a dynamic spin coating method at a coating speed of 5000 rpm for 30 seconds. After annealing at 70°C for 5 minutes, a photoresponsive molecular layer 20 with a thickness of 2 nm is formed.

[0095] Step 4) involves irradiating the photoresponsive molecular layer with 365nm ultraviolet light for 20 minutes. Before irradiation, the surface static water contact angle is 94.7°, indicating a hydrophobic state. After irradiation, the surface contact angle decreases to 39.8°, indicating a hydrophilic state.

[0096] Example 6

[0097] The preparation process of this embodiment is basically the same as that of Example 1. The main difference is that the concentration of Me-4PACZ solution in step 2) of this embodiment is 0.1 mg / mL.

[0098] Example 7

[0099] The preparation process of this embodiment is basically the same as that of Example 1. The main difference is that the concentration of Me-4PACZ solution in step 2) of this embodiment is 1 mg / mL.

[0100] Example 8

[0101] The preparation process of this embodiment is basically the same as that of embodiment 1. The main difference is that the thickness of the hole transport layer 10 in step 2) of this embodiment is 1 nm.

[0102] Comparative Example 1

[0103] The preparation process of this comparative example is basically the same as that of Example 1. The main difference is that steps 3) and 4) are not included in this comparative example, that is, the photoresponsive molecular layer 20 is not set on the hole transport layer 10.

[0104] Performance testing

[0105] (1) Contact angle test: The water contact angle of the photoresponse hole transport composite layer 1 in Examples 1-5 and the hole transport layer 10 in Comparative Example 1 was tested using a water contact angle tester. The results are shown in Table 1 below.

[0106] (2) The open-circuit voltage (Voc), current (Isc), fill factor (FF), and initial power conversion efficiency (PCE) of the perovskite solar cells were tested using a solar simulator and a Keithley 2400 source meter. The performance of the perovskite solar cells prepared in the examples and comparative examples was tested, and the results are shown in Table 1 below.

[0107] (3) PCE retention rate test: The aging conditions were 85℃ and 85% RH. The results are shown in Table 2 below.

[0108] Table 1

[0109]

[0110] As shown in Table 1, the water contact angles of Examples 1-5 are all smaller than the water contact angle (77.8°) of Comparative Example 1. Since the smaller the water contact angle, the stronger the interaction between the material surface and water, the better the spreading performance of the liquid on the material surface, i.e., the better the wettability. Therefore, compared with the single self-assembled monomolecular hole transport layer 10 in Comparative Example 1, the photoresponsive hole transport composite layer 1 provided in this application has better surface wettability.

[0111] Meanwhile, as can be seen from Table 1, the perovskite solar cells prepared in Examples 1-5 have better cell efficiencies compared to the cell efficiency (21.8%) in Comparative Example 1.

[0112] Table 2

[0113]

[0114] As shown in Table 2, after 14 days of rigorous aging, the performance retention rate of the example group was significantly higher than that of the comparative example. This indicates that the photoresponsive molecular layer 20 provided by this application provides protection for the hole transport layer 10, solving the technical problem of poor storage stability of prefabricated products.

[0115] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0116] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical concept of this application, and these modifications and improvements all fall within the protection scope of this application. Therefore, the protection scope of this application should be determined by the appended claims.

Claims

1. A photoresponsive hole transport composite layer, characterized in that, It includes a hole transport layer and a photoresponsive molecular layer disposed on the hole transport layer; The hole transport layer is a self-assembled monolayer, comprising self-assembled monomolecule materials; The photoresponsive molecular layer includes at least one of azobenzene derivatives and spiropyran derivatives.

2. The photoresponsive hole transport composite layer according to claim 1, characterized in that, The azobenzene derivatives include at least one of 4-carboxyazobenzene, 4-aminoazobenzene, N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo)aniline, 4,4'-dihydroxyazobenzene, and azobenzene-4,4'-dicarboxylic acid.

3. The photoresponsive hole transport composite layer according to claim 1, characterized in that, The spiropyran derivatives include at least one of 6-nitrospiropyran, 8-methoxyspiropyran, bromospiropyran, dinitrospiropyran, and carboxyspiropyran.

4. The photoresponsive hole transport composite layer according to claim 1, characterized in that, The hole transport layer has a thickness of 1 nm to 2 nm; and / or the photoresponsive molecular layer has a thickness of 1 nm to 2 nm.

5. The photoresponsive hole transport composite layer according to any one of claims 1-4, characterized in that, The self-assembled monomolecule materials include [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethoxy-9H-carbazole-9-yl)hexyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethyl-9H-carbazole-9-yl)propyl]phosphonic acid, [6-(3,6-dimethyl-9H-carbazole-9-yl)hexyl]phosphonic acid, [1-(3,6-dimethyl-9H-carbazole-9-yl)methyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [8-(3 [6-Dimethyl-9H-carbazole-9-yl)octyl]phosphate, [1-(9H-carbazole-9-yl)methyl]phosphate, (2-(9H-carbazole-9-yl)ethyl)phosphate, [3-(9H-carbazole-9-yl)propyl]phosphate, [4-(9H-carbazole-9-yl)butyl]phosphate, [6-(9H-carbazole-9-yl)hexyl]phosphate, [8-(9H-carbazole-9-yl)octyl]phosphate, [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl]phosphate, 2,3,4,5,6-pentafluorobenzyl phosphate, [2-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphate, [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphate, [6 ... [9-yl)butyl]phosphoric acid, [4-(diphenylamino)phenyl)ethyl]phosphoric acid, [4-(diphenylamino)phenyl)propyl]phosphoric acid, [4-(10H-phenthiazin-10-yl)butyl]phosphoric acid, [2-(7H-dibenzocarbazole-7-yl)ethyl]phosphoric acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, [3-(3,6-dibromo-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphoric acid, [6-(3,6-dibromo-9H-carbazole-9-yl)hexyl]phosphoric acid, [1-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphoric acid, [2 ...3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(10H-phenthiazin-10-yl)butyl]phosphoric acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(10H-phenthiazin-10-yl)butyl]phosphoric acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, [4-(7H-dibenzocarbazole- [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphate, [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphate, [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphate, [8-(3,6-di-tert-butyl-9H-carbazole-9-yl)octyl]phosphate, [1-(3,6-diphenyl-9H-carbazole-9-yl)methyl]phosphate, [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphate, [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphate, [4-(3,6-diphenyl ...phenyl-9H-carbazole-9-yl)ethyl]phosphate, [6-(3,6-diphenyl-9H-carbazole-9-yl)hexyl]phosphate, [6-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphate, [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphate, [4-(3,6-diAt least one of the following: [6-diphenyl-9H-carbazole-9-yl)hexyl]phosphoric acid, [8-(3,6-diphenyl-9H-carbazole-9-yl)octyl]phosphoric acid, [2-(10H-phenoxazine-10-yl)ethyl]phosphoric acid, [4-(3,7-dibromo-10H-phenthiazine-10-yl)butyl]phosphoric acid, and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphoric acid.

6. A method for preparing a photoresponsive hole transport composite layer as described in any one of claims 1-5, characterized in that, Includes the following steps: A hole transport layer was prepared by coating a self-assembled monomolecule material solution. At least one of azobenzene derivative solution, spiropyran derivative solution, and a mixed solution of azobenzene derivative and spiropyran derivative is coated on the surface of the hole transport layer to form a photoresponsive molecular layer on the hole transport layer.

7. The method for preparing the photoresponsive hole transport composite layer according to claim 6, characterized in that, At least one of the following conditions must be met: (1) The solute concentration of the self-assembled monomolecular material solution is 0.1 mg / mL to 1 mg / mL; (2) The solute concentration of the azobenzene derivative solution is 0.1 mM to 0.8 mM; (3) The solute concentration of the spiropyran derivative solution is 0.1 mM to 0.8 mM; (4) The solute concentration of the mixed solution of the azobenzene derivative and the spiropyran derivative is 0.2mM~0.8mM.

8. The method for preparing the photoresponsive hole transport composite layer according to claim 6, characterized in that, The solvents for the self-assembled monomolecule material solution, the azobenzene derivative solution, the spiropyran derivative solution, and the mixed solution of the azobenzene derivative and the spiropyran derivative are each independently selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

9. A perovskite solar cell, characterized in that, The photoresponsive hole transport composite layer includes the photoresponsive hole transport composite layer prepared by the preparation method of the photoresponsive hole transport composite layer according to any one of claims 1-5 or any one of claims 6-8.

10. An electrical device, characterized in that, Including the perovskite solar cell of claim 9.

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