Modified hole transport layer and preparation method thereof, perovskite solar cell, and electrical device

Abstract

This application discloses a modified hole transport layer and its preparation method, a perovskite solar cell, and an electrical device, belonging to the field of solar cell technology. The modified hole transport layer of this application includes a hole transport layer and a modified layer disposed on the surface of the hole transport layer away from the substrate; the material of the hole transport layer includes a self-assembled monolayer material and an organic amine salt; the material of the modified layer includes an organic amine salt. This application uses organic amine salts as additives to modify the self-assembled monolayer material to prepare the hole transport layer, and further uses organic amine salts as surface treatment agents to modify the hole transport layer. This can solve the problems of uniform distribution and surface wettability of the self-assembled monolayer material, effectively improving the efficiency of large-area perovskite modules and meeting the needs of large-area processing.

Description

Technical Field

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

[0002] Inverted perovskite solar cells boast high efficiency (>26%), and by fabricating tandem solar cells, device efficiency can be further improved to over 30%. Currently, high-efficiency perovskite solar cells mostly employ self-assembled monolayer (SAM) materials as the hole transport layer. SAM small-molecule materials exhibit structural variability; through structural design and processing optimization, they can be combined with different perovskite materials to fabricate high-performance perovskite solar cells. Commonly used SAM materials such as 2PACz, Me-4PACz, and 4PADCB have demonstrated good device performance, but problems such as uneven distribution of the SAM film on the substrate and poor surface wettability still exist during processing. Uneven distribution of the SAM film on the substrate has various causes, such as self-aggregation of SAM before coating into a liquid film to form microcapsule structures, or the formation of coffee rings during solvent evaporation after large-area SAM coating into a liquid film. Poor surface wettability of SAM is related to the packing density of hydrophobic groups at the SAM head; hydrophobic SAM at the head has poor contact with the perovskite.

[0003] To ensure uniform distribution of SAM films on the substrate, methods include adding solvents to disrupt SAM microcapsules in solution, and using co-adsorbed additives to fill in uncovered areas. To modify surface wettability, methods include fabricating SAM on NiOx films, and altering the molecular design of SAM to use SAM with hydrophilic groups. However, these improved methods only meet the requirements of small-area devices, exhibiting poor repeatability in large-area components, and failing to effectively solve the problems of SAM material processing uniformity and surface wettability in large-area components. Summary of the Invention

[0004] Based on this, the main objective of this application is to provide a modified hole transport layer that has good distribution uniformity and surface wettability, which can meet the needs of large-area processing and effectively improve the efficiency of large-area perovskite modules.

[0005] In a first aspect, this application provides a modified hole transport layer, comprising a hole transport layer and a modified layer disposed on the side surface of the hole transport layer away from the substrate;

[0006] The hole transport layer is made of self-assembled monolayer materials and organic amine salts;

[0007] The material of the modified layer includes organic amine salts;

[0008] The cation of the organic amine salt is selected from at least one of benzylamine cation, phenethylamine cation, amphetamine cation, 4-fluorophenylmethylamine cation, 2-(4-fluorophenyl)ethylamine cation, 3-(4-fluorophenyl)propylamine cation, 4-methylbenzylamine cation, and 2-(4-methylphenyl)ethylamine cation;

[0009] The anions of the organic amine salt include at least one of hydrohalate, tetrafluoroborate, acetate, cyanide, and thiocyanate.

[0010] In some embodiments, the self-assembled monolayer material includes [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazole-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid (Me-2PACz), [3 ... [3,6-Dimethyl-9H-carbazole-9-yl)propyl]phosphate (Me-3PACz), [6-(3,6-dimethyl-9H-carbazole-9-yl)hexyl]phosphate (Me-6PACz), [1-(3,6-dimethyl-9H-carbazole-9-yl)methyl]phosphate (Me-1PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphate (Me-4PACz), [8-(3,6-dimethyl-9H-carbazole-9-yl)octyl]phosphate (Me-8PACz), [ 1-(9H-carbazole-9-yl)methyl]phosphoric acid (1PACz), (2-(9H-carbazole-9-yl)ethyl)phosphoric acid (2PACz), [3-(9H-carbazole-9-yl)propyl]phosphoric acid (3PACz), [4-(9H-carbazole-9-yl)butyl]phosphoric acid (4PACz), [6-(9H-carbazole-9-yl)hexyl]phosphoric acid (6PACz), [8-(9H-carbazole-9-yl)octyl]phosphoric acid (8PACz), [4-(N,N-di(4-methoxyphenylamino)phenyl) [Propyl]phosphoric acid (MeO-TPA-3PA), 2,3,4,5,6-pentafluorobenzylphosphoric acid (F5BPA), [2-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphoric acid (2PABCz), [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)butyl]phosphoric acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphoric acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphoric acid (TPA-3PA), [4- [10H-phenthiazin-10-yl)butyl]phosphoric acid (4PAPT), [2-(7H-dibenzocarbazole-7-yl)ethyl]phosphoric acid (2PADCB), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB), [3-(3,6-dibromo-9H-carbazole-9-yl)propyl]phosphoric acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphoric acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazole-9-yl)hexyl]phosphoric acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphoric acid (tBu-1PACz), [2 ...[6-Di-tert-butyl-9H-carbazole-9-yl)ethyl]phosphate (tBu-2PACz), [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphate (tBu-3PACz), [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphate (tBu-4PACz), [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphate (tBu-6PACz), [ 8-(3,6-di-tert-butyl-9H-carbazole-9-yl)octyl]phosphate (tBu-8PACz), [1-(3,6-diphenyl-9H-carbazole-9-yl)methyl]phosphate (Ph-1PACz), [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphate (Ph-2PACz), [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphate (Ph-3PACz), [4- At least one of the following: (3,6-diphenyl-9H-carbazole-9-yl)butyl]phosphate (Ph-4PACz), [6-(3,6-diphenyl-9H-carbazole-9-yl)hexyl]phosphate (Ph-6PACz), [8-(3,6-diphenyl-9H-carbazole-9-yl)octyl]phosphate (Ph-8PACz), [2-(10H-phenoxazine-10-yl)ethyl]phosphate (2PAPXZ), [4-(3,7-dibromo-10H-phenthiazine-10-yl)butyl]phosphate (2Br-4PAPT), and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphate (2Br-4PAPXZ).

[0011] In some embodiments, in the hole transport layer, the mass ratio of the self-assembled monolayer material to the organic amine salt is 1000:0.5-50; preferably 1000:1-20.

[0012] In some embodiments, the thickness of the hole transport layer is 1 nm-5 nm;

[0013] And / or, the thickness of the modified layer is 2nm-8nm.

[0014] A second aspect of this application provides a method for preparing the modified hole transport layer described in the first aspect, comprising the following steps:

[0015] A hole transport layer is formed by coating a self-assembled monolayer material and an organic amine salt solution onto the substrate surface.

[0016] An organic amine salt solution is coated on the surface of the hole transport layer to form a modified hole transport layer.

[0017] In some embodiments, the solute concentration of the mixed solution of the self-assembled monolayer material and the organic amine salt is 0.05 mg / mL to 2 mg / mL;

[0018] And / or, the solute concentration of the organic amine salt solution is 0.05 mg / mL to 3 mg / mL;

[0019] And / or, the solvent of the self-assembled monolayer material and the organic amine salt mixture solution and the solvent of the organic amine salt solution are each independently selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP).

[0020] In some embodiments, the coating includes at least one of spin coating, blade coating, slot coating, and inkjet printing.

[0021] A third aspect of this application provides a perovskite solar cell, comprising the modified hole transport layer described in the first aspect or the modified hole transport layer prepared by the preparation method described in the second aspect.

[0022] In some embodiments, the perovskite solar cell includes a transparent conductive substrate, a modified hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, and a back electrode stacked together.

[0023] A fourth aspect of this application provides an electrical device comprising the perovskite solar cell described in the third aspect.

[0024] The beneficial effects of this application are:

[0025] 1. The modified hole transport layer of this application consists of a hole transport layer and a modified layer. Organic amine salts are used as additives to modify the self-assembled monolayer material to prepare the hole transport layer. Furthermore, organic amine salts are used as surface treatment agents to modify the hole transport layer. This can solve the problems of uniform distribution and surface wettability of the self-assembled monolayer material, effectively improve the efficiency of large-area perovskite modules, and meet the needs of large-area processing.

[0026] 2. The preparation process of the modified hole transport layer in this application is simple and suitable for mass production. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. The drawings are only for illustrating preferred embodiments and are not intended to limit this application. Throughout the drawings, the same reference numerals denote the same parts. In the drawings:

[0028] Figure 1 The water contact angle of the modified hole transport layer in Example 1;

[0029] Figure 2The water contact angle of the hole transport layer in Comparative Example 1;

[0030] Figure 3 The water contact angle of the hole transport layer in Comparative Example 2;

[0031] Figure 4 The water contact angle is that of the modified hole transport layer in Comparative Example 3. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this application clearer and to provide a more thorough and comprehensive understanding of the disclosure of this application, the technical solutions of this application will be clearly and completely described below in conjunction with specific embodiments and corresponding drawings. The described embodiments are only some embodiments of this application, and not all embodiments.

[0033] The implementation of this application will be described in detail below with reference to the accompanying drawings. This embodiment is implemented based on the technical solution of this application, and provides detailed implementation methods and specific operation processes, but the protection scope of this application is not limited to the following embodiments.

[0034] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in this application and in its specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0035] the term

[0036] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0037] In this application, the terms "multiple" or "various" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" or "at least one" means one or more of two.

[0038] In this application, terms such as "further" and "especially" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0039] 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.

[0040] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0041] In this application, unless otherwise specified, the temperature parameters are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control. Fluctuations are permitted within ranges such as ±5℃, ±4℃, ±3℃, ±2℃, and ±1℃.

[0042] The term “and / or” as used in this application includes any and all combinations of one or more of the associated listed items.

[0043] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0044] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0045] In this application, unless otherwise specified, the temperature parameter can be either constant temperature treatment or treatment within a certain temperature range. The constant temperature treatment allows temperature fluctuations within the precision range controlled by the instrument.

[0046] In a first aspect, this application provides a modified hole transport layer, comprising a hole transport layer and a modified layer disposed on the side surface of the hole transport layer away from the substrate;

[0047] The hole transport layer is made of self-assembled monolayer materials and organic amine salts;

[0048] The material of the modified layer includes organic amine salts;

[0049] The cation of the organic amine salt is selected from at least one of benzylamine cation, phenethylamine cation, amphetamine cation, 4-fluorophenylmethylamine cation, 2-(4-fluorophenyl)ethylamine cation, 3-(4-fluorophenyl)propylamine cation, 4-methylbenzylamine cation, and 2-(4-methylphenyl)ethylamine cation;

[0050] The anions of the organic amine salt include at least one of hydrohalate, tetrafluoroborate, acetate, cyanide, and thiocyanate.

[0051] Organic amine salts possess a structure with one hydrophilic side and the other hydrophobic side, exhibiting surfactant functions. When used as additives in SAM solutions, they effectively disrupt microcapsules formed by SAM in solution, preventing SAM aggregation and promoting SAM coverage of the substrate. When used as surface treatment agents for SAM layers, their hydrophobic side can generate conjugated interactions with the SAM head, while the hydrophilic tail groups can contact the perovskite solution, improving the wettability of the perovskite. Furthermore, organic amine salts can interact with halide ions in the perovskite, promoting perovskite crystallization and passivating perovskite defects. This application uses organic amine salts as additives to modify self-assembled monolayer materials to prepare hole transport layers, and further uses organic amine salts as surface treatment agents to modify the hole transport layers. This addresses the issues of uniform distribution and surface wettability of self-assembled monolayer materials, prevents direct contact between the conductive substrate and perovskite leading to potential barriers, effectively improves the efficiency of large-area perovskite modules, and meets the needs of large-area processing.

[0052] In one specific example, the hydrohalate ion includes at least one of hydrofluoric acid ion, hydrochloric acid ion, hydrobromic acid ion, and hydroiodate ion.

[0053] In a specific example, the self-assembled monolayer material includes [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazole-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid (Me-2PACz), [3-(3... [6-(3,6-dimethyl-9H-carbazole-9-yl)propyl]phosphate (Me-3PACz), [6-(3,6-dimethyl-9H-carbazole-9-yl)hexyl]phosphate (Me-6PACz), [1-(3,6-dimethyl-9H-carbazole-9-yl)methyl]phosphate (Me-1PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphate (Me-4PACz), [8-(3,6-dimethyl-9H-carbazole-9-yl)octyl]phosphate (Me-8PACz) [1-(9H-carbazole-9-yl)methyl]phosphate (1PACz), (2-(9H-carbazole-9-yl)ethyl)phosphate (2PACz), [3-(9H-carbazole-9-yl)propyl]phosphate (3PACz), [4-(9H-carbazole-9-yl)butyl]phosphate (4PACz), [6-(9H-carbazole-9-yl)hexyl]phosphate (6PACz), [8-(9H-carbazole-9-yl)octyl]phosphate (8PACz), [4-(N,N-di(4-methoxyphenylamino)phenyl]phosphate [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)ethyl]phosphoric acid (MeO-TPA-3PA), [4-(9H-9'-phenyl-3,3'-dicarbazole-9-yl)butyl]phosphoric acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphoric acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphoric acid (TPA-3PA), [4- [10H-phenthiazin-10-yl)butyl]phosphoric acid (4PAPT), [2-(7H-dibenzocarbazole-7-yl)ethyl]phosphoric acid (2PADCB), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB), [3-(3,6-dibromo-9H-carbazole-9-yl)propyl]phosphoric acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphoric acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazole-9-yl)hexyl]phosphoric acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphoric acid (tBu-1PACz), [2-(3,[6-Di-tert-butyl-9H-carbazole-9-yl)ethyl]phosphate (tBu-2PACz), [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphate (tBu-3PACz), [4-(3,6-di-tert-butyl-9H-carbazole-9-yl)butyl]phosphate (tBu-4PACz), [6-(3,6-di-tert-butyl-9H-carbazole-9-yl)hexyl]phosphate (tBu-6PACz), [ 8-(3,6-di-tert-butyl-9H-carbazole-9-yl)octyl]phosphate (tBu-8PACz), [1-(3,6-diphenyl-9H-carbazole-9-yl)methyl]phosphate (Ph-1PACz), [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphate (Ph-2PACz), [3-(3,6-diphenyl-9H-carbazole-9-yl)propyl]phosphate (Ph-3PACz), [4- At least one of the following: (3,6-diphenyl-9H-carbazole-9-yl)butyl]phosphate (Ph-4PACz), [6-(3,6-diphenyl-9H-carbazole-9-yl)hexyl]phosphate (Ph-6PACz), [8-(3,6-diphenyl-9H-carbazole-9-yl)octyl]phosphate (Ph-8PACz), [2-(10H-phenoxazine-10-yl)ethyl]phosphate (2PAPXZ), [4-(3,7-dibromo-10H-phenthiazine-10-yl)butyl]phosphate (2Br-4PAPT), and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphate (2Br-4PAPXZ).

[0054] In a specific example, in the hole transport layer, the mass ratio of the self-assembled monolayer material to the organic amine salt is 1000:0.5-50; preferably 1000:1-20, and specifically can be 1000:0.5, 1000:1, 1000:2, 1000:3, 1000:4, 1000:5, 1000:10, 1000:15, 1000:20, 1000:30, 1000:40, 1000:50, etc.

[0055] In a specific example, the thickness of the hole transport layer is 1nm-5nm, such as 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, 5nm, etc.

[0056] In a specific example, the thickness of the modified layer is 2nm-8nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc.

[0057] A second aspect of this application provides a method for preparing the modified hole transport layer described in the first aspect, comprising the following steps:

[0058] A hole transport layer is formed by coating a self-assembled monolayer material and an organic amine salt solution onto the substrate surface.

[0059] An organic amine salt solution is coated on the surface of the hole transport layer to form a modified hole transport layer.

[0060] This application uses organic amine salts as additives to modify self-assembled monolayer materials to prepare hole transport layers, and further uses organic amine salts as surface treatment agents to modify the hole transport layers. This solves the problems of uniform distribution and surface wettability of self-assembled monolayer materials, effectively improving the efficiency of large-area perovskite modules and meeting the needs of large-area processing. Furthermore, the preparation process is simple and suitable for mass production.

[0061] In a specific example, the solute concentration of the mixed solution of the self-assembled monolayer material and the organic amine salt is 0.05 mg / mL to 2 mg / mL; for example, 0.05 mg / mL, 0.1 mg / mL, 0.2 mg / mL, 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, etc.

[0062] In a specific example, the solute concentration of the organic amine salt solution is 0.05 mg / mL to 3 mg / mL; for example, 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 0.9 mg / mL, 1 mg / mL, 1.2 mg / mL, 1.4 mg / mL, 1.6 mg / mL, 1.8 mg / mL, 2.0 mg / mL, 2.5 mg / mL, 3 mg / mL, etc.

[0063] In one specific example, the solvent of the self-assembled monolayer material and the organic amine salt mixture solution and the solvent of the organic amine salt solution are each independently selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).

[0064] In one specific example, the coating includes at least one of spin coating, blade coating, slot coating, and inkjet printing.

[0065] A third aspect of this application provides a perovskite solar cell, comprising the modified hole transport layer described in the first aspect or the modified hole transport layer prepared by the preparation method described in the second aspect.

[0066] The modified hole transport layer of this application can effectively improve the efficiency of large-area perovskite modules and meet the needs of large-area processing.

[0067] In a specific example, the perovskite solar cell includes a transparent conductive substrate, a modified hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, and a back electrode stacked together.

[0068] In a specific example, the substrate is an FTO substrate.

[0069] In one specific example, the material of the perovskite layer includes perovskite.

[0070] In a specific example, the general formula of the perovskite is AB(X n Y 1-n )3, where A is a monovalent cation, B is a divalent metal ion, X and Y are each an halogen anion independently, and 0≤n≤1.

[0071] In one specific example, the electron transport layer is an n-type semiconductor.

[0072] In one specific example, the material of the electron transport layer includes C60 and / or PCBM.

[0073] In one specific example, the material of the buffer layer includes ALD SnO2 and / or BCP.

[0074] In one specific example, the electrode material includes at least one of ITO, IZO, and Cu.

[0075] A fourth aspect of this application provides an electrical device comprising the perovskite solar cell described in the third aspect.

[0076] Unless otherwise specified, the raw materials used in the following experiments can be purchased from the market.

[0077] The following are specific examples.

[0078] Example 1

[0079] Fabrication of modified hole transport layer and perovskite solar cell module:

[0080] The self-assembled monolayer material SAM is 4PADCB, and the organic amine salt is phenylethylamine hydrochloride.

[0081] The specific steps are as follows:

[0082] 1) Prepare a solution of 4PADCB with a concentration of 0.3 mg / mL (solution A) and a solution of phenylethylamine hydrochloride with a concentration of 0.3 mg / mL (solution B); the solvent for both solution A and solution B is methanol; taking solution A as 100%, add 0.1% volume of solution B to solution A to prepare a mixed solution of self-assembled monolayer material and organic amine salt.

[0083] 2) A large-size FTO substrate (200mm×200mm) is scribed with P1 laser. A mixture of self-assembled monolayer material and organic amine salt is slit-coated onto the treated FTO substrate (200mm×200mm) and then annealed. Solution B is then coated to form a modified hole transport layer (the thickness of the hole transport layer and the modified layer are 3nm and 5nm, respectively). The coating parameters of the mixture of self-assembled monolayer material and organic amine salt and solution B are the same: gap is 70μm, coating speed is 10mm / s, and injection speed is 10μL / s.

[0084] 3) A perovskite layer (500 nm Cs) was sequentially prepared on the modified hole transport layer. 0.17 FA 0.83 PbI 2.25 Br 0.75 ), electron transport layer (15nm C) 60 The perovskite solar cell module is fabricated by first preparing a buffer layer (15nm SnO2) and then performing P2 laser scribing; then proceeding to prepare the back electrode (120nm Cu) and performing P3 laser scribing, and finally performing P4 laser edge cleaning.

[0085] Example 2

[0086] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is benzylamine tetrafluoroborate, the concentrations of solutions A and B are both 0.1 mg / mL, and the thicknesses of the hole transport layer and the modified layer are 1 nm and 2 nm, respectively, the rest is the same as in Example 1.

[0087] Example 3

[0088] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is phenylalanine acetate, the concentration of solution A is 0.1 mg / mL, the concentration of solution B is 2 mg / mL, and the thicknesses of the hole transport layer and the modified layer are 1 nm and 8 nm, respectively, the rest is the same as in Example 1.

[0089] Example 4

[0090] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is 4-fluorophenylmethylamine cyano salt, the concentration of solution A is 0.8 mg / mL, the concentration of solution B is 2 mg / mL, and the thicknesses of the hole transport layer and the modified layer are 4 nm and 8 nm, respectively, the rest is the same as in Example 1.

[0091] Example 5

[0092] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is 4-methylbenzylamine thiocyanate, the concentration of solution A is 2 mg / mL, the concentration of solution B is 0.1 mg / mL, and the thicknesses of the hole transport layer and the modified layer are 5 nm and 2 nm, respectively, the rest is the same as in Example 1.

[0093] Comparative Example 1

[0094] Except that solution A is directly coated onto the FTO substrate to form a hole transport layer, and solution B is not used to modify the surface of the hole transport layer (neither organic amine salt is used as an additive nor as a surface treatment agent), the rest is the same as in Example 1.

[0095] Comparative Example 2

[0096] Except for not using solution B to modify the hole transport layer surface (only organic amine salts are used as additives, not as surface treatment agents), the rest is the same as in Example 1.

[0097] Comparative Example 3

[0098] Except for directly coating solution A onto the FTO substrate to form a hole transport layer (without using organic amine salts as additives, only using organic amine salts as surface treatment agents), the rest is the same as in Example 1.

[0099] Comparative Example 4

[0100] Except that the organic amine salt is 1-butyl-3-methylimidazolium tetrafluoroborate (i.e., the cation is 1-butyl-3-methylimidazolium cation), the rest is the same as in Example 2.

[0101] Test Case

[0102] 1. The water contact angles of the modified hole transport layer of Example 1, the hole transport layers of Comparative Examples 1-2, and the modified hole transport layer of Comparative Example 3 were tested using a water contact angle tester. The results are shown in the appendix. Figures 1-4 .

[0103] It can be seen that the water contact angle of Example 1 is 68.2°, which is smaller than that of Comparative Examples 1-3 (73.3°-92.9°). The smaller the water contact angle, the stronger the interaction between the material surface and water, and the better the spreading performance of the liquid on the material surface, i.e., the better the wettability. Therefore, Example 1 achieved significantly better surface wettability.

[0104] 2. The open-circuit voltage (Voc), current (Isc), fill factor (FF), and initial power conversion efficiency (PCE) of the perovskite solar cell modules were tested using a solar simulator and a Keithley 2400 source meter. Performance tests were conducted on the perovskite solar cell modules prepared in the examples and comparative examples; the results are shown in Table 1.

[0105] Table 1 Summary of Performance of Examples and Comparative Examples

[0106]

[0107] As can be seen from Table 1, the large-area perovskite solar cell modules prepared in Examples 1-5 have good cell efficiency (>16.5%), which is significantly better than that of the unmodified Comparative Example 1 (14%).

[0108] Comparing Example 1 and Comparative Examples 1-3, it can be seen that the sum of the improvement (2.5%) of Example 1 compared to Comparative Example 1 is worse than that of Example 1 compared to Comparative Example 1 (3.7%) when only organic amine salts are used as additives or surface treatment agents for self-assembled monolayer materials (SAM). This shows that using organic amine salts as both additives and surface treatment agents for self-assembled monolayer materials (SAM) can have a synergistic effect and improve the modification effect.

[0109] Comparing Example 2 and Comparative Example 4, it can be seen that the specific type of organic amine salt cation has a significant impact on its modification effect. The effect of using 1-butyl-3-methylimidazolium cation is not good, and its effect is even worse than that of the unmodified Comparative Example 1.

[0110] 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.

[0111] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art could make various modifications and improvements without departing from the spirit of the present application, all of which fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. A modified hole transport layer, characterized in that, It includes a hole transport layer and a modified layer disposed on the side of the hole transport layer away from the substrate; The hole transport layer is made of a self-assembled monolayer material and an organic amine salt; The material of the modified layer is an organic amine salt; The cation of the organic amine salt is selected from at least one of benzylamine cation, phenethylamine cation, amphetamine cation, 4-fluorophenylmethylamine cation, 2-(4-fluorophenyl)ethylamine cation, 3-(4-fluorophenyl)propylamine cation, 4-methylbenzylamine cation, and 2-(4-methylphenyl)ethylamine cation; The anions of the organic amine salt include at least one of hydrohalate, tetrafluoroborate, acetate, cyanide, and thiocyanate. The mass ratio of the self-assembled monolayer material to the organic amine salt is 1000:0.5-50; The thickness of the hole transport layer is 1nm-5nm; The thickness of the modified layer is 2nm-8nm.

2. The modified hole transport layer as described in claim 1, characterized in that, The self-assembled monolayer material includes [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)butyl]phosphonic acid, and [8-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid. [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 ... [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)methyl]phosphoric acid, [2-(3,6-di-tert-butyl-9H-carbazole-9-yl)methyl]phosphoric acid, [3-(3,6-di-tert-butyl-9H-carbazole-9-yl)propyl]phosphoric acid, [4-(3,6-dibromo-9H-carbazole-9-yl)methyl]phosphoric acid, [4-(3,6-di-tert-butyl ... [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.

3. The method for preparing the modified hole transport layer according to any one of claims 1-2, characterized in that, Includes the following steps: A hole transport layer is formed by coating a self-assembled monolayer material and an organic amine salt solution onto the substrate surface. An organic amine salt solution is coated on the surface of the hole transport layer to form a modified hole transport layer.

4. The method for preparing the modified hole transport layer as described in claim 3, characterized in that, The solute concentration of the mixed solution of the self-assembled monolayer material and the organic amine salt is 0.05 mg / mL to 2 mg / mL; And / or, the solute concentration of the organic amine salt solution is 0.05 mg / mL to 3 mg / mL; And / or, the solvent of the self-assembled monolayer material and the organic amine salt mixture solution and the solvent of the organic amine salt solution are each independently selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-isobutanol, N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.

5. The method for preparing the modified hole transport layer as described in claim 3 or 4, characterized in that, The coating includes at least one of spin coating, blade coating, slot coating, and inkjet printing.

6. A perovskite solar cell, characterized in that, It includes the modified hole transport layer according to any one of claims 1-2 or the modified hole transport layer prepared by the preparation method according to any one of claims 3-5.

7. The perovskite solar cell according to claim 6, characterized in that, The perovskite solar cell comprises a transparent conductive substrate, a modified hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, and a back electrode stacked together.

8. An electrical device, characterized in that, Including the perovskite solar cell of claim 7.

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