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

Abstract

The invention discloses a modified hole transport layer and a preparation method thereof, a perovskite solar cell and a power utilization device, and belongs to the technical field of solar cells. The modified hole transport layer comprises a hole transport layer and a modified layer arranged on the surface of one side, far away from a substrate, of the hole transport layer; the material of the hole transport layer comprises a self-assembly single-layer material and an organic amine salt; and the material of the modified layer comprises organic amine salt. The organic amine salt is used as an additive to modify the self-assembled single-layer material to prepare the hole transport layer, and the organic amine salt is further used as a surface treating agent to modify the hole transport layer, so that the problems of distribution uniformity and surface wettability of the self-assembled single-layer material can be solved; the efficiency of the large-area perovskite assembly is effectively improved, and the large-area processing requirement is met.

Description

Technical Field

[0001] The present application relates to the technical field of solar cells, in particular to a modified hole transport layer and a preparation method thereof, a perovskite solar cell, and an electrical device. Background Art

[0002] Inverted perovskite solar cells have the advantage of high efficiency (>26%), and by fabricating tandem solar cells, the device efficiency can be further increased to more than 30%. Currently, most high-efficiency perovskite solar cells use self-assembled monolayer (SAM) materials as the hole transport layer. SAM small molecule materials have structural variability. Through structural design and processing method optimization, they can be paired with different perovskite materials to fabricate high-performance perovskite solar cells. Commonly used SAM materials such as 2PACz, Me-4PACz, 4PADCB, etc. have shown good device performance, but there are still problems such as uneven distribution of the SAM film on the substrate and poor surface wettability during the processing. There are various reasons for the uneven distribution of the SAM film on the substrate. For example, microcapsule structures are formed by self-aggregation of the SAM before coating it into a liquid film, or coffee rings are formed during the solvent evaporation process after the SAM is coated into a large-area liquid film. The poor surface wettability of the SAM is related to the packing density of the hydrophobic groups at the head of the SAM. The SAM with a hydrophobic head has poor contact with the perovskite.

[0003] To make the SAM film evenly distributed on the substrate, there are methods to use an additive solvent to destroy the microcapsules of the SAM in the solution, and there are also methods to use a co-adsorbed additive to complement the uncoated part of the SAM. To change the surface wettability, there are methods to fabricate the SAM on a NiOx film, and there are also methods to change the molecular design of the SAM and use a SAM with a hydrophilic group. However, the above improvement methods can only meet the usage requirements of small-area devices, have poor repeatability on large-area components, and do not effectively solve the problems of the processing uniformity and surface wettability of the SAM material on large-area components. Summary of the Invention

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

[0005] In the first aspect of the present application, a modified hole transport layer is provided, which includes a hole transport layer and a modified layer disposed on the surface of the hole transport layer away from the substrate;

[0006] The material of the hole transport layer includes a self-assembled monolayer material and an organic amine salt;

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

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

[0009] The anion of the organic amine salt includes at least one of hydrohalide, tetrafluoroborate, acetate, cyanide ion, and thiocyanate ion.

[0010] In some embodiments, the self-assembled monolayer material comprises [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl]phosphonic acid (Me-3PACz), [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Me-6PACz), [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl]phosphonic acid (Me-1PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl]phosphonic acid (Me-8PACz), [1-(9H-carbazol-9-yl)methyl]phosphonic acid (1PACz), (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz), [3-(9H-carbazol-9-yl)propyl]phosphonic acid (3PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [6-(9H-carbazol-9-yl)hexyl]phosphonic acid (6PACz), [8-(9H-carbazol-9-yl)octyl]phosphonic acid (8PACz), [4-(N,N-bis(4-methoxyphenylamino)phenyl)propyl]phosphonic acid (MeO-TPA-3PA), 2,3,4,5,6-pentafluorobenzylphosphonic acid (F5BPA), [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl]phosphonic acid (2PABCz), [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl]phosphonic acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphonic acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphonic acid (TPA-3PA), [4-(10H-phenothiazin-10-yl)butyl]phosphonic acid (4PAPT), [2-(7H-dibenzocarbazol-7-yl)ethyl]phosphonic acid (2PADCB), [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid (4PADCB), [3-(3,6-dibromo-9H-carbazol-9-yl)propyl]phosphonic acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazol-9-yl)butyl]phosphonic acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl]phosphonic acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl]phosphonic acid (tBu-1PACz), [2-(3,At least one of (6 - di - tert - butyl - 9H - carbazol - 9 - yl) ethyl] phosphoric acid (tBu - 2PACz), [3 - (3,6 - di - tert - butyl - 9H - carbazol - 9 - yl) propyl] phosphoric acid (tBu - 3PACz), [4 - (3,6 - di - tert - butyl - 9H - carbazol - 9 - yl) butyl] phosphoric acid (tBu - 4PACz), [6 - (3,6 - di - tert - butyl - 9H - carbazol - 9 - yl) hexyl] phosphoric acid (tBu - 6PACz), [8 - (3,6 - di - tert - butyl - 9H - carbazol - 9 - yl) octyl] phosphoric acid (tBu - 8PACz), [1 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) methyl] phosphoric acid (Ph - 1PACz), [2 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) ethyl] phosphoric acid (Ph - 2PACz), [3 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) propyl] phosphoric acid (Ph - 3PACz), [4 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) butyl] phosphoric acid (Ph - 4PACz), [6 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) hexyl] phosphoric acid (Ph - 6PACz), [8 - (3,6 - diphenyl - 9H - carbazol - 9 - yl) octyl] phosphoric acid (Ph - 8PACz), [2 - (10H - phenoxazine - 10 - yl) ethyl] phosphoric acid (2PAPXZ), [4 - (3,7 - dibromo - 10H - phenothiazine - 10 - yl) butyl] phosphoric acid (2Br - 4PAPT) and [4 - (3,7 - dibromo - 10H - phenoxazine - 10 - yl) butyl] phosphoric acid (2Br - 4PAPXZ).

[0011] In some embodiments, in the hole - transporting 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 - transporting layer is 1 nm - 5 nm;

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

[0014] In a second aspect of the present application, there is provided a method for preparing the modified hole - transporting layer described in the first aspect, comprising the following steps:

[0015] Coating a mixed solution of a self - assembled monolayer material and an organic amine salt on the surface of a substrate to form a hole - transporting layer;

[0016] Coating an organic amine salt solution on the surface of the hole - transporting layer to form a modified hole - transporting 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 - 2 mg / mL;

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

[0019] And / or, the solvents of the mixed solution of the self-assembled monolayer material and the organic amine salt 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 die coating, and inkjet printing.

[0021] In a third aspect of the present application, a perovskite solar cell is provided, including 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 which are stacked.

[0023] In a fourth aspect of the present application, an electrical device is provided, including the perovskite solar cell described in the third aspect.

[0024] Advantages of the present application:

[0025] 1. The modified hole transport layer of the present application is composed of a hole transport layer and a modified layer. The self-assembled monolayer material is modified by using an organic amine salt as an additive to prepare the hole transport layer, and further the hole transport layer is modified by using the organic amine salt as a surface treatment agent, which can solve the problems of the distribution uniformity and surface wettability of the self-assembled monolayer material, effectively improve the efficiency of large-area perovskite components, and meet the requirements of large-area processing.

[0026] 2. The preparation process of the modified hole transport layer of the present application is simple and suitable for batch production. Description of the Drawings

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present application. Throughout the drawings, the same reference numerals are used to represent the same components. 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 of Comparative Example 1;

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

[0031] Figure 4 The water contact angle of the modified hole transport layer of Comparative Example 3. Detailed implementation manners

[0032] To make the objectives, technical solutions and advantages of the present application clearer and the understanding of the disclosed content of the present application more thorough and comprehensive, the technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments of the present application and the corresponding drawings. The described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments.

[0033] The implementation of the present application will be described in detail below with reference to the drawings. This embodiment is implemented on the premise of the technical solution of the present application, and detailed implementation manners and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0034] Unless otherwise defined, all technical and scientific terms used in the present application have the same meanings as those commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application.

[0035] Terms

[0036] Unless otherwise stated or there are contradictions, the terms or phrases used in the present application have the following meanings:

[0037] In the present application, when it comes to "a plurality of", "a variety of", etc., unless otherwise specified, it means greater than 2 or equal to 2 in quantity. For example, "one or more", "at least one" means one or greater than or equal to two.

[0038] In the present application, "further", "especially", etc. are used to describe the purpose and indicate the difference in content, but should not be construed as a limitation on the protection scope of the present application.

[0039] In the present application, for the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, as well as an open technical solution including the listed features.

[0040] In this application, when it comes to numerical intervals (i.e., numerical ranges), unless otherwise specified, the distribution of the selectable numerical values within the numerical interval is considered continuous, and includes the two numerical endpoints of the numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all sub-ranges subsumed therein. The "numerical values" in the numerical interval can be any quantitative values, such as numbers, percentages, ratios, etc. The "numerical interval" is allowed to broadly include numerical interval types such as percentage intervals, ratio intervals, and ratio value intervals.

[0041] In this application, unless otherwise specified, the temperature parameter is allowed to be a constant temperature treatment, and is also allowed to vary within a certain temperature interval. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0042] The term "and / or" used in this application includes any and all combinations of one or more of the related listed items.

[0043] In this application, for the percentage content involved, unless otherwise specified, it refers to the mass percentage for solid-liquid mixtures and solid-solid mixtures, and the volume percentage for liquid-liquid mixtures.

[0044] In this application, for the percentage concentration involved, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added component in the system after adding the component.

[0045] In this application, for the temperature parameter, unless otherwise specified, it is allowed to be a constant temperature treatment, and is also allowed to be processed within a certain temperature interval. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0046] In the first aspect of this application, a modified hole transport layer is provided, which includes a hole transport layer and a modified layer provided on the surface of the hole transport layer away from the substrate;

[0047] The material of the hole transport layer includes 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, phenylpropylamine cation, 4-fluorobenzylamine cation, 2-(4-fluorophenyl)ethylamine cation, 3-(4-fluorophenyl)propylamine cation, 4-methylbenzylamine cation and 2-(4-methylphenyl)ethylamine cation;

[0050] The anion of the organic amine salt includes at least one of hydrohalide, tetrafluoroborate, acetate, cyanide ion and thiocyanate ion.

[0051] The organic amine salt has a structure with one hydrophilic side and one hydrophobic side, and has the function of a surfactant. When used as an additive in the SAM solution, it can effectively destroy the microcapsules formed by SAM in the solution, prevent SAM aggregation, and promote the coverage of SAM on the substrate; when used as a surface treatment agent for the SAM layer, its hydrophobic side can produce a conjugate interaction with the head of SAM, and the hydrophilic tail group can contact the perovskite solution to improve the wettability of the perovskite. In addition, the organic amine salt can interact with the halogen ions in the perovskite to promote perovskite crystallization and passivate perovskite defects. In this application, the organic amine salt is used as an additive to modify the self-assembled monolayer material to prepare a hole transport layer, and further the organic amine salt is used as a surface treatment agent to modify the hole transport layer, which can solve the problems of the distribution uniformity and surface wettability of the self-assembled monolayer material, and prevent the generation of a potential barrier caused by the direct contact between the conductive substrate and the perovskite, effectively improving the efficiency of large-area perovskite components and meeting the requirements of large-area processing.

[0052] In a specific example, the hydrohalide includes at least one of hydrofluoric acid root, hydrochloric acid root, hydrobromic acid root and hydroiodic acid root.

[0053] In a specific example, the self-assembled monolayer material includes [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl]phosphonic acid (Me-3PACz), [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Me-6PACz), [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl]phosphonic acid (Me-1PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl]phosphonic acid (Me-8PACz), [1-(9H-carbazol-9-yl)methyl]phosphonic acid (1PACz), (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz), [3-(9H-carbazol-9-yl)propyl]phosphonic acid (3PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [6-(9H-carbazol-9-yl)hexyl]phosphonic acid (6PACz), [8-(9H-carbazol-9-yl)octyl]phosphonic acid (8PACz), [4-(N,N-bis(4-methoxyphenylamino)phenyl)propyl]phosphonic acid (MeO-TPA-3PA), 2,3,4,5,6-pentafluorobenzylphosphonic acid (F5BPA), [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl]phosphonic acid (2PABCz), [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl]phosphonic acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphonic acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphonic acid (TPA-3PA), [4-(10H-phenothiazin-10-yl)butyl]phosphonic acid (4PAPT), [2-(7H-dibenzocarbazol-7-yl)ethyl]phosphonic acid (2PADCB), [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid (4PADCB), [3-(3,6-dibromo-9H-carbazol-9-yl)propyl]phosphonic acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazol-9-yl)butyl]phosphonic acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl]phosphonic acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl]phosphonic acid (tBu-1PACz), [2-(3,At least one of (6-di-tert-butyl-9H-carbazol-9-yl)ethyl]phosphonic acid (tBu-2PACz), [3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl]phosphonic acid (tBu-3PACz), [4-(3,6-di-tert-butyl-9H-carbazol-9-yl)butyl]phosphonic acid (tBu-4PACz), [6-(3,6-di-tert-butyl-9H-carbazol-9-yl)hexyl]phosphonic acid (tBu-6PACz), [8-(3,6-di-tert-butyl-9H-carbazol-9-yl)octyl]phosphonic acid (tBu-8PACz), [1-(3,6-diphenyl-9H-carbazol-9-yl)methyl]phosphonic acid (Ph-1PACz), [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Ph-2PACz), [3-(3,6-diphenyl-9H-carbazol-9-yl)propyl]phosphonic acid (Ph-3PACz), [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl]phosphonic acid (Ph-4PACz), [6-(3,6-diphenyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Ph-6PACz), [8-(3,6-diphenyl-9H-carbazol-9-yl)octyl]phosphonic acid (Ph-8PACz), [2-(10H-phenoxazine-10-yl)ethyl]phosphonic acid (2PAPXZ), [4-(3,7-dibromo-10H-phenothiazine-10-yl)butyl]phosphonic acid (2Br-4PAPT), and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphonic acid (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 1 nm - 5 nm, such as 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, etc.

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

[0057] In the second aspect of the present application, a method for preparing the modified hole transport layer described in the first aspect is provided, including the following steps:

[0058] A mixed solution of a self-assembled monolayer material and an organic amine salt is coated on the substrate surface to form a hole transport layer;

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

[0060] In this application, an organic amine salt is used as an additive to modify the self-assembled monolayer material to prepare a hole transport layer, and further an organic amine salt is used as a surface treatment agent to modify the hole transport layer, which can solve the problems of the distribution uniformity and surface wettability of the self-assembled monolayer material, effectively improve the efficiency of large-area perovskite components, and meet the large-area processing requirements. And the preparation process is simple and suitable for batch 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 - 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 - 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 a specific example, the solvents of the mixed solution of the self-assembled monolayer material and the organic amine salt 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 a specific example, the coating includes at least one of spin coating, blade coating, slot die coating, and inkjet printing.

[0065] In the third aspect of this application, a perovskite solar cell is provided, which includes 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 the present application can effectively improve the efficiency of large-area perovskite modules and meet the requirements 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 arranged in layers.

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

[0069] In a 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 independently a halogen anion, and 0 ≤ n ≤ 1.

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

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

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

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

[0075] In the fourth aspect of the present application, an electrical device is provided, including the perovskite solar cell described in the third aspect.

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

[0077] The following are specific examples.

[0078] Example 1

[0079] Preparation of the modified hole transport layer and the perovskite cell module:

[0080] The self-assembled monolayer material SAM is 4PADCB, and the organic amine salt is phenethylamine 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 phenethylamine hydrochloride with a concentration of 0.3 mg / mL (solution B); the solvents of solution A and solution B are both methanol; taking solution A as 100%, add one-thousandth of the volume of solution B to solution A to prepare a mixed solution of self-assembled monolayer material and organic amine salt;

[0083] 2) Perform P1 laser scribing on a large-sized FTO substrate (200 mm × 200 mm). After spin-coating the mixed solution of self-assembled monolayer material and organic amine salt on the treated FTO substrate (200 mm × 200 mm), perform annealing treatment; then spin-coat solution B to form a modified hole transport layer (the thicknesses of the hole transport layer and the modified layer are 3 nm and 5 nm respectively); the coating parameters of the mixed solution of self-assembled monolayer material and organic amine salt and solution B are the same, with a gap of 70 μm, a coating speed of 10 mm / s, and an injection speed of 10 μL / s.

[0084] 3) Sequentially prepare a perovskite layer (500 nm Cs 0.17 FA 0.83 PbI 2.25 Br 0.75 ), an electron transport layer (15 nm C 60 ), and a buffer layer (15 nm SnO2) on the modified hole transport layer, and perform P2 laser scribing; continue to prepare a back electrode (120 nm Cu) and then perform P3 laser scribing, and finally perform P4 laser edge cleaning to complete the preparation of the perovskite solar cell module.

[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 solution A and solution 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 Example 1.

[0087] Example 3

[0088] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is phenylpropylamine 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 Example 1.

[0089] Example 4

[0090] Except that the self-assembled monolayer material SAM is Me-4PACz, the organic amine salt is 4-fluorophenylmethylamine cyanide 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 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 on the FTO substrate to form the hole transport layer, and solution B is not used to modify the surface of the hole transport layer (neither using the organic amine salt as an additive nor as a surface treatment agent), the rest is the same as in Example 1.

[0095] Comparative Example 2

[0096] Except that solution B is not used to modify the surface of the hole transport layer (only using the organic amine salt as an additive, not using the organic amine salt as a surface treatment agent), the rest is the same as in Example 1.

[0097] Comparative Example 3

[0098] Except that solution A is directly coated on the FTO substrate to form the hole transport layer (not using the organic amine salt as an additive, only using the organic amine salt as a surface treatment agent), 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 Example

[0102] 1. Use a water contact angle tester to test 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. 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°). And 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, that is, the better the wettability. Therefore, Example 1 obtained significantly better surface wettability.

[0104] 2. The open circuit voltage (Voc), short circuit 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. The performance of the perovskite solar cell modules prepared in the examples and comparative examples was tested, and the results are shown in Table 1.

[0105] Table 1 Summary of the 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 Comparative Example 1 (14%) without modification.

[0108] By comparing Example 1 with Comparative Examples 1-3, it can be seen that when only using organic amine salts as additives or surface treatment agents for the self-assembled monolayer material SAM, the additive effect (2.5%) is inferior to the improvement degree of Example 1 compared to Comparative Example 1 (3.7%). It can be seen that using organic amine salts as additives and surface treatment agents for the self-assembled monolayer material SAM simultaneously can achieve synergistic effects and improve the modification effect.

[0109] By comparing Example 2 with Comparative Example 4, it can be seen that the specific type of organic amine salt cation has an obvious influence on its modification effect. Using 1-butyl-3-methylimidazolium cation has poor effects, and its effect is even inferior to that of unmodified Comparative Example 1.

[0110] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, 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, it should be considered as the scope described in this specification.

[0111] The above-described embodiments only represent several implementation manners of the present application. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to 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 one 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; The cation of the organic amine salt is selected from at least one of benzylamine cation, phenethylamine cation, phenylpropylamine cation, 4-fluorobenzylamine cation, 2-(4-fluorophenyl)ethylamine cation, 3-(4-fluorophenyl)propylamine cation, 4-methylbenzylamine cation and 2-(4-methylphenyl)ethylamine cation; The anion of the organic amine salt includes at least one of hydrohalide, tetrafluoroborate, acetate, cyanide ion and thiocyanate ion.

2. The modified hole transport layer according to claim 1, wherein The self-assembled monolayer material includes [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl]phosphonic acid, [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid, [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl]phosphonic acid, [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl]phosphonic acid, [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid, [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl]phosphonic acid, [1-(9H-carbazol-9-yl)methyl]phosphonic acid, (2-(9H-carbazol-9-yl)ethyl)phosphonic acid, [3-(9H-carbazol-9-yl)propyl]phosphonic acid, [4-(9H-carbazol-9-yl)butyl]phosphonic acid, [6-(9H-carbazol-9-yl)hexyl]phosphonic acid, [8-(9H-carbazol-9-yl)octyl]phosphonic acid, [4-(N,N-bis(4-methoxyphenylamino)phenyl)propyl]phosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl]phosphonic acid, [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl]phosphonic acid, [4-(diphenylamino)phenyl)ethyl]phosphonic acid, [4-(diphenylamino)phenyl)propyl]phosphonic acid, [4-(10H-phenothiazin-10-yl)butyl]phosphonic acid, [2-(7H-dibenzocarbazol-7-yl)ethyl]phosphonic acid, [4-(7H-dibenzocarbazol-7-yl)butyl]phosphonic acid, [3-(3,6-dibromo-9H-carbazol-9-yl)propyl]phosphonic acid, [4-(3,6-dibromo-9H-carbazol-9-yl)butyl]phosphonic acid, [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl]phosphonic acid, [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl]phosphonic acid, [2-(3,6-di-tert-butyl-9H-carbazol-9-yl)ethyl]phosphonic acid, [3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl]phosphonic acid, [4-(3,6-di-tert-butyl-9H-carbazol-9-yl)butyl]phosphonic acid, [6-(3,6-di-tert-butyl-9H-carbazol-9-yl)hexyl]phosphonic acid, [8-(3,6-di-tert-butyl-9H-carbazol-9-yl)octyl]phosphonic acid, [1-(3,6-diphenyl-9H-carbazol-9-yl)methyl]phosphonic acid, [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl]phosphonic acid, [3-(3,6-diphenyl-9H-carbazol-9-yl)propyl]phosphonic acid, [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl]phosphonic acid, [6-(3,At least one of [6-(3,6-diphenyl-9H-carbazol-9-yl)hexyl]phosphonic acid, [8-(3,6-diphenyl-9H-carbazol-9-yl)octyl]phosphonic acid, [2-(10H-phenoxazin-10-yl)ethyl]phosphonic acid, [4-(3,7-dibromo-10H-phenothiazin-10-yl)butyl]phosphonic acid, and [4-(3,7-dibromo-10H-phenoxazin-10-yl)butyl]phosphonic acid., 3. The modified hole transport layer according to claim 1 or 2, wherein In the hole transport layer, the mass ratio of the self-assembled monolayer material to the organic amine salt is 1000:0.5 - 50.

4. The modified hole transport layer according to claim 1 or 2, characterized in that The thickness of the hole transport layer is 1 nm - 5 nm; And / or, the thickness of the modified layer is 2 nm - 8 nm.

5. The preparation method of the modified hole transport layer according to any one of claims 1-4, characterized in that, It includes the following steps: Coat a mixed solution of a self-assembled monolayer material and an organic amine salt on the surface of the substrate to form a hole transport layer; Coat an organic amine salt solution on the surface of the hole transport layer to form a modified hole transport layer.

6. The preparation method of the modified hole transport layer according to claim 5, 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 - 2 mg / mL; And / or, the solute concentration of the organic amine salt solution is 0.05 mg / mL - 3 mg / mL; And / or, the solvents of the mixed solution of the self-assembled monolayer material and the organic amine salt 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.

7. The preparation method of the modified hole transport layer according to claim 5 or 6, characterized in that, The coating includes at least one of spin coating, blade coating, slot die coating and inkjet printing.

8. A perovskite solar cell, characterized in that, It includes the modified hole transport layer according to any one of claims 1 - 4 or the modified hole transport layer prepared by the preparation method according to any one of claims 5 - 7.

9. The perovskite solar cell according to claim 8, wherein, 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 which are stacked.

10. An electrical device, characterized in that, It includes the perovskite solar cell according to claim 9.

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