Self-polymerization material and preparation method thereof, hole transport material, hole transport layer and perovskite solar cell

Abstract

The application discloses a kind of self-polymerization material and its preparation method, hole transport material, hole transport layer and perovskite solar cell, it is related to solar cell technical field.The structural formula of self-polymerization material of the application is as follows: Wherein, Y is N, S, O, single bond or non-existent;R is or, wherein, al is C1~C6 alkylene, R1 And R2 Each independently is C1~C6 alkyl ester radical, C1~C6 alkyl acyl, C1~C6 alkyl sulfonyl, C1~C6 alkyl containing at least one halogen group, fluorine radical, amino, hydroxyl, cyano, amidine radical any one of them.The self-polymerization material described in the application solves the technical problem that the long-term stability of perovskite solar cell in the prior art is poor.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and more specifically, to a self-polymerizing material and its preparation method, a hole transport material, a hole transport layer, and a perovskite solar cell. Background Technology

[0002] Metal halide perovskite solar cells (PSCs) possess high power conversion efficiency and low manufacturing cost. Currently, phosphonic acid-based self-assembled monolayers (PA-SAMs) are widely used as hole transport materials due to their excellent performance. These monolayer materials can not only be anchored on transparent conductive oxide (TCO) substrates through phosphonic acid groups, but also precisely control the interfacial energy level matching, significantly improving hole extraction and transport efficiency. Simultaneously, PA-SAMs can effectively passivate surface defects in perovskite films and suppress carrier recombination, thereby enhancing the stability of perovskite solar cells.

[0003] In fabricating the hole transport layer (HTL) of perovskite solar cells, a solution-based method is typically used. PA-SAMs are prepared on a TCO substrate through spin coating, coating, or spraying. Annealing then allows the hydroxyl groups on the phosphonic acid groups to dehydrate and condense with the hydroxyl groups on the TCO surface, forming covalent bonds and anchoring the PA-SAMs material to the TCO substrate. However, this method results in a certain amount of unanchored phosphonic acid groups facing the upper perovskite layer. Although phosphonic acid groups have a good passivation effect on perovskite, during long-term use, these acidic groups readily react with the perovskite, leading to iodide oxidation, cation decomposition, and lead reduction. These reactions are significantly accelerated under high temperature and ultraviolet light, thus affecting the long-term stability of perovskite solar cells.

[0004] However, hole transport materials with non-phosphonic acid groups are difficult to form a stable thin film layer on TCO substrates due to the lack of anchoring groups, and thus cannot effectively improve the long-term stability of perovskite solar cells. Summary of the Invention

[0005] The main objective of this application is to provide a self-polymerizing material and its preparation method, a hole transport material, a hole transport layer, and a perovskite solar cell, so as to solve the technical problem of poor long-term stability of perovskite solar cells in the prior art.

[0006] To achieve the above objectives, according to a first aspect of this application, a self-polymerizing material is provided, the structural formula of which is shown in Formula I:

[0007] Formula I;

[0008] Where Y represents N, S, O, a single bond, or is absent; R represents... or In this application, al is a C1-C6 alkylene group, and R1 and R2 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halogroup, fluorine, amino, hydroxy, cyano, and amidine groups; This is the connection site.

[0009] According to a second aspect of this application, a method for preparing a self-polymerizing material is provided, comprising the following steps:

[0010] S1, dissolve the first compound in the first solvent, add the first alkaline agent, and obtain the first mixture;

[0011] S2, the second compound is mixed with the first mixture to undergo the first reaction, yielding the first intermediate product;

[0012] S3, the first intermediate product is mixed with palladium acetate, triphenylphosphine, a second alkali agent, vinyltrimethylsilane, and a second solvent, and a second reaction is carried out under a protective atmosphere to obtain a second intermediate product; the second intermediate product undergoes a third reaction with an acid agent to obtain the self-polymerizing material;

[0013] The structural formula of the first compound is shown in Formula II: Formula II, wherein X1 is at least one of Br, Cl, and F; Y' is N, S, O, a single bond, or does not exist;

[0014] The structural formula of the second compound is shown in Formula III or Formula IV: Formula III Formula IV; wherein, al' is a C1-C6 alkylene group, X2 and X3 are each independently at least one of Br, Cl, and F; R3 and R4 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halogroup, fluorine, amino, hydroxyl, cyano, amidine, and amidine tert-butyl carbonate;

[0015] The structural formula of the first intermediate product is shown in formula V: Equation V; R' is or In this case, R1' and R3 are the same; R2' and R4 are the same.

[0016] According to a second aspect of this application, a hole transport material is provided, which is a polymer whose structural units are derived from the self-polymerizing material of the first aspect of this application.

[0017] According to a third aspect of this application, a hole transport layer is provided, which is formed by self-polymerization of a self-polymerizing material; the self-polymerizing material is the self-polymerizing material of the first aspect of this application or the self-polymerizing material prepared by the preparation method of the second aspect of this application.

[0018] According to a fourth aspect of this application, a perovskite solar cell is provided, which includes a hole transport layer according to a third aspect of this application.

[0019] By applying the technical solution of this application, the structure of the self-polymerizing material is designed to have a double-ended carboxyl structure, which helps to form a dense hole transport layer in situ on the TCO substrate surface, thereby improving the stability of the hole transport layer. In addition, by controlling the types of groups and bonds in the self-polymerizing material, the passivation effect of the self-polymerizing material on the perovskite layer can be improved, thereby increasing the photoelectric conversion efficiency. Furthermore, since there are no acidic groups, side reactions between the hole transport layer and the perovskite layer under the influence of light, heat, etc., can be avoided, which helps to improve the long-term stability of the perovskite solar cell made from the above-mentioned self-polymerizing material. Attached Figure Description

[0020] Figure 1 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 1 of this application;

[0021] Figure 2 This is a SEM image of the cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 2 of this application;

[0022] Figure 3 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 3 of this application;

[0023] Figure 4 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 4 of this application;

[0024] Figure 5 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 5 of this application;

[0025] Figure 6 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 6 of this application;

[0026] Figure 7 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 7 of this application;

[0027] Figure 8This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 8 of this application;

[0028] Figure 9 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 9 of this application;

[0029] Figure 10 This is a SEM image of a cross-section of the perovskite solar cell prepared using the self-polymerizing material in Example 10 of this application;

[0030] Figure 11 A cross-sectional SEM image of a perovskite solar cell prepared using the materials in Comparative Example 1 of this application;

[0031] Figure 12 The stability test results are shown for the crystalline silicon-perovskite tandem solar cell devices prepared using the materials in Example 1 and Comparative Example 1 of this application. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0033] As described in the background section of this application, existing perovskite solar cells suffer from poor long-term stability. To address this issue, in a typical embodiment of this application, a self-polymerizing material is provided, with the structural formula shown in Formula I:

[0034] Formula I;

[0035] Where Y represents N, S, O, a single bond, or is absent; R represents... or In this application, al is a C1-C6 alkylene group, and R1 and R2 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halide group, fluorine, amino, hydroxyl, cyano, and amidine groups. Represents the connection site.

[0036] In the above embodiments of this application, by designing the structure of the self-polymerizing material to have a double-ended carboxyl structure, it is helpful to form a dense hole transport layer in situ on the TCO substrate surface, thereby improving the stability of the hole transport layer. In addition, by controlling the types of groups and bonds in the self-polymerizing material, it is helpful to improve the passivation effect of the self-polymerizing material on the perovskite layer and improve the photoelectric conversion efficiency. Furthermore, since there are no acidic groups, side reactions between the hole transport layer and the perovskite layer under the action of light, heat, etc., can be avoided, thereby helping to improve the long-term stability of the perovskite solar cell made of the above-mentioned self-polymerizing material.

[0037] In some embodiments, R1 and R2 are each independently any one of C1-C3 alkyl ester, C1-C3 alkyl acyl, C1-C3 alkyl sulfonyl, C1-C3 alkyl containing at least one halogenated group, fluorine, amino, hydroxy, cyano, and amidine.

[0038] In the above embodiments of this application, by selecting the types of characteristic groups R1 and R2, it is helpful to improve the passivation effect of the self-polymerized material on the perovskite layer, and to avoid the negative impact of acidic groups such as phosphonic acid groups on the stability of perovskite solar cells; thus, it helps to further improve the long-term stability of perovskite solar cells.

[0039] In some embodiments, R1 and R2 are each independently any one of acetyl, methanesulfonyl, amido, cyano, amino, trifluoromethyl, fluoro, and ethyl ester; and / or, al is a C2-C4 alkyl group.

[0040] In the embodiments described above in this application, the aforementioned characteristic groups facilitate the interaction of Pb in the perovskite layer. 2+ By forming coordination bonds, under the above-mentioned structural system with carbazole, thiophene, phenoxazine, and triphenylamine as the parent nucleus, the passivation effect of self-polymerized materials on the perovskite layer can be effectively improved, thereby enhancing the stability and photoelectric conversion efficiency of perovskite solar cells.

[0041] In some implementations, Y is S, a single bond, or does not exist.

[0042] In the above embodiments of this application, the self-polymerizing material of the parent core can effectively passivate the interface defects of the perovskite layer, suppress non-radiative recombination, and its specific conjugated structure can promote hole extraction and transport, thereby helping to improve the stability and photoelectric conversion efficiency of the perovskite solar cell and enhance its overall performance.

[0043] In some implementations, R is .

[0044] In the above embodiments of this application, selecting R as a characteristic group of the above structure helps to improve the film-forming properties of the self-polymerized material, improve the hydrophobicity and hole mobility of the hole transport layer formed by the self-polymerized material, and thus help to improve the long-term stability and photoelectric conversion efficiency of the perovskite solar cell.

[0045] In some embodiments, R2 is an amido, amino, or cyano group.

[0046] In the above embodiments of this application, by screening the types of R2, it is helpful to balance the charge transport performance, hole mobility, and passivation effect of perovskite defects, thereby improving the overall performance of perovskite solar cells and broadening their application range.

[0047] In some embodiments, the self-polymerizing material is selected from at least one of the compounds shown in Formulas 1 to 18:

[0048] Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17 Formula 18.

[0049] In the embodiments described above, the self-polymerizing materials can all form a dense polymer film layer in situ on the TCO substrate surface, i.e., form a stable hole transport layer, which helps improve the long-term stability of perovskite solar cells. In addition, the self-polymerizing materials have a good passivating effect on the perovskite layer, thereby helping to reduce non-radiative recombination and improve the stability of the perovskite layer, thus contributing to improved photoelectric conversion performance and stability of perovskite solar cells.

[0050] In some embodiments, the method for preparing the self-polymerizing material includes the following steps:

[0051] S1, dissolve the first compound in the first solvent, add the first alkaline agent, and obtain the first mixture;

[0052] S2, the second compound is mixed with the first mixture to undergo the first reaction, yielding the first intermediate product;

[0053] S3, the first intermediate product is mixed with palladium acetate, triphenylphosphine (PPh3), a second alkali agent, a vinyl compound, and a second solvent, and a second reaction is carried out under a protective atmosphere to obtain a second intermediate product; the second intermediate product undergoes a third reaction with an acid agent to obtain a self-polymerizing material;

[0054] The structural formula of the first compound is shown in Formula II: Formula II, wherein X1 is at least one of Br, Cl, and F; Y' is N, S, O, a single bond, or does not exist;

[0055] The structural formula of the second compound is shown in Formula III or Formula IV: Formula III Formula IV; wherein, al' is a C1-C6 alkylene group, X2 and X3 are each independently at least one of Br, Cl, and F; R3 and R4 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halogroup, fluorine, amino, hydroxyl, cyano, amidine, and amidine tert-butyl carbonate;

[0056] The structural formula of the first intermediate product is shown in formula V: Equation V; R' is or Where R1' and R3 are the same; R2' and R4 are the same;

[0057] The structural formula of the second intermediate product is shown in Formula VI: Formula VI;

[0058] Vinyl compounds include at least one of vinyltrimethylsilane, vinylboric acid, and vinyltin.

[0059] In the above embodiments of this application, the first reaction helps to introduce characteristic groups, thereby helping to passivate the perovskite layer; the second reaction, namely the Heck reaction, helps to introduce alkenyl groups; and the third reaction helps to form terminal alkenyl structures, giving the resulting material self-polymerization properties and enabling the formation of a dense hole transport layer in situ on the TCO substrate surface, thereby helping to improve the long-term stability of perovskite solar cells.

[0060] In some embodiments, the molar ratio of the first compound and the second compound is 1:(1 to 1.5). Specifically, but not limitingly, the molar ratio of the first compound and the second compound is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or any value within the range of any two of the above values.

[0061] In the above embodiments of this application, controlling the molar ratio of the first compound and the second compound within the above range helps to enable the first compound and the second compound to react fully and form a first intermediate product with a specific structure; the utilization rate of raw materials is relatively higher.

[0062] In some embodiments, the molar ratio of the first compound to the first base is 1:(1~2). Specifically, but not limitingly, the molar ratio of the first compound to the first base is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, or any value within the range of any two of the above values.

[0063] In the above embodiments of this application, adjusting the molar ratio of the first compound and the first alkali within the above range can promote the reaction between the first compound and the second compound, introduce characteristic groups on the basis of the core structure, and improve the passivation effect of the self-polymerizing material on the perovskite layer.

[0064] In some embodiments, the molar amount of the first compound to the volume ratio of the first solvent is 1 mol: (3~10) L. Specifically, but not limitingly, 1 mol of the first compound corresponds to 8 L, 9 L, 10 L, 11 L, 12 L, 13 L, 14 L or 15 L of the first solvent.

[0065] In the above embodiments of this application, adjusting the ratio of the first compound to the first solvent within the above range helps the first compound and the second compound to dissolve fully in the first solvent, thereby helping to promote the uniformity of the first reaction.

[0066] In some embodiments, the molar ratio of the first intermediate product, palladium acetate, triphenylphosphine, and the second alkali is (8~12):1:2:(20~30). Specifically, but not limitingly, the molar ratio of the first intermediate product, palladium acetate, triphenylphosphine, and the second alkali can be 8:1:2:20, 9:1:2:20, 10:1:2:25, 11:1:2:30, 12:1:2:20, or any value within the range of any two of the above ratios.

[0067] In the embodiments described above in this application, palladium acetate and triphenylphosphine can form bis(triphenylphosphine)palladium acetate in solution, which is a commonly used Heck reaction catalyst and facilitates the formation of the second intermediate product with the structure shown in Formula VI. Adjusting the molar ratio of the above materials within the aforementioned range helps the second reaction proceed rapidly, thereby improving production efficiency and economic benefits.

[0068] In some embodiments, the molar ratio of the first intermediate to the vinyl compound is 1:(2~2.5). Specifically, but not limitingly, the molar ratio of the first intermediate to the vinyl compound can be 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, or any value within the range of any two of the above ratios.

[0069] In the above embodiments of this application, controlling the molar ratio of the first intermediate product to vinyltrimethylsilane within the above range helps to form a bi-terminated alkenyl self-polymerizing material, which in turn helps to form a dense hole transport layer in situ on the TCO substrate surface, thereby improving the stability and photoelectric conversion efficiency of perovskite solar cells.

[0070] In some embodiments, the molar amount of the first intermediate product to the volume ratio of the second solvent is 1 mol: (8~15) L. Specifically, but not limitingly, 1 mol of the first compound corresponds to 8 L, 9 L, 10 L, 11 L, 12 L, 13 L, 14 L or 15 L of the second solvent.

[0071] In the above embodiments of this application, controlling the volume ratio of the first intermediate product to the second solvent within the above range helps to fully dissolve the first intermediate product in the second solvent, which is beneficial to the full progress of the second reaction and to the full utilization of each raw material.

[0072] In some embodiments, the molar amount of the first intermediate product to the volume ratio of the acid is 1 mol: (25~35) L. Specifically, but not limitingly, the volume of the acid relative to 1 mol of the first intermediate product is 25 L, 26 L, 27 L, 28 L, 29 L, 30 L, 31 L, 32 L, 33 L, 34 L, 35 L, or any value within the range of any two of the above values.

[0073] In the above embodiments of this application, controlling the amount of the first intermediate product and the acid agent within the above range helps to fully remove the silane from the second intermediate product, forming a self-polymerizing material with a double-terminated alkenyl structure, improving the purity and yield of the product, thereby facilitating the formation of a dense hole transport layer on the TCO substrate surface during subsequent perovskite solar cell fabrication, and improving the stability and photoelectric performance of the perovskite solar cell.

[0074] Specifically, but not limitingly, the first solvent includes at least one of tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and acetonitrile; the first alkali includes at least one of potassium tert-butoxide, sodium hydroxide, and sodium tert-butoxide; the second alkali includes at least one of triethylamine, potassium carbonate, and potassium acetate; and the second solvent includes at least one of N,N-dimethylformamide (DMF), toluene, and dioxane.

[0075] In some embodiments, the acid is a hydrochloric acid solution with a concentration of 0.5 mol / L to 1.5 mol / L.

[0076] In the above embodiments of this application, the use of an acid agent helps to form a self-polymerizing material with dual-terminated alkenyl groups, and also helps to reduce the acoustic field probability of by-products, thereby increasing the yield and purity of the self-polymerizing material. This, in turn, helps to improve the uniformity and density of the hole transport layer formed by the self-polymerizing material, and enhances the overall performance of the perovskite solar cell.

[0077] Specifically, but not limitingly, the protective atmosphere includes at least one of nitrogen and an inert gas; the inert gas includes at least one of argon, helium, and neon.

[0078] In some embodiments, the temperature of the first reaction is 20°C to 30°C; the time of the first reaction is 12h to 18h.

[0079] In the above embodiments of this application, regulating the conditions of the first reaction within the above range helps the first reaction proceed smoothly and form the first intermediate product with the desired structure.

[0080] In some embodiments, in S2, after the first reaction is completed, the product of the first reaction is subjected to a first concentration and a first purification process to obtain the first intermediate product.

[0081] In the embodiments described above in this application, the first concentration and first purification processes help improve the purity of the first intermediate product and reduce the content of by-products, thereby helping to improve the consistency of the hole transport layer material and enhance the long-term stability of the perovskite solar cell. Specifically, but not limitingly, silica gel column chromatography is used for the first purification process.

[0082] In some embodiments, the temperature of the second reaction is 70°C to 90°C; the time of the second reaction is 12h to 18h.

[0083] In the above embodiments of this application, regulating the conditions of the second reaction within the above range helps to improve the reaction efficiency and obtain a second intermediate product having an alkenyl group.

[0084] In some embodiments, the temperature of the third reaction is 20°C to 30°C; the time of the third reaction is 5 min to 20 min.

[0085] In the above embodiments of this application, regulating the conditions of the third reaction within the above range helps to improve the yield of self-polymerizing materials with a di-terminated alkenyl structure.

[0086] In some embodiments, in step S3, after the third reaction is completed, the product of the third reaction is extracted to obtain an organic phase, which is then subjected to a second concentration and a second purification process to obtain a self-polymerizing material. Specifically, but not limitingly, column chromatography is used for the second purification process.

[0087] In another typical embodiment of this application, a hole transport material is provided, which is a polymer. The structural units of the polymer are derived from the self-polymerizing material in the above embodiments of this application. That is, the polymer is formed by the self-polymerizing material in the above embodiments of this application through double bond opening and single bond connection.

[0088] Since the specific structure of the aforementioned self-polymerizing materials helps improve the long-term stability of perovskite solar cells, hole transport materials polymerized from these self-polymerizing materials as monomers also help improve the long-term stability of perovskite solar cells.

[0089] In a typical embodiment of this application, a hole transport layer is provided. This hole transport layer is formed by the self-polymerization of the self-polymerizing material described in the above embodiments of this application, or by the self-polymerization of a self-polymerizing material prepared using the preparation method described in the above embodiments of this application. Because the aforementioned self-polymerizing material can self-polymerize to form a dense hole transport layer, this hole transport layer possesses excellent hole extraction and transport capabilities, as well as good stability, which helps improve the overall performance of perovskite solar cells.

[0090] In another typical embodiment of this application, a perovskite solar cell is also provided, which includes the hole transport layer described in the above embodiments of this application. Because the material in the hole transport layer has a good passivation effect on the perovskite layer and a good anchoring effect on the TCO substrate, the perovskite solar cell in this embodiment exhibits good long-term stability.

[0091] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0092] Example 1

[0093] One embodiment of the self-polymerizing material of this application is shown in the following flowchart:

[0094]

[0095] The preparation method is as follows:

[0096] S1, 1.0 mol of di(4-bromophenyl)amine was dissolved in 10 L of THF, and then 1.5 mol of potassium carbonate was added to obtain the first mixture;

[0097] S2, after stirring the first mixture for ten minutes, 1.2 mol of p-bromobenzomidine tert-butyl carbonate was added, and the reaction was carried out at room temperature (25℃) for 16 hours. The reaction was monitored by TLC until complete, and then directly concentrated and purified by silica gel column chromatography to obtain the intermediate product IM1, yield: 63%, with the following structural formula:

[0098] IM1; its NMR data are as follows:

[0099] 1H NMR (400MHz, CDCl3, ppm): 10.68(br, 1H), 9.21(br, 1H), 7.79(m, 4H), 7.34(m, 2H), 7.20(m, 2H), 7.15(m, 4H), 1.42(s, 9H);

[0100] 13C NMR (400 MHz, CDCl3, ppm): 165.1, 153.5, 144.3, 135.3, 132.1,130.4, 127.3, 125.9, 125.5, 123.5, 84.9, 28.4.

[0101] S3, 1 mol IM1, 0.1 mol Pd(OAc)2, 0.2 mol PPh3, 2.5 mol triethylamine, and 2.2 mol vinyltrimethylsilane were added to 10 L of DMF. The mixture was heated to 80 °C under a nitrogen atmosphere and stirred for 16 hours to obtain IM2. The reaction was confirmed to be complete by TLC. The mixture was then cooled to room temperature (25 °C), and 30 L of 1 M hydrochloric acid solution was added. The mixture was stirred for 3 hours, and the pH of the reaction solution was adjusted to 8 with sodium carbonate. The mixture was extracted twice with 20 L of dichloromethane. After separation, the organic phase was dried over anhydrous sodium sulfate and concentrated. Column chromatography was used to separate the solid TM1, and the yield was concentrated to obtain solid TM1 (30%). The structural formula is as follows:

[0102] TM1, its NMR data are as follows:

[0103] 1H NMR(400MHz, CDCl3, ppm):10.68(br, 1H), 7.78(m, 4H), 7.74(m, 4H), 7.30(m, 2H), 7.13(m, 2H), 6.90(br, 2H), 6.73(m, 2H), 5.26(m,2H), 5.12(m,2H);

[0104] 13C NMR (400 MHz, CDCl3, ppm): 163.0, 139.5, 129.3, 128.3, 127.1,127.4, 126.9, 125.9, 125.5, 120.6, 116.3.

[0105] Example 2

[0106] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that tert-butyl p-bromobenzamide carbonate is used instead of tert-butyl p-bromobenzamide carbonate to obtain self-polymerizing material TM2, whose structural formula is as follows:

[0107] TM2; its NMR data are as follows:

[0108] 1H NMR(400MHz, CDCl3, ppm):7.76(m, 4H), 7.40(m, 2H), 7.34(m, 4H),7.11(m, 2H), 6.70(m, 2H), 5.24(m, 2H), 5.11(m, 2H), 4.50(br, 2H);

[0109] 13C NMR (400 MHz, CDCl3, ppm): 139.1, 129.5, 127.3, 127.1, 127.0, 125.9, 125.1, 125.5, 123.6, 116.6.

[0110] Example 3

[0111] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that p-bromoacetophenone is used instead of p-bromobenzomidine tert-butyl carbonate to obtain the self-polymerizing material TM3, whose structural formula is as follows:

[0112] TM3; its NMR data are as follows:

[0113] 1H NMR(400MHz, CDCl3, ppm):7.79(m, 4H), 7.77(m, 2H), 7.34(m, 2H),7.13(m, 4H), 6.74(m, 2H), 5.14(m, 2H), 5.10(m, 2H), 2.50(s, 3H);

[0114] 13C NMR (400 MHz, CDCl3, ppm): 138.1, 130.5, 129.3, 127.4, 127.1,125.6, 125.1, 125.0, 124.6, 115.8, 26.8.

[0115] Example 4

[0116] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that p-methanesulfonylbromobenzene is used instead of p-bromobenzamide tert-butyl carbonate to obtain the self-polymerizing material TM4, whose structural formula is as follows:

[0117] TM4; its NMR results are as follows:

[0118] 1H NMR(400MHz, CDCl3, ppm):7.80(m, 4H), 7.75(m, 2H), 7.30(m, 2H),7.19(m, 4H), 6.54(m, 2H), 5.33(m, 2H), 5.20(m, 2H), 4.11(s, 3H);

[0119] 13C NMR (400 MHz, CDCl3, ppm): 143.1, 129.1, 127.4, 127.0, 126.0, 125.9, 125.7, 125.3, 123.6, 118.6, 47.8.

[0120] Example 5

[0121] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that p-fluorobromobenzene is used instead of p-bromobenzamide tert-butyl carbonate to obtain the self-polymerizing material TM5, whose structural formula is as follows:

[0122] TM5; its NMR data are as follows:

[0123] 1H NMR(400MHz, CDCl3, ppm):7.79(m, 4H), 7.25(m, 4H), 7.22(m, 2H),7.09(m, 2H), 6.53(m, 2H), 5.31(m, 2H), 5.26(m, 2H);

[0124] 13C NMR (400 MHz, CDCl3, ppm): 145.1, 129.5, 127.0, 126.6, 126.1, 125.8, 125.9, 125.3, 122.6, 118.9.

[0125] Example 6

[0126] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that p-trifluoromethylbromobenzene is used instead of p-bromobenzamide tert-butyl carbonate to obtain the self-polymerizing material TM6, whose structural formula is as follows:

[0127] TM6; its NMR data are as follows:

[0128] 1H NMR (400MHz, CDCl3, ppm): 7.75(m, 4H), 7.29(m, 4H), 7.21(m, 2H), 7.05(m, 2H), 6.51(m, 2H), 5.30(m, 2H), 5.28(m, 2H).

[0129] 13C NMR (400 MHz, CDCl3, ppm): 145.0, 138.1, 132.4, 129.9, 128.8, 126.1, 125.9, 125.1, 124.9, 123.6, 118.6.

[0130] Example 7

[0131] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that p-cyanobromobenzene is used instead of p-bromobenzamide tert-butyl carbonate to obtain the self-polymerizing material TM7, whose structural formula is as follows:

[0132] TM7; its NMR data are as follows:

[0133] 1H NMR(400MHz, CDCl3, ppm):7.80(m, 4H), 7.61(m, 2H), 7.29(m, 2H),7.25(m, 4H), 6.31(m, 2H), 5.25(m, 2H), 5.20(m, 2H);

[0134] 13C NMR (400 MHz, CDCl3, ppm): 143.0, 135.2, 132.3, 131.9, 128.8,126.1, 125.9, 125.1, 124.9, 113.6, 108.6.

[0135] Example 8

[0136] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that ethyl p-bromobenzoate is used instead of tert-butyl p-bromobenzoamide carbonate to obtain the self-polymerizing material TM8, whose structural formula is as follows:

[0137] TM8; its NMR data are as follows:

[0138] 1H NMR(400MHz, CDCl3, ppm):7.78(m, 4H), 7.74(m, 2H), 7.30(m, 2H),7.13(m, 2H), 6.73(m, 2H), 5.26(m, 2H), 5.12(m, 2H), 4.35(q, 2H), 1.30(t, 3H);

[0139] 13C NMR (400 MHz, CDCl3, ppm): 165.0, 139.5, 129.3, 128.3, 127.1,127.4, 126.9, 125.9, 125.5, 120.6, 116.3, 60.5, 14.3.

[0140] Example 9

[0141] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that 3,6-dibromocarbazole is used instead of di(4-bromophenyl)amine to obtain the self-polymerizing material TM9, whose structural formula is as follows:

[0142] TM9; its NMR data are as follows:

[0143] 1H NMR (400MHz, CDCl3, ppm): 10.68(br, 1H), 7.79(m, 4H), 7.76(m, 2H), 7.35(m, 2H), 7.13(m, 2H), 6.92(br, 2H), 6.71(m, 2H), 5.22(m,2H), 5.11(m,2H);

[0144] 13C NMR (400 MHz, CDCl3, ppm): 163.1, 139.4, 129.5, 128.1, 127.6, 127.2, 126.5, 125.6, 125.4, 120.1, 116.4.

[0145] Example 10

[0146] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that 3,7-dibromo-10H-phenthiazide is used instead of di(4-bromophenyl)amine to obtain the self-polymerizing material TM10, whose structural formula is as follows:

[0147] TM10; its NMR data are as follows:

[0148] 1H NMR(400MHz, CDCl3, ppm):7.74(m, 4H), 7.41(m, 2H), 7.37(m, 2H),7.12(m, 2H), 6.74(m, 2H), 5.14(m, 2H), 5.13(m, 2H), 4.55(br, 2H).

[0149] 13C NMR (400 MHz, CDCl3, ppm): 139.5, 129.1, 127.2, 127.0, 126.8, 125.6, 125.9, 125.2, 123.2, 116.7.

[0150] Example 11

[0151] One embodiment of the self-polymerizing material of this application differs from that of Example 1 only in that 5-bromopentanidine (CAS No.: 885959-45-5) is used instead of tert-butyl p-bromobenzamide carbonate, and 3,6-dibromocarbazole is used instead of di(4-bromophenyl)amine to obtain the self-polymerizing material TM11, whose structural formula is as follows:

[0152] TM11; its NMR data are as follows:

[0153] 1H NMR(400MHz, CDCl3, ppm):10.61(br, 1H), 7.77(m, 2H), 7.74(m, 2H),7.31(m, 2H), 6.95(br, 2H), 6.73(m, 2H), 5.26(m, 2H), 5.12(m, 2H), 4.13(m,2H), 2.03(m, 2H), 1.93(m, 2H), 1.85(m, 2H);

[0154] 13C NMR (400 MHz, CDCl3, ppm): 163.0, 139.5, 129.3, 128.3, 127.8,127.4, 126.9, 120.6, 116.3, 59.1, 28.9, 19.8, 19.0.

[0155] Comparative Example 1

[0156] Comparative Example 1 is [2-(9H-carbazole-9-yl)ethyl]phosphonic acid.

[0157] Performance testing

[0158] I. SEM Testing:

[0159] SEM images of the cross-sections of perovskite solar cells based on TM1-TM10 and Comparative Example 1 were obtained using a SEM instrument.

[0160] II. Performance Testing of Perovskite Solar Cells:

[0161] 1. Fabrication of crystalline silicon-perovskite tandem solar cell devices:

[0162] (1) Provide crystalline silicon solar cell: The crystalline silicon solar cell includes a silver electrode with a thickness of 100 nm, an indium tin oxide (ITO) layer with a thickness of 100 nm, a P-type amorphous silicon thin film with a thickness of 10 nm, an N-type monocrystalline silicon substrate with a thickness of 150 μm and a 10 nm N-type amorphous silicon thin film stacked sequentially.

[0163] (2) An ITO transparent conductive oxide layer with a thickness of 100 nm is deposited on the surface of the N-type amorphous silicon thin film away from the N-type single crystal silicon substrate as an interconnect layer.

[0164] (3) In a glove box under a nitrogen atmosphere, 1 mg of self-polymerizing material was weighed and dissolved in 1 mL of DMF to obtain a hole transport layer solution; then the hole transport layer solution was spin-coated onto a transparent conductive oxide layer at a speed of 4000 rpm, annealed at 120 °C for 30 min, and cooled to room temperature to form a hole transport layer with a thickness of 5 nm.

[0165] (4) In a glove box under nitrogen atmosphere, spin-coat a 1.2 mg / mL perovskite precursor solution on the surface of the hole transport layer at a speed of 4000 rpm, and then anneal at 150 °C for 30 min to form a perovskite active layer with a thickness of 0.8 μm.

[0166] (5) Vacuum evaporation is used (vacuum degree is 5×10). -4 C60 was deposited on the perovskite active layer using a method of deposition rate of 0.5 Å / s (Pa, evaporation rate of 0.5 Å / s) to obtain an electron transport layer with a thickness of 30 nm.

[0167] (6) SnO2 was deposited on the electron transport layer by ALD atomic layer deposition to obtain a tin oxide buffer layer with a thickness of 15 nm;

[0168] (7) A transparent top electrode layer of indium zinc oxide (IZO) with a thickness of 150 nm and a silver electrode layer with a thickness of 200 nm are sequentially deposited on the buffer layer by magnetron sputtering to obtain a perovskite solar cell.

[0169] 2. IV test

[0170] Photovoltaic performance testing: The perovskite solar cells prepared in the above examples and comparative examples were placed in a solar simulator (manufacturer: Wavelabs). Under the illumination of a certain solar intensity, a bias voltage (Vp, bias voltage range of -0.1V~2.0V) was applied to the device using a test source meter, and the output current of the device was tested to obtain the bias voltage-current density curve.

[0171] Open-circuit voltage (Voc): The terminal voltage of the solar cell when no load is connected, i.e., when the current density in the bias-current density curve is 0 mA·cm. -2 The bias voltage value at that time.

[0172] Short-circuit current density (Jsc): The output current per unit area of ​​the solar cell when it is short-circuited, i.e., the current density when the bias voltage is 0V in the bias voltage-current density curve.

[0173] Fill factor (FF): FF = (Vmp × Jmp) / (Jsc × Voc), where Jmp and Vmp represent the current density and voltage at the maximum power point (Pm), respectively.

[0174] Photoelectric conversion efficiency (PCE): PCE = Voc × Jsc × FF.

[0175] Long-term stability: The stability of the crystalline silicon-perovskite tandem solar cell device was tested under sunlight at 85°C and 85% humidity for 5000 hours.

[0176] The test results are shown in Table 1 and Figures 1-12 As shown.

[0177] Table 1

[0178]

[0179] As shown in Table 1, the device containing the hole transport layer formed by the self-polymerization of the self-polymerizing material in this application has both good photoelectric conversion performance and stability, while the stability of Comparative Example 1 is significantly worse than that of the embodiment.

[0180] Depend on Figures 1-11 It can be seen that the hole transport layer formed by the self-polymerization of the self-polymerizing material in this application is more uniform, while the hole transport layer made with the material in Comparative Example 1 has void defects.

[0181] Depend on Figure 12 It is known that the hole transport layer formed by the self-polymerization of the self-polymerizing material in Embodiment 1 of this application has high stability, and the device containing the above-mentioned hole transport layer has significantly higher long-term stability.

[0182] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A self-polymerizing material, characterized in that, The structural formula of the self-polymerizing material is shown in Formula I: Equation I; Where Y represents N, S, O, a single bond, or is absent; R represents... or In this context, al is a C1-C6 alkylene group, and R1 and R2 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halogroup, fluorine, amino, hydroxyl, cyano, and amidine.

2. The self-polymerizing material according to claim 1, characterized in that, R1 and R2 are each independently any one of C1-C3 alkyl ester, C1-C3 alkyl acyl, C1-C3 alkyl sulfonyl, C1-C3 alkyl containing at least one halogenated group, fluorine, amino, hydroxy, cyano, and amidine.

3. The self-polymerizing material according to claim 2, characterized in that, R1 and R2 are each independently one of acetyl, methanesulfonyl, amido, cyano, amino, trifluoromethyl, fluoro, and ethyl ester; and / or, al is a C2-C4 alkyl group.

4. The self-polymerizing material according to any one of claims 1 to 3, characterized in that, At least one of the following conditions must be met: (1) Y is S, a single bond, or does not exist; (2) The R is ; (3) R2 is amido, amino, or cyano.

5. The self-polymerizing material according to claim 1, characterized in that, The self-polymerizing material is selected from at least one of the compounds shown in Formulas 1 to 18: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17 Formula 18.

6. A method for preparing a self-polymerizing material according to any one of claims 1 to 5, comprising the following steps: S1, dissolve the first compound in the first solvent, add the first alkaline agent, and obtain the first mixture; S2, the second compound is mixed with the first mixture to undergo a first reaction, yielding a first intermediate product; S3, the first intermediate product is mixed with palladium acetate, triphenylphosphine, a second alkali agent, a vinyl compound, and a second solvent, and a second reaction is carried out under a protective atmosphere to obtain a second intermediate product; the second intermediate product undergoes a third reaction with an acid agent to obtain the self-polymerizing material; in, The structural formula of the first compound is shown in Formula II: Formula II, wherein X1 is at least one of Br, Cl, and F; Y' is N, S, O, a single bond, or does not exist; The structural formula of the second compound is shown in Formula III or Formula IV: Formula III Formula IV; wherein, al' is a C1-C6 alkylene group, X2 and X3 are each independently at least one of Br, Cl, and F; R3 and R4 are each independently any one of C1-C6 alkyl ester, C1-C6 alkyl acyl, C1-C6 alkyl sulfonyl, C1-C6 alkyl containing at least one halogroup, fluorine, amino, hydroxyl, cyano, amidine, and amidine tert-butyl carbonate; The structural formula of the first intermediate product is shown in formula V: Equation V; R' is or Where R1' is the same as R3; R2' is the same as R4; The structural formula of the second intermediate product is shown in Formula VI: Formula VI; The vinyl compound includes at least one of vinyltrimethylsilane, vinylboric acid, and vinyltin.

7. The method for preparing the self-polymerizing material according to claim 6, characterized in that, At least one of the following conditions must be met: (1) The molar ratio of the first compound to the second compound is 1:(1~1.5); (2) The molar ratio of the first compound to the first alkali is 1:(1~2); (3) The molar ratio of the first compound to the volume ratio of the first solvent is 1 mol: (8~15) L; (4) The molar ratio of the first intermediate product, the palladium acetate, the triphenylphosphine and the second alkali is (8~12):1:2:(20~30); (5) The molar ratio of the first intermediate product to the vinyl compound is 1:(2~2.5); (6) The molar ratio of the first intermediate product to the volume ratio of the second solvent is 1 mol: (8~15) L; (7) The molar ratio of the first intermediate product to the volume ratio of the acid agent is 1 mol: (25~35) L; (8) The first solvent includes at least one of tetrahydrofuran, N,N-dimethylformamide, and acetonitrile; (9) The first alkaline agent includes at least one of potassium tert-butoxide, sodium hydroxide, and sodium tert-butoxide; (10) The second alkaline agent includes at least one of triethylamine, potassium carbonate, and potassium acetate; (11) The second solvent includes at least one of N,N-dimethylformamide, toluene, and dioxane; (12) The acid is a hydrochloric acid solution with a concentration of 0.5 mol / L to 1.5 mol / L; (13) The protective atmosphere includes at least one of nitrogen and an inert gas; the inert gas includes at least one of argon, helium, and neon; (14) The temperature of the first reaction is 20℃~30℃; (15) The reaction time for the first reaction is 12h~18h; (16) The preparation method further includes the following steps: In S2, after the first reaction is completed, the product of the first reaction is subjected to a first concentration and a first purification treatment to obtain the first intermediate product; (17) The temperature of the second reaction is 70℃~90℃; (18) The second reaction takes 12 to 18 hours; (19) The temperature of the third reaction is 20℃~30℃; (20) The time for the third reaction is 5 min to 20 min; (21) The preparation method further includes the following steps: In S3, after the third reaction is completed, the product of the third reaction is extracted to obtain an organic phase, and the organic phase is subjected to a second concentration and a second purification to obtain the self-polymerizing material.

8. A hole transport material, characterized in that, The hole transport material is a polymer, and the structural units of the polymer are derived from the self-polymerizing material of any one of claims 1 to 5.

9. A hole transport layer, characterized in that, The hole transport layer is formed by self-polymerization of a self-polymerizing material; the self-polymerizing material is the self-polymerizing material according to any one of claims 1 to 5 or the self-polymerizing material prepared by the preparation method according to any one of claims 6 to 7; or, the material of the hole transport layer is the hole transporting material according to claim 8.

10. A perovskite solar cell, characterized in that, It includes the hole transport layer as described in claim 9.

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