Perovskite solar cell module self-assembled monomolecular hole transport material and preparation method thereof

Abstract

The application belongs to the field of solar cells, and particularly relates to a perovskite solar cell module self-assembled monomolecular hole transport material and a preparation method thereof. The self-assembled monomolecular hole transport material of the perovskite solar cell module is a triphenylphosphine phosphonic acid carbazole compound, and the preparation steps are as follows: etching the surface of a conductive substrate; dissolving the triphenylphosphine phosphonic acid carbazole compound in a solvent to obtain a triphenylphosphine phosphonic acid carbazole compound solution, depositing the triphenylphosphine phosphonic acid carbazole compound on the surface of the conductive substrate by a chemical bath method to obtain a hole transport layer; sequentially depositing a perovskite layer and an electron transport layer on the surface of the hole transport layer by a coating technology, and then etching the surface of the electron transport layer; depositing a counter electrode layer on the surface of the electron transport layer, and then etching the surface of the counter electrode layer. The prepared perovskite solar cell module can improve the long-term operation stability of a large-area perovskite photovoltaic module.

Description

Technical Field

[0001] This invention belongs to the field of solar cells, specifically relating to a self-assembled single-molecule hole transport material for perovskite solar cell modules and its preparation method. Background Technology

[0002] Perovskite solar cells are currently one of the most promising photovoltaic technologies. However, the p-type organic small molecule Spiro-OMeTAD, commonly used in nip-type inverted perovskite devices, suffers from problems such as difficulty in large-area coating, susceptibility to water absorption, and poor thermal stability, which greatly restricts the large-scale fabrication of these cells. Recently, pin-type inverted perovskite devices using p-type self-assembled molecules (SAMs) with low carrier recombination loss as the hole transport layer have achieved a photoelectric conversion efficiency exceeding 26%, attracting significant attention from researchers. Importantly, the large-area fabrication of the SAM hole transport layer through a simple low-temperature solution coating method ensures the large-scale fabrication of large-area inverted perovskite solar modules.

[0003] Nevertheless, under actual operating conditions of "light field / electric field / thermal stress," the Pb-I bonds in the perovskite photoactive layer of inverted perovskite solar modules are prone to breakage, generating elemental iodine. Elemental iodine, under illumination, damages the crystal structure and induces the formation of more harmful elemental iodine, causing the decomposition of perovskite materials to exhibit a self-accelerating trend, severely affecting the stability of perovskite photovoltaic modules. To address this, Chinese invention patent CN 118785794 A proposes a method using crown ether additives to capture elemental iodine in perovskite films, preventing further corrosion of the perovskite by iodine. Simultaneously, crown ether additives can transform yellow-phase formamidinium-iodide perovskite into black-phase perovskite, improving the stability of the perovskite film. Furthermore, Chinese invention patent CN117295343 A proposes a method for constructing a multi-carbon chain fluorine-based molecular barrier layer in perovskite devices to capture harmful elemental iodine generated in the perovskite film, improving the stability of the device under bias conditions.

[0004] In existing technology (CN 118852249 A), triphenylphosphine molecules are used alone as hole transport materials. However, due to the low π-π stacking density, their hole transport capability is insufficient. Furthermore, the dipole moment of the disclosed triphenylphosphine molecules is too low (0.8D), resulting in a weak response to electric fields and difficulty in forming strong interactions at the perovskite interface, leading to poor interfacial contact. The low dipole moment also results in weak affinity between triphenylphosphine and the perovskite surface, reducing the wettability of the perovskite precursor solution and hindering the large-area fabrication of perovskite thin films. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a self-assembled single-molecule hole transport material for perovskite solar cell modules and its preparation method, aiming to solve the technical problems of poor stability and difficulty in large-area fabrication of perovskite solar cell modules in existing technologies.

[0006] According to a first aspect of the present invention, a hole transport material is provided, comprising a triphenylphosphine-carbazole compound, wherein the triphenylphosphine-carbazole compound is selected from at least one compound shown in Formula I, Formula II, or Formula III:

[0007]

[0008]

[0009] R1 is selected from C1-C8 alkyl chains or aromatic chains; R2 and R3 are independently selected from one of oxygen atoms, sulfur atoms, and selenium atoms.

[0010] According to another aspect of the present invention, a method for preparing a hole transport material is provided, wherein the method for preparing the triphenylphosphine-phosphonic carbazole compound is as follows: using phenylphosphine-p-aniline and a brominated phosphine carbazole compound as reactants, a nucleophilic substitution reaction is carried out under the action of a catalyst, an organic ligand, and a base to prepare the triphenylphosphine-phosphonic carbazole compound.

[0011] Preferably, the phenylphosphine-p-aniline is selected from one of the following compounds:

[0012]

[0013] R2 and R3 are independently selected from one of the following: oxygen atom, sulfur atom, and selenium atom;

[0014] The bromophosphonic acid carbazole compound is:

[0015]

[0016] R1 is selected from C1-C8 alkyl chains or aromatic chains.

[0017] Preferably, the molar ratio of phenylphosphine p-aniline to brominated carbazole is 1:0.5 to 1:2, the reaction temperature of phenylphosphine p-aniline and brominated carbazole is 120-180℃, and the reaction time is 12-24h.

[0018] Preferably, the catalyst is a metal halide, selected from one or more of cuprous chloride, ferrous chloride, zinc chloride, cuprous bromide, ferrous bromide, zinc bromide, cuprous iodide, ferrous iodide, and zinc iodide; the organic ligand is one or more of 2,2′-bipyridine, trifluoroacetic acid, ethylenediaminetetraacetic acid, cyclooctatetraene, triacetamipridyltriethylamine, and imidazole; the base is one or more of triethylamine, ammonia, sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and potassium bicarbonate; and the molar ratio of the catalyst, organic ligand, and base is 0.1:1:3 to 1:5:10.

[0019] According to another aspect of the present invention, a perovskite solar cell module is provided, comprising, from top to bottom, a conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, and a counter electrode layer, wherein the hole transport layer material is the triphenylphosphine carbazole compound as described in claim 1.

[0020] According to another aspect of the present invention, a method for preparing the perovskite solar cell module described above is provided, characterized by comprising the following steps:

[0021] (1) Etching the surface of the conductive substrate;

[0022] (2) Dissolve triphenylphosphonic carbazole compounds in a solvent to obtain a triphenylphosphonic carbazole compound solution. Immerse a conductive substrate in the triphenylphosphonic carbazole compound solution by a chemical bath method to deposit triphenylphosphonic carbazole compounds on the surface of the conductive substrate to obtain a hole transport layer.

[0023] (3) A perovskite layer and an electron transport layer are sequentially deposited on the surface of the hole transport layer by coating technology, and then the surfaces of the hole transport layer, the perovskite layer and the electron transport layer are etched.

[0024] (4) Deposit a counter electrode layer on the surface of the electron transport layer, and then etch the surfaces of the hole transport layer, perovskite layer, electron transport layer and counter electrode layer.

[0025] Preferably, in step (2), the solvent is selected from one of the following: a mixed solvent of ethanol and water, a mixed solvent of acetonitrile and water, a mixed solvent of methanol and toluene, a mixed solvent of acetone and water, and a mixed solvent of dichloromethane and ethanol; the concentration of the triphenylphosphine carbazole compound in the triphenylphosphine carbazole compound solution is 0.1 to 5 mg / mL.

[0026] Preferably, in the chemical bath method described in step (2), the chemical bath temperature is 25-80°C; and the chemical bath deposition time is 1-30 minutes.

[0027] Preferably, the surface of the hole-modified layer obtained in step (2) is cleaned in stages. In the first stage, one or more cleaning solvents selected from toluene, dichloromethane, petroleum ether, tetrahydrofuran and ethyl acetate are used for cleaning. In the second stage, one or more cleaning solvents selected from methanol, isopropanol, ethanol and N-methylpyrrolidone are used for cleaning.

[0028] In summary, compared with the prior art, the above-described technical solutions conceived by this invention mainly possess the following technical advantages:

[0029] (1) This invention utilizes the nucleophilic phosphorus atom lone pair electrons in triphenylphosphine carbazole compounds to form chemical bonds with iodine, thereby removing the elemental iodine generated in the perovskite active layer and inhibiting the self-accelerated degradation process of perovskite, thus improving the long-term operational stability of large-area perovskite photovoltaic modules.

[0030] (2) In this invention, R2 and R3 on the triphenylphosphine carbazole molecule are selected from oxygen, sulfur, or selenium atoms, and their lone pair electrons can interact with the unsaturated metal cation orbitals at the bottom of the perovskite (such as Pb). 2+ Electrons are supplied by the d orbitals (or empty p orbitals) to form coordinate bonds. This interaction enhances the bonding between the molecule and the perovskite surface, improving the wettability of the perovskite precursor solution on the surface of the triphenylphosphine carbazole molecule, thus facilitating the fabrication of large-area, high-quality perovskite thin films. Furthermore, the interaction between the triphenylphosphine carbazole molecule and the perovskite optimizes the interfacial energy level arrangement, improving the charge transport capability of the device. This invention provides a framework for the large-scale application of large-area, highly efficient, and stable perovskite solar modules.

[0031] (3) The triphenylphosphine-based phosphonate carbazole molecules used in this invention have high dipole moment characteristics, which enable them to form a high built-in electric field at the perovskite interface. This facilitates the separation of electrons and holes, enhances the separation and transport efficiency of charge carriers, and thus improves the photoelectric performance of perovskite photovoltaic modules. In addition, the high π-π stacking density in the triphenylphosphine-based phosphonate carbazole molecules can enhance the intermolecular interaction forces and improve the structural stability of molecules or thin films. At the same time, the strong π-π stacking characteristics can reduce the degree of freedom of the material and reduce structural changes caused by heat and light, thereby improving the long-term stability of the battery.

[0032] (4) In view of the key problems of expensive palladium metal catalysts and low yield in the nucleophilic substitution reaction, this invention uses inexpensive and highly active metal halides as catalysts. With the synergistic effect of ligands and bases, the yield of nucleophilic substitution to prepare triphenylphosphine carbazole molecules can be greatly improved. This can effectively solve the key problems of low yield and high cost in the synthesis of traditional single-molecule hole transport materials, and promote the rapid development of low-cost, large-area, high-efficiency and stable perovskite batteries.

[0033] (5) The surface of the hole-modified layer of the present invention is cleaned in stages. The first stage removes the physically adsorbed unreacted triphenylphosphonic carbazole molecules, and the second stage removes the weakly adsorbed triphenylphosphonic carbazole molecules and irregular assembly to obtain a high-quality, dense monolayer of triphenylphosphonic carbazole compounds. Attached Figure Description

[0034] Figure 1 This describes the preparation process of triphenylphosphine-carbazole compounds.

[0035] Figure 2 This is a schematic diagram of a perovskite solar module.

[0036] In the figure, 1. Conductive substrate; 2. Hole transport layer; 3. Perovskite layer; 4. Electron transport layer; 5. Counter electrode layer. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0038] This invention provides a perovskite solar cell module, comprising, from top to bottom, a conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, and a counter electrode layer, wherein the hole transport layer material is the aforementioned triphenylphosphine-carbazole compound.

[0039] This invention provides a method for preparing a perovskite solar cell module, comprising the following steps:

[0040] (1) Etching the surface of the conductive substrate;

[0041] (2) Dissolve triphenylphosphonic carbazole compounds in a solvent to obtain a triphenylphosphonic carbazole compound solution. Immerse a conductive substrate in the triphenylphosphonic carbazole compound solution by a chemical bath method to deposit triphenylphosphonic carbazole compounds on the surface of the conductive substrate to obtain a hole transport layer.

[0042] (3) A perovskite layer and an electron transport layer are sequentially deposited on the surface of the hole transport layer by coating technology, and then the surfaces of the hole transport layer, the perovskite layer and the electron transport layer are etched.

[0043] (4) Deposit a counter electrode layer on the surface of the electron transport layer, and then etch the surfaces of the hole transport layer, perovskite layer, electron transport layer and electrode layer.

[0044] In some embodiments, in step (2), the solvent is selected from one of the following: a mixed solvent of ethanol and water, a mixed solvent of acetonitrile and water, a mixed solvent of methanol and toluene, a mixed solvent of acetone and water, and a mixed solvent of dichloromethane and ethanol; the concentration of the triphenylphosphonic carbazole compound in the triphenylphosphonic carbazole compound solution is 0.1 to 5 mg / mL.

[0045] In some embodiments, in the chemical bath method described in step (2), the chemical bath temperature is 25–80°C; and the chemical bath deposition time is 1–30 minutes.

[0046] In some embodiments, the surface of the hole-modified layer obtained in step (2) is cleaned in stages. In the first stage, one or more cleaning solvents selected from toluene, dichloromethane, petroleum ether, tetrahydrofuran, and ethyl acetate are used for cleaning. In the second stage, one or more cleaning solvents selected from methanol, isopropanol, ethanol, and N-methylpyrrolidone are used for cleaning.

[0047] In some embodiments, the cleaning is performed 3-5 times.

[0048] In some embodiments, the material formula of the perovskite layer is Cs. x (FA y FACs 1-y ) 1-x Pb t Sn 1-t (I z Br 1-z 3, 0 ≤ x < 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ t ≤ 1;

[0049] In some embodiments, the electron transport layer is one or more of C60, SnO2, ZnO, and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline).

[0050] This invention provides an application of a perovskite solar cell module, which is used in electrical equipment.

[0051] Example 1

[0052] Preparation of 4,4′-dithiophenylphosphine p-aniline: 4-Bromoaniline and 4,4′-dithiophenylphosphine were weighed in a molar ratio of 1:1.2 under dry, inert conditions. 0.1 mol of cuprous bromide, 1 mol of pyridine, and 3 mol of potassium carbonate were added to DMSO containing 4-bromoaniline and 4,4′-dithiophenylphosphine. The reaction solution was heated to 120 °C and reacted for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The organic layers were combined, dried, and the solvent was removed. 4,4′-dithiophenylphosphine p-aniline was obtained by recrystallization and purification.

[0053] Synthesis steps of thiotriphenylphosphine phosphonate carbazole compound: 1 mol of 4,4′-dithiophenylphosphine p-aniline, 0.5 mol of [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid (manufacturer: Tokyo Chemical Industry Co., Ltd.), and 150 mL of N,N-dimethylformamide (DMF) were added to a 500 mL three-necked flask. The mixture was stirred for 12 h at 120 °C under a high-purity nitrogen atmosphere. The chemical reaction formula is as follows: Figure 1 As shown in Table 1, after the reaction cooled to room temperature, the crude product was washed three times each with 50 ml of deionized water and 80 ml of methanol. The washed product was then purified by column chromatography to obtain pure thiotriphenylphosphonic phosphonate carbazole. Under these conditions, the yield of thiotriphenylphosphonic phosphonate carbazole was 92%, as shown in Table 1.

[0054] Fabrication steps of inverse perovskite solar cell modules: Indium-doped tin oxide (ITO) glass with dimensions of 100×100×1.5 mm (length, width, and thickness) was etched using a laser scribing process. Subsequently, the ITO glass was ultrasonically cleaned for 15 minutes each with detergent, acetone, and industrial ethanol, followed by UV ozone cleaning for 30 minutes. The substrate was then chemically immersed in a 2 mg / mL isopropanol solution of thiotriphenylphosphine phosphonate carbazole at 25°C for 10 minutes, followed by cleaning with ethyl acetate for 50 seconds and methanol for 10 seconds to remove unanchored thiotriphenylphosphine phosphonate carbazole molecules. The substrate was then annealed at 100°C in air for 10 minutes. 1.3 M Cs was then coated using a slot-fed process. 0.05 MA 0.05 FA 0.9PbI3 perovskite solution was coated onto the hole transport layer surface, and the solvent in the perovskite precursor was rapidly evaporated under high-pressure nitrogen air knife. When the film color turned brown, the perovskite film was transferred to a hot stage at 100°C for annealing for 1 hour, followed by annealing at 150°C for 10 minutes, resulting in a perovskite film with high crystallinity. Subsequently, electron transport layer materials C60 and BCP were sequentially deposited on its surface using a vapor deposition process. The surfaces of the hole transport layer, perovskite layer, and electron transport layer were etched using a laser scribing process. Subsequently, copper electrodes were vapor deposited on its surface. Finally, the surfaces of the hole transport layer, perovskite layer, electron transport layer, and electrode layer were etched using a laser scribing process to realize the series connection of each sub-cell, such as... Figure 2 As shown in Table 2, the photoelectric conversion efficiency and stability of the perovskite solar modules are as follows.

[0055] Example 2

[0056] The steps are the same as in Example 1, except that the molar ratio of 4,4′-dithiophenylphosphine p-aniline to [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid is adjusted to 1:2, and the yield of thiotriphenylphosphine phosphonate carbazole is 95%.

[0057] Example 3

[0058] The steps were the same as in Example 2, except that the reaction temperature of 4,4′-dithiophenylphosphine p-aniline with [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid was adjusted to 180°C, and the yield of thiotriphenylphosphine phosphonate carbazole was 96%.

[0059] Example 4

[0060] The steps are the same as in Example 3, except that the molar ratio of 4,4′-dithiophenylphosphine p-aniline to [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid is adjusted to 1:1, and the yield of thiotriphenylphosphine phosphonate carbazole is 92%.

[0061] Example 5

[0062] The steps were the same as in Example 4, except that the reaction temperature of 4,4′-dithiophenylphosphine p-aniline with [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid was adjusted to 150°C, and the yield of thiotriphenylphosphine phosphonate carbazole was 93%.

[0063] Example 6

[0064] The steps are the same as in Example 5, except that the molar ratio of cuprous bromide, pyridine, and potassium carbonate is adjusted to 0.1:2:5, and the yield of thiotriphenylphosphonic phosphonate carbazole is 96%.

[0065] Example 7

[0066] The steps are the same as in Example 5, except that the molar ratio of cuprous bromide, pyridine, and potassium carbonate is adjusted to 1:5:10, and the yield of thiotriphenylphosphonic phosphonate carbazole is 92%.

[0067] Example 8

[0068] The steps are the same as in Example 6, except that cuprous bromide is replaced with ferrous bromide, and the yield of thiotriphenylphosphonic phosphonate carbazole is 98%.

[0069] Example 9

[0070] The steps were the same as in Example 8, except that the concentration of the thiotriphenylphosphine phosphonate carbazole solution was adjusted to 1 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0071] Example 10

[0072] The steps were the same as in Example 8, except that the concentration of the carbazole thiotriphenylphosphonic phosphonate solution was adjusted to 3 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0073] Example 11

[0074] The steps were the same as in Example 8, except that the concentration of the carbazole thiotriphenylphosphine carboxylate solution was adjusted to 4 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0075] Example 12

[0076] The steps were the same as in Example 8, except that the concentration of the thiotriphenylphosphine phosphonate carbazole solution was adjusted to 5 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0077] Example 13

[0078] The steps are the same as in Example 10, except that the chemical bath temperature is 80°C. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0079] Example 14

[0080] The steps are the same as in Example 10, except that the chemical bath deposition time is 30 minutes. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0081] Comparative Example 1

[0082] The steps are the same as in Example 1, except that carbazole thiotriphenylphosphonic acid is replaced with triphenylphosphonic acid. The photoelectric conversion efficiency and stability of the perovskite solar module are shown in Table 2.

[0083] Comparison 2

[0084] The steps are the same as in Example 10, except that ethyl acetate is used only once in the step of cleaning the thiotriphenylphosphonic phosphonate carbazole molecules. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0085] Table 1. Yields of carbazole thiotriphenylphosphonic acid in different examples.

[0086] Example Yield (%) Example 1 92 Example 2 95 Example 3 96 Example 4 92 Example 5 93 Example 6 96 Example 7 92 Example 8 98

[0087] Table 2. Photovoltaic conversion efficiency of batteries in different embodiments (module area per 100 cm²) 2 Active area 75.4 cm² 2 ).

[0088]

[0089]

[0090] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A hole transporting material, characterized by, The triphenylphosphine carbazole phosphonic acid compound is selected from at least one of compounds shown in formula I, formula II, formula III: Formula I Formula II Formula III Wherein, R1 is selected from C1-C8 alkyl chain; R2 and R3 are independently selected from one of oxygen atom, sulfur atom and selenium atom.

2. The method for preparing a hole transport material according to claim 1, characterized in that, The phenyl phosphine aniline and the brominated carbazole phosphonic acid compound are used as raw materials, and a nucleophilic substitution reaction is carried out under the action of a catalyst, an organic ligand and a base to prepare the triphenylphosphine carbazole phosphonic acid compound; the catalyst is a metal halide, and the metal halide is selected from one or more of cuprous chloride, ferrous chloride, zinc chloride, cuprous bromide, ferrous bromide, zinc bromide, cuprous iodide, ferrous iodide and zinc iodide; the organic ligand is one or more of 2,2'-dipyridyl, trifluoroacetic acid, ethylenediaminetetraacetic acid, cyclooctatetraene, triacetyl triethylamine and imidazole; and the base is one or more of triethylamine, ammonia, sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate and potassium bicarbonate.

3. The method for preparing a hole transport material according to claim 2, characterized in that, The phenyl phosphine aniline is selected from one of the following compounds: Wherein, R2 and R3 are independently selected from one of oxygen atom, sulfur atom and selenium atom; The brominated carbazole phosphonic acid compound is: Wherein, R1 is selected from C1-C8 alkyl chain or aromatic chain.

4. The method of claim 3, wherein the hole-transport material is prepared by the steps of: The molar ratio of the phenyl phosphine aniline to the brominated carbazole phosphonic acid compound is 1:0.5-1:2, the reaction temperature of the phenyl phosphine aniline and the brominated carbazole phosphonic acid compound is 120-180 DEG C, and the reaction time is 12-24 hours.

5. A method for preparing a hole transport material according to claim 4, characterized in that, The molar ratio of the catalyst, the organic ligand and the base is 0.1:1:3-1:5:

10.

6. A perovskite solar cell module, characterized by, From top to bottom are a conductive substrate, a self-assembled monomolecular hole transport layer, a perovskite layer, an electron transport layer and a counter electrode layer, and the material of the self-assembled monomolecular hole transport layer is the triphenylphosphine carbazole phosphonic acid compound of claim 1.

7. The method for preparing a perovskite solar cell module according to claim 6, characterized in that, The method comprises the following steps: (1) etching the surface of the conductive substrate; (2) dissolving the triphenylphosphine carbazole phosphonic acid compound in a solvent to obtain a triphenylphosphine carbazole phosphonic acid compound solution, immersing the conductive substrate in the triphenylphosphine carbazole phosphonic acid compound solution by a chemical bath method to deposit the triphenylphosphine carbazole phosphonic acid compound on the surface of the conductive substrate, and obtaining a hole transport layer; (3) performing segmented cleaning on the surface of the hole transport layer obtained in step (2), using one or more of toluene, dichloromethane, petroleum ether, tetrahydrofuran and ethyl acetate as a cleaning solvent in the first stage, and using one or more of methanol, isopropanol, ethanol and N-methyl pyrrolidone as a cleaning solvent in the second stage; sequentially depositing a perovskite layer and an electron transport layer on the surface of the hole transport layer by a coating technique, and then etching the surfaces of the hole transport layer, the perovskite layer and the electron transport layer; (4) depositing a counter electrode layer on the surface of the electron transport layer, and then etching the surfaces of the hole transport layer, the perovskite layer, the electron transport layer and the counter electrode layer.

8. The method for preparing a perovskite solar cell module according to claim 7, characterized in that, In step (2), the solvent is selected from one of the following: a mixture of ethanol and water, a mixture of acetonitrile and water, a mixture of methanol and toluene, a mixture of acetone and water, and a mixture of dichloromethane and ethanol; and the concentration of the triphenylphosphine carbazole phosphonic acid compound in the solution of the triphenylphosphine carbazole phosphonic acid compound is 0.1-5 mg / mL.

9. The method for preparing a perovskite solar cell module according to claim 8, characterized in that, In step (2), the temperature of the chemical bath is 25-80 ℃; and the time for chemical bath deposition is 1-30 minutes.

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