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

Abstract

The invention belongs to the field of solar cells, and particularly relates to a self-assembled monomolecular hole transport material of a perovskite solar cell module and a preparation method of the self-assembled monomolecular hole transport material of the perovskite solar cell module, and the self-assembled monomolecular hole transport material of the perovskite solar cell module is a triphenylphosphino phosphonic acid carbazole compound. The preparation method comprises the following steps: etching the surface of the conductive substrate; the preparation method comprises the following steps: dissolving a triphenylphosphino carbazole phosphonate compound in a solvent to obtain a triphenylphosphino carbazole phosphonate compound solution, and depositing the triphenylphosphino carbazole phosphonate compound on the surface of a conductive substrate through 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 through a coating technology, and then etching the surface of the electron transport layer; and 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] The invention belongs to the field of solar cells, and in particular relates to a self-assembled single-molecule hole transport material of a perovskite solar cell component and a preparation method thereof. Background Art

[0002] Perovskite solar cells are currently one of the most promising photovoltaic technologies. The p-type organic small molecule Spiro-OMeTAD commonly used in nip formal structure perovskite devices has problems such as difficulty in large-area coating, easy water absorption and poor thermal stability, which greatly restricts the large-scale preparation of cells. Recently, pin trans-structured perovskite devices using p-type self-assembled molecules (SAM) with low carrier recombination losses as hole transport layers have achieved a cell photoelectric conversion efficiency of over 26%, which has attracted much attention from researchers. Importantly, the large-area preparation of SAM hole transport layers can be achieved through a simple low-temperature solution coating method, which can ensure the large-scale preparation of large-area trans-perovskite solar modules.

[0003] Nevertheless, under the actual working conditions of "light field / electric field / thermal stress", the Pb-I bond of the perovskite photoactive layer in the trans-perovskite solar module is easily broken to produce iodine. When iodine destroys the crystal structure under light, it induces the formation of more harmful iodine, causing the decomposition of the perovskite material to show a self-accelerating trend, which seriously affects the stability of the perovskite photovoltaic module. To this end, Chinese invention patent CN 118785794 A proposes a method of using crown ether additives to capture elemental iodine in perovskite films to prevent iodine from further corroding the perovskite. At the same time, crown ether additives can convert yellow phase formamidine iodine-based perovskite into black phase perovskite, improving the stability of the perovskite film. In addition, Chinese invention patent CN117295343 A proposes a method for constructing a multi-carbon chain fluorine-based molecular barrier layer in a perovskite device to capture harmful iodine produced in the perovskite film and improve the stability of the device under bias conditions.

[0004] In the prior art (CN 118852249 A), triphenylphosphine molecules are used alone as hole transport materials. Due to the low π-π stacking density, the hole transport capacity is insufficient, and the dipole moment of the triphenylphosphine molecules disclosed is too low (0.8D), the response to the electric field is weak, and it is difficult to form a strong interaction at the perovskite interface, resulting in poor interface contact. The low dipole moment leads to a weak affinity between triphenylphosphine and the perovskite surface, which reduces the wettability of the perovskite precursor solution and is not conducive to the expansion and preparation of large-area perovskite films. Summary of the invention

[0005] In view of the defects of the prior art, the present invention provides a self-assembled single-molecule hole transport material for a perovskite solar cell module and a preparation method thereof, which aims to solve the technical problems of poor stability and difficulty in large-scale preparation of perovskite solar modules in the prior art.

[0006] According to a first aspect of the present invention, a hole transport material is provided, comprising a triphenylphosphinophosphonic acid carbazole compound, wherein the triphenylphosphinophosphonic acid carbazole compound is selected from at least one of the compounds represented by formula I, formula II, and formula III:

[0007]

[0008]

[0009] Wherein, R1 is selected from a C1-C8 alkyl chain or an aromatic chain; R2 and R3 are independently selected from one of an oxygen atom, a sulfur atom and a selenium atom.

[0010] According to another aspect of the present invention, a method for preparing a hole transport material is provided. The method for preparing the triphenylphosphinophosphonic acid carbazole compound comprises taking phenylphosphine-paraphenylamine and bromophosphonic acid carbazole compound as reaction raw materials, carrying out a nucleophilic substitution reaction under the action of a catalyst, an organic ligand and a base to prepare the triphenylphosphinophosphonic acid carbazole compound.

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

[0012]

[0013] Wherein, R2 and R3 are independently selected from one of an oxygen atom, a sulfur atom and a selenium atom;

[0014] The brominated phosphonic acid carbazole compound is:

[0015]

[0016] Wherein, R1 is selected from a C1-C8 alkyl chain or an aromatic chain.

[0017] Preferably, the molar ratio of phenylphosphine to phenylamine and bromophosphonic acid carbazole compound is 1:0.5-1:2, the reaction temperature of phenylphosphine to phenylamine and bromophosphonic acid carbazole compound is 120-180°C, and the reaction time is 12-24h.

[0018] Preferably, 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′-bipyridine, trifluoroacetic acid, ethylenediaminetetraacetic acid, cyclooctatetraene, triacetamidotriethylamine, and imidazole; the base is one or more of triethylamine, ammonia water, sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and potassium bicarbonate; the molar ratio of the catalyst, the organic ligand, and the 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, which comprises, 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 triphenylphosphinophosphonic acid carbazole compound according to claim 1.

[0020] According to another aspect of the present invention, a method for preparing the perovskite solar cell module is provided, characterized in that it comprises the following steps:

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

[0022] (2) dissolving a triphenylphosphinophosphonic acid carbazole compound in a solvent to obtain a triphenylphosphinophosphonic acid carbazole compound solution, and immersing a conductive substrate in the triphenylphosphinophosphonic acid carbazole compound solution by a chemical bath method to deposit the triphenylphosphinophosphonic acid carbazole compound on the surface of the conductive substrate to obtain a hole transport layer;

[0023] (3) depositing a perovskite layer and an electron transport layer on the surface of the hole transport layer in sequence by coating technology, and then etching the surfaces of the hole transport layer, the perovskite layer, and the electron transport layer;

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

[0025] Preferably, in step (2), the solvent is selected from 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; and the concentration of the triphenylphosphinophosphonic acid carbazole compound in the triphenylphosphinophosphonic acid 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 to 80° C.; and the chemical bath deposition time is 1 to 30 minutes.

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

[0028] In general, the above technical solution conceived by the present invention has the following technical advantages compared with the prior art:

[0029] (1) The present invention utilizes the nucleophilic lone pair electrons of phosphorus atoms in triphenylphosphinophosphonic acid carbazole compounds to form chemical bonds with elemental iodine, thereby removing elemental iodine produced in the perovskite active layer and inhibiting the self-accelerated degradation process of perovskite, thereby improving the long-term operating stability of large-area perovskite photovoltaic modules.

[0030] (2) R2 and R3 on the triphenylphosphinophosphonic acid carbazole molecule of the present invention are selected from oxygen atoms, sulfur atoms or selenium atoms, and the lone pair electrons on the atoms can interact with the unsaturated metal cation orbital (such as Pb) at the bottom of the perovskite. 2+ The d orbital or empty p orbital of the molecule is used to supply electrons, thereby forming a coordination bond. This interaction will enhance the binding of the molecule to the perovskite surface, help improve the wettability of the perovskite precursor solution on the surface of the triphenylphosphinophosphonic acid carbazole molecule, and help prepare large-area high-quality perovskite films. In addition, the interaction between the triphenylphosphinophosphonic acid carbazole molecule and the perovskite can optimize the interface energy level arrangement and improve the charge transfer capacity of the device. The patent of this invention provides ideas for realizing the large-scale application of large-area, efficient and stable perovskite solar panels.

[0031] (3) The triphenylphosphinophosphonic acid carbazole molecules used in the present invention have high dipole moment characteristics, so that they can form a high built-in electric field at the perovskite interface, which is conducive to the separation of electrons and holes, and enhances the separation and transmission efficiency of carriers, thereby improving the photoelectric performance of perovskite photovoltaic modules. In addition, the high π-π stacking density in the triphenylphosphinophosphonic acid carbazole molecules can enhance the interaction between molecules and improve the structural stability of molecules or films. At the same time, the strong π-π stacking characteristics can reduce the degree of freedom of the material and reduce the structural changes caused by heat and light, thereby improving the long-term stability of the battery.

[0032] (4) In order to solve the key problems of expensive palladium metal catalysts and low yield in the nucleophilic substitution reaction, the present invention adopts cheap and highly active metal halides as catalysts. Under the synergistic effect of ligands and bases, the yield of triphenylphosphinophosphonic acid carbazole molecules prepared by nucleophilic substitution can be greatly improved, which can effectively solve the key problems of low yield and high cost in the synthesis process 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 modification layer of the present invention is cleaned in stages. The first stage removes physically adsorbed unreacted triphenylphosphinophosphonic acid carbazole molecules, and the second stage removes weakly adsorbed triphenylphosphinophosphonic acid carbazole molecules and irregular assemblies to obtain a high-quality, dense triphenylphosphinophosphonic acid carbazole compound monolayer. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The invention relates to a preparation process of triphenylphosphinophosphonic acid carbazole compounds.

[0035] Figure 2 Schematic diagram of a perovskite solar panel.

[0036] In the figure, 1, conductive substrate; 2, hole transport layer; 3, perovskite layer; 4, electron transport layer; 5, counter electrode layer DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0038] The present invention provides a perovskite solar cell assembly, which comprises, 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 above-mentioned triphenylphosphine phosphonic acid carbazole compound.

[0039] The present 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) dissolving a triphenylphosphinophosphonic acid carbazole compound in a solvent to obtain a triphenylphosphinophosphonic acid carbazole compound solution, and immersing a conductive substrate in the triphenylphosphinophosphonic acid carbazole compound solution by a chemical bath method to deposit the triphenylphosphinophosphonic acid carbazole compound on the surface of the conductive substrate to obtain a hole transport layer;

[0042] (3) depositing a perovskite layer and an electron transport layer on the surface of the hole transport layer in sequence by coating technology, and then etching the surfaces of the hole transport layer, the perovskite layer, and the electron transport layer;

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

[0044] In some embodiments, in step (2), the solvent is selected from 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; and the concentration of the triphenylphosphinophosphonic acid carbazole compound in the triphenylphosphinophosphonic acid 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 to 80° C.; and the chemical bath deposition time is 1 to 30 minutes.

[0046] In some embodiments, the surface of the hole modification 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] The present invention provides an application of a perovskite solar cell module, and the perovskite solar cell module is applied to electrical equipment.

[0051] Example 1

[0052] Preparation of 4,4′-dithiophenylphosphine-p-aniline: In a dry, inert environment, weigh 4-bromoaniline and 4,4′-dithiophenylphosphine at a molar ratio of 1:1.2. Add 0.1 mol of cuprous bromide, 1 mol of pyridine and 3 mol of potassium carbonate to DMSO containing 4-bromoaniline and 4,4′-dithiophenylphosphine. Heat the reaction solution to 120°C for 24 hours. After the reaction is completed, cool to room temperature, dilute with water and extract with ethyl acetate. Combine the organic layers, dry and remove the solvent. Separate and purify by recrystallization to obtain 4,4′-dithiophenylphosphine-p-aniline.

[0053] The synthesis steps of thiotriphenylphosphinophosphonic acid carbazole compound are as follows: 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) are added into a 500 ml three-necked flask, and stirred for 12 h at 120° C. in a high-purity nitrogen atmosphere. The chemical reaction formula is as follows: Figure 1 As shown. Subsequently, after the reaction temperature is reduced to room temperature, the crude reaction product is washed three times with 50 ml of ionized water and 80 ml of methanol respectively, and the washed product is purified by column chromatography to prepare a pure thiotriphenylphosphinophosphonic acid carbazole compound. Under this condition, the yield of thiotriphenylphosphinophosphonic acid carbazole is 92%, as shown in Table 1.

[0054] Preparation steps of trans-perovskite solar cell modules: Etching is performed on 100◇100◇1.5 (length, width, thickness, in millimeters) indium-doped tin oxide (ITO) glass by laser scribing process. Subsequently, the ITO glass is ultrasonically cleaned with detergent, acetone and industrial ethanol for 15 minutes respectively, and then cleaned with ultraviolet ozone for 30 minutes. The above substrate is immersed in a 2mg / mL isopropanol solution of thiotriphenylphosphinophosphonic acid carbazole by chemical bath method, immersed at 25°C for 10 minutes, then washed with ethyl acetate for 50 seconds, and then washed with methanol for 10 seconds to remove the unanchored thiotriphenylphosphinophosphonic acid carbazole molecules on the surface, and annealed in an air atmosphere at 100°C for 10 minutes. 1.3M Cs 0.05 MA 0.05 FA 0.9The PbI3 perovskite solution is coated on the surface of the hole transport layer, and the high-pressure nitrogen wind knife causes the solvent in the perovskite precursor to evaporate quickly. When the color of the film turns brown, the perovskite film is transferred to a hot stage at 100°C for annealing for 1 hour, and annealed at 150°C for 10 minutes to obtain a perovskite film with high crystalline quality. Subsequently, the electron transport layer materials C60 and BCP are coated on its surface in sequence through a vapor deposition process. The surface of the hole transport layer, perovskite layer, and electron transport layer are etched through a laser scribing process. Subsequently, a metal copper electrode is evaporated on its surface. Finally, the hole transport layer, perovskite layer, electron transport layer, and counter electrode layer are etched through a laser scribing process to realize the series connection of each sub-battery, such as Figure 2 The photoelectric conversion efficiency and stability of the perovskite solar module are shown in Table 2.

[0055] Example 2

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

[0057] Example 3

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

[0059] Example 4

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

[0061] Example 5

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

[0063] Example 6

[0064] The steps were the same as those in Example 5, except that the molar ratio of cuprous bromide, pyridine and potassium carbonate was adjusted to 0.1:2:5, and the yield of thiotriphenylphosphinophosphonic acid carbazole was 96%.

[0065] Example 7

[0066] The steps are the same as those 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 thiotriphenylphosphinophosphonic acid carbazole is 92%.

[0067] Example 8

[0068] The steps were the same as those in Example 6, except that cuprous bromide was replaced by ferrous bromide, and the yield of thiotriphenylphosphinophosphonic acid carbazole was 98%.

[0069] Example 9

[0070] The steps are the same as those in Example 8, except that the concentration of the triphenylphosphinothiocarbazole solution is 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 are the same as those in Example 8, except that the concentration of the triphenylphosphinothiocarbazole solution is adjusted to 3 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0073] Embodiment 11

[0074] The steps are the same as those in Example 8, except that the concentration of the triphenylphosphinothiocarbazole solution is 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 are the same as those in Example 8, except that the concentration of the triphenylphosphinothiocarbazole solution is adjusted to 5 mg / mL. The photoelectric conversion efficiency and stability test results of the perovskite solar module are shown in Table 2.

[0077] Embodiment 13

[0078] The steps are the same as those 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] Embodiment 14

[0080] The steps are the same as those 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 those in Example 1, except that triphenylphosphinophosphonic acid carbazole is replaced with triphenylphosphinophosphonic acid. The photoelectric conversion efficiency and stability of the perovskite solar cell module are shown in Table 2.

[0083] Comparison 2

[0084] The steps are the same as those in Example 10, except that ethyl acetate is used only once in the step of cleaning the thiotriphenylphosphinophosphonic acid 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 thiotriphenylphosphinophosphonic acid carbazole 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 Photoelectric conversion efficiency of cells in different embodiments (module area 100cm 2 , active area 75.4cm 2 ).

[0088]

[0089]

[0090] It will be easily understood by those skilled in the art that the above description is only 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 in the protection scope of the present invention.

Claims

1. A hole transport material, characterized in that: It includes a triphenylphosphinophosphonic acid carbazole compound, wherein the triphenylphosphinophosphonic acid carbazole compound is selected from at least one of the compounds represented by formula I, formula II, and formula III: Wherein, R1 is selected from a C1-C8 alkyl chain or an aromatic chain; R2 and R3 are independently selected from one of an oxygen atom, a sulfur atom and a selenium atom.

2. The method for preparing a hole transport material according to claim 1, characterized in that: Phenylphosphine-p-aniline and bromophosphonic acid carbazole compounds are used as reaction raw materials, and a nucleophilic substitution reaction is carried out under the action of a catalyst, an organic ligand and a base to prepare triphenylphosphine-phosphonic acid carbazole compounds.

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

4. The method for preparing a hole transport material according to claim 3, characterized in that: The molar ratio of the phenylphosphine-paraphenylamine to the bromophosphonic acid carbazole compound is 1:0.5-1:2, the reaction temperature of the phenylphosphine-paraphenylamine and the bromophosphonic acid carbazole compound is 120-180°C, and the reaction time is 12-24 hours.

5. The method for preparing a hole transport material according to claim 4, characterized in that: 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′-bipyridine, trifluoroacetic acid, ethylenediaminetetraacetic acid, cyclooctatetraene, triacetamidotriethylamine, and imidazole; the base is one or more of triethylamine, ammonia water, sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and potassium bicarbonate; the molar ratio of the catalyst, the organic ligand, and the base is 0.1:1:3 to 1:5:

10.

6. A perovskite solar cell module, characterized in that: From top to bottom, they are respectively a conductive substrate, a self-assembled monomolecular hole transport layer, a perovskite layer, an electron transport layer, and a counter electrode layer. The self-assembled monomolecular hole transport layer material is the triphenylphosphinophosphonic acid carbazole compound as described in claim 1.

7. The method for preparing a perovskite solar cell module according to any one of claims 1 to 6, characterized in that: The steps include: (1) etching the surface of the conductive substrate; (2) dissolving a triphenylphosphinophosphonic acid carbazole compound in a solvent to obtain a triphenylphosphinophosphonic acid carbazole compound solution, and immersing a conductive substrate in the triphenylphosphinophosphonic acid carbazole compound solution by a chemical bath method to deposit the triphenylphosphinophosphonic acid carbazole compound on the surface of the conductive substrate to obtain a hole transport layer; (3) depositing a perovskite layer and an electron transport layer on the surface of the hole transport layer in sequence by coating technology, 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 surface 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 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; and the concentration of the triphenylphosphinophosphonic acid carbazole compound in the triphenylphosphinophosphonic acid carbazole compound solution is 0.1 to 5 mg / mL.

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

10. The method for preparing a perovskite solar cell module according to claim 9, characterized in that: The surface of the hole modification 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.

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