Self-assembled monomolecular hole transport material and preparation method and application thereof, perovskite solar cell and preparation method thereof, and photovoltaic module

Abstract

The invention relates to the technical field of solar cells, in particular to a self-assembled monomolecular hole transport material, a preparation method and application thereof, a perovskite solar cell, a preparation method thereof and a photovoltaic module. The self-assembled monomolecular hole transport material provided by the invention has a structure as shown in a formula I. In the formula I, A1, A2 and A3 are respectively and independently anchor groups or hydrogen atoms; the anchoring groups are independently selected from phosphate groups respectively; g is selected from a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenothiazinyl group, and a substituted or unsubstituted phenoxazinyl group. The self-assembled monomolecular hole transport material provided by the invention has stronger anchoring binding capacity, conjugation in molecules is enhanced through the aromatic connection unit, and transport of carriers is facilitated; polyphosphonic acid anchoring in the self-assembled monomolecular hole transport material provided by the invention can enhance adsorption and uniformity of molecules, and a formed hole transport interface has better charge transport and defect passivation effects.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to a self-assembled single-molecule hole transport material and its preparation method and application, perovskite solar cells and their preparation method, and photovoltaic modules. Background Technology

[0002] Currently, monocrystalline silicon solar cells are the most widely used, but they are still constrained by inherent defects in their manufacturing process, such as high energy consumption and heavy pollution. In recent years, perovskite solar cells (PSCs), which are cost-effective and easy to process, have developed extremely rapidly, surpassing polycrystalline silicon and thin-film silicon, and are comparable to CdTe and CIGS solar cells, showing great application potential and commercial prospects.

[0003] However, while pursuing high performance, ensuring the long-term stable operation of PSCs has become a major challenge for researchers. The hole transport layer is a key component affecting device performance. Traditional high-performance liquid chromatography (HTL) materials, such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), although widely used, suffer from high cost and poor compatibility with perovskite interfaces, limiting the large-scale commercialization of PSCs. Against this backdrop, self-assembled monolayers (SAMs) have gradually emerged as a novel type of HTL material. SAMs possess unique structural characteristics: they can be directly bonded to the substrate surface via chemical bonds to form a uniform and dense film; simultaneously, the energy level matching between SAMs and perovskites can be tuned, thereby optimizing charge separation efficiency. Furthermore, compared to traditional organic HTL materials, SAMs require extremely low quantities, which not only helps reduce production costs but also minimizes environmental impact. More importantly, appropriately selected or modified SAMs can significantly improve the operational stability of PSCs.

[0004] Therefore, exploring efficient, stable and economical self-assembled hole transport materials suitable for perovskite solar cells has become one of the current research hotspots, and is expected to provide new ideas and technical support for solving the problems encountered in the industrialization of PSCs.

[0005] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the Invention

[0006] This application provides a self-assembled single-molecule hole transport material, its preparation method and application, a perovskite solar cell, its preparation method and photovoltaic module, to solve or alleviate one or more of the technical problems mentioned above.

[0007] In a first aspect, embodiments of this application provide a self-assembled monomolecular hole transport material, the self-assembled monomolecular hole transport material having the structure shown in Formula I:

[0008] Formula I Wherein, A1, A2, and A3 are each and independently anchoring groups or hydrogen atoms; the anchoring groups are each independently selected from phosphate groups; G is selected from substituted or unsubstituted carbazolyl, substituted or unsubstituted acridinel, substituted or unsubstituted phenothiazinel, or substituted or unsubstituted phenothiazinel.

[0009] Optionally, at least two of A1, A2 and A3 are anchoring groups, and the anchoring groups are phosphate groups.

[0010] Optionally, the number of carbon atoms in G is limited to 6 to 30.

[0011] Optionally, G is selected from one of the following structural formulas: , , , , , , , , , , ; Among them, X1-X 12 Each and every one is selected independently from one of the following groups: hydrogen atom, methyl, methoxy, methylthio, phenyl, methylphenyl, methoxyphenyl, thiophene, furanyl, and aromatic amino group; X 13 It is selected from one of the following: oxygen atom, sulfur atom, and dialkyl-substituted methylene group.

[0012] Optionally, the molecule corresponding to G is selected from one of the following structural formulas:

[0013]

[0014]

[0015]

[0016]

[0017] .

[0018] Optionally, the self-assembled monomolecular hole transport material is selected from the following structures: , , , , , , .

[0019] Secondly, embodiments of this application provide a method for preparing a self-assembled single-molecule hole transport material, comprising the following steps: Step 1: The molecule corresponding to the terminal functional group G undergoes a coupling reaction with a haloaromatic compound to generate intermediate a; Step 2: Intermediate a from Step 1 undergoes a substitution reaction with a phosphite compound to generate intermediate b; Step 3: React intermediate b from step 2 with a halosilane, and then perform a hydrolysis reaction after the reaction is complete to obtain a self-assembled monomolecular hole transport material.

[0020] Optionally, the method for preparing the self-assembled single-molecule hole transport material includes the following steps: Step 1: The molecule corresponding to the terminal functional group G undergoes a coupling reaction with a haloaromatic compound to generate intermediate a; Step 2: Intermediate a from Step 1 undergoes a substitution reaction with a phosphite compound to generate intermediate b; Step 3: Dissolve intermediate b from step 2 in an organic solvent, add a halosilane compound to react, remove the organic solvent after the reaction is complete, add an alcohol compound, add water to carry out a hydrolysis reaction until the reaction product precipitates, and filter to obtain a self-assembled single-molecule hole transport material.

[0021] Thirdly, embodiments of this application provide an application of a self-assembled monolayer hole transport material, which is applied to a perovskite solar cell.

[0022] Fourthly, embodiments of this application provide a perovskite solar cell, which includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and an electrode stacked sequentially, wherein the hole transport layer is made of the self-assembled single-molecule hole transport material described above.

[0023] Optionally, a hole blocking layer is further provided between the electron transport layer and the electrode.

[0024] like Figure 6 As shown, the perovskite solar cell provided in this application embodiment includes a conductive substrate 110, a hole transport layer 120, a perovskite light-absorbing layer 130, an electron transport layer 140, a hole blocking layer 150, and an electrode 160.

[0025] Fifthly, embodiments of this application provide a method for fabricating a perovskite solar cell, comprising: providing a conductive substrate; The self-assembled monomolecular hole transport material described above is dispersed in a solvent to obtain a hole transport material dispersion; then the hole transport material dispersion is placed on the upper surface of a conductive substrate, and spin-coated and heated for annealing to obtain a hole transport layer. A perovskite light-absorbing layer is formed on the upper surface of the hole transport layer; An electron transport layer is formed on the upper surface of the perovskite light-absorbing layer; An electrode is formed on the upper surface of the electron transport layer.

[0026] Sixthly, embodiments of this application provide a photovoltaic module, including a perovskite solar cell as described above or a perovskite solar cell prepared by the method described above.

[0027] The embodiments of this application employing the above-described technical solution may have the following advantages: The self-assembled single-molecule hole transport material provided in this application adopts polyphosphonic acid aromatic anchoring groups, which enhances the anchoring ability without affecting the dipole interaction of the self-assembled single-molecule hole transport material molecules. Moreover, it expands the molecular structure of the self-assembled single-molecule hole transport material and provides different terminal functional groups to meet the requirements of different perovskite compositions for the HOMO energy level of the hole transport material.

[0028] The self-assembled single-molecule hole transport material provided in this application has stronger anchoring and binding capabilities. The aromatic linking units enhance intramolecular conjugation, which is conducive to carrier transport. The polyphosphonic acid anchoring in the self-assembled single-molecule hole transport material provided in this application can enhance molecular adsorption and uniformity, and the hole transport interface formed has better charge transport and defect passivation effects.

[0029] The hole transport layer obtained by the self-assembled single-molecule hole transport material provided in this application can improve the light absorption effect, charge separation and transport effect, low charge transport loss, and high photoelectric conversion efficiency of perovskite solar cells. Attached Figure Description

[0030] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0031] Figure 1 This is the NMR spectrum of the self-assembled monomolecular hole transport material provided in Example 1 of this application.

[0032] Figure 2 This is the mass spectrum of the self-assembled monomolecular hole transport material provided in Example 2 of this application.

[0033] Figure 3 This is the mass spectrum of the self-assembled monomolecular hole transport material provided in Example 3 of this application.

[0034] Figure 4 This is the mass spectrum of the self-assembled monomolecular hole transport material provided in Example 5 of this application.

[0035] Figure 5 This is the mass spectrum of the self-assembled monomolecular hole transport material provided in Example 7 of this application.

[0036] Figure 6 This is a structural diagram of the perovskite solar cell provided in the embodiments of this application.

[0037] Explanation of reference numerals in the attached figures: Figure 6 In the middle: conductive substrate 110, hole transport layer 120, perovskite light-absorbing layer 130, electron transport layer 140, hole blocking layer 150 and electrode 160. Detailed Implementation

[0038] The embodiments of this application are described in detail below, examples of which are illustrated in the accompanying drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Throughout, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0039] It should be understood that when an element or layer is referred to as "on," "adjacent to," "connected to," or "coupled to" other elements or layers, it may be directly on, adjacent to, connected to, or coupled to other elements or layers, or there may be intervening elements or layers. Conversely, when an element is referred to as "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" other elements or layers, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc., may be used to describe various elements, components, areas, layers, and / or portions, these elements, components, areas, layers, and / or portions should not be limited by these terms. These terms are only used to distinguish one element, component, area, layer, or portion from another element, component, area, layer, or portion. Therefore, without departing from the teachings of this disclosure, the first element, component, area, layer, or portion discussed below may be referred to as a second element, component, area, layer, or portion. And the discussion of a second element, component, area, layer, or portion does not imply that the first element, component, area, layer, or portion necessarily exists in this application.

[0040] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise expressly limited. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0041] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0042] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0043] Exemplary embodiments according to this application will now be described in more detail with reference to the accompanying drawings. It should be understood that these exemplary embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.

[0044] This application provides a self-assembled single-molecule hole transport material. This self-assembled single-molecule hole transport material has the structure shown in Formula I:

[0045] Formula I Wherein, A1, A2, and A3 are each and independently anchoring groups or hydrogen atoms; the anchoring groups are each independently selected from one of phosphate groups, carboxylic acid groups, sulfonic acid groups, cyanoacrylate, and cycloheptatrienolone. G is selected from substituted or unsubstituted carbazolyl, substituted or unsubstituted acridinel, substituted or unsubstituted phenothiazinel, or substituted or unsubstituted phenothiazinel.

[0046] In an optional embodiment, at least two of A1, A2 and A3 are anchoring groups, and the anchoring groups are phosphate groups.

[0047] In an optional embodiment, the number of carbon atoms in G is limited to 6 to 30 (exemplary, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30).

[0048] In an optional embodiment, G is selected from one of the following structural formulas: , , , , , , , , , , ; Among them, X1-X 12 Each and every one is selected independently from one of the following groups: hydrogen atom, methyl, methoxy, methylthio, phenyl, methylphenyl, methoxyphenyl, thiophene, furanyl, and aromatic amino group; X 13 It is selected from one of the following: oxygen atom, sulfur atom, and dialkyl-substituted methylene group.

[0049] In an optional embodiment, the molecule corresponding to G is selected from one of the following structural formulas:

[0050]

[0051]

[0052] .

[0053] In an optional embodiment, the self-assembled monomolecular hole transport material is selected from the following structures: , , , , , , , .

[0054] This application also provides a method for preparing a self-assembled single-molecule hole transport material.

[0055] The preparation method includes the following steps: Step 1: The molecule corresponding to the terminal functional group G undergoes a coupling reaction with a haloaromatic compound to generate intermediate a; Step 2: Intermediate a from Step 1 undergoes a substitution reaction with a phosphite compound to generate intermediate b; Step 3: React intermediate b from step 2 with a halosilane, and then perform a hydrolysis reaction after the reaction is complete to obtain a self-assembled monomolecular hole transport material.

[0056] In an optional embodiment, the method for preparing the self-assembled single-molecule hole transport material includes the following steps: Step 1: The molecule corresponding to the terminal functional group G undergoes a coupling reaction with a haloaromatic compound to generate intermediate a; Step 2: Intermediate a from Step 1 undergoes a substitution reaction with a phosphite compound to generate intermediate b; Step 3: Dissolve intermediate b from step 2 in an organic solvent, add a halosilane compound to react, remove the organic solvent after the reaction is complete, add an alcohol compound, add water to carry out a hydrolysis reaction until the reaction product precipitates, and filter to obtain a self-assembled single-molecule hole transport material.

[0057] In optional embodiments, the haloaromatic compound includes, but is not limited to, 3,5-dibromoiodobenzene.

[0058] In optional embodiments, the phosphite compounds include, but are not limited to, diethyl phosphite.

[0059] In optional embodiments, the halosilane includes, but is not limited to, trimethylbromosilane.

[0060] In an optional embodiment, the preparation method includes the following steps: Step 1: The molecule corresponding to the terminal functional group undergoes a coupling reaction with 3,5-dibromoiodobenzene to generate intermediate a; Step 2: Intermediate a from Step 1 undergoes a substitution reaction with diethyl phosphite to generate intermediate b; Step 3: Dissolve intermediate b from Step 2 in an organic solvent and react it with trimethylbromosilane. Then add alcohol and water to carry out hydrolysis. The resulting reaction product precipitates out and is filtered to obtain a self-assembled monomolecular hole transport material.

[0061] In an optional embodiment, the preparation method includes the following steps: Step 1: The molecule corresponding to the terminal functional group G, 3,5-dibromoiodobenzene, potassium phosphate, cuprous iodide, and dimethylethylenediamine were added to a reaction flask. Toluene was added under nitrogen protection, and the mixture was heated and stirred to initiate a coupling reaction. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a. Step 2: Mix intermediate a and diethyl phosphite, add potassium acetate, triethylamine, bis(diphenylphosphine)ferrocene palladium dichloride and tetrahydrofuran, and heat to prepare phosphate intermediate b. Step 3: Dissolve intermediate b in an organic solvent, then add trimethylbromosilane to react. After the reaction is complete, remove the organic solvent by rotary evaporation, then add methanol and water. The hydrolyzed reaction product precipitates out and is filtered to obtain a self-assembled single-molecule hole transport material.

[0062] In an optional embodiment, the organic solvent in step three includes dichloromethane.

[0063] This application embodiment can also provide an application of a self-assembled monolayer hole transport material, which is applied to a perovskite solar cell.

[0064] This application embodiment can also provide a perovskite solar cell, including a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer and an electrode stacked sequentially, wherein the hole transport layer includes the self-assembled single-molecule hole transport material described above.

[0065] In an optional embodiment, a hole blocking layer is further provided between the electron transport layer and the electrode.

[0066] like Figure 6 As shown, the specific structure of the perovskite solar cell is as follows: It includes a conductive substrate 110, a hole transport layer 120, a perovskite light-absorbing layer 130, an electron transport layer 140, a hole blocking layer 150, and an electrode 160, which are stacked in sequence.

[0067] This application embodiment can also provide a method for preparing a perovskite solar cell, including: Provide a conductive substrate; The self-assembled monomolecular hole transport material described above is dispersed in a solvent to obtain a hole transport material dispersion; then the hole transport material dispersion is placed on the upper surface of a conductive substrate, and spin-coated and heated for annealing to obtain a hole transport layer. A perovskite light-absorbing layer is formed on the upper surface of the hole transport layer; An electron transport layer is formed on the upper surface of the perovskite light-absorbing layer; An electrode is formed on the upper surface of the electron transport layer.

[0068] In an optional embodiment, the method for fabricating the perovskite solar cell includes the following steps: (1) The TCO conductive glass was ultrasonically cleaned with deionized water, acetone and isopropanol in sequence, and then placed in a drying oven for drying. The dried TCO glass substrate was placed in an ultraviolet ozone machine to remove organic impurities on its surface and optimize its surface wettability. (2) The self-assembled single-molecule hole transport material is dispersed in an ethanol solution; ultrasonication is performed to obtain a hole transport material dispersion. (3) Take the hole transport material dispersion and drop it onto the TCO glass. Spin coat it at a speed of 4000-6000 rpm (exemplary, such as 4000 rpm, 4300 rpm, 4500 rpm, 4800 rpm, 5000 rpm, 5300 rpm, 5500 rpm, 5800 rpm, 6000 rpm) for 10-50 s (exemplary, such as 10 s, 15 s, 20 s, 25 s, 30 s, 35 s, 40 s, 45 s, 50 s). Place the TCO glass on a hot stage for heating and annealing to obtain the hole transport layer. (4) Dissolve lead iodide and methyl iodide solids in N,N-dimethylformamide (DMF) and stir at room temperature until completely dissolved to obtain a perovskite precursor solution; in a nitrogen glove box, drop the perovskite precursor solution onto the ITO conductive glass forming the hole transport layer, first spin-coating at 500-2000 rpm (exemplary, such as 500 rpm, 800 rpm, 1000 rpm, 1200 rpm, 1500 rpm, 1800 rpm, 2000 rpm) for 5-20 s (exemplary, such as 5 s, 10 s, 15 s, 20 s), then spin-coating at 4000-6000 rpm (exemplary, such as 40 ...4000 rpm, 800 rpm, 1000 rpm, 1500 rpm, 1800 rpm, 2000 rpm) for 5-20 s (exemplary, such as 4000 rpm, 800 rpm, 1000 rpm, 1500 rpm, 1800 rpm, 180 Spin coat the TCO glass at speeds of 0 rpm, 4300 rpm, 4500 rpm, 4800 rpm, 5000 rpm, 5300 rpm, 5500 rpm, 5800 rpm, and 6000 rpm for 10-50 seconds (exemplary values ​​such as 10 s, 15 s, 20 s, 25 s, 30 s, 35 s, 40 s, 45 s, and 50 s). During this process, rapidly add chlorobenzene at 20-30 seconds (exemplary values ​​such as 20 s, 21 s, 22 s, 23 s, 24 s, 25 s, 26 s, 27 s, 28 s, 29 s, and 30 s). Then, place the TCO glass on a hot stage for heating and annealing to form a perovskite light-absorbing layer. (5) Dissolve methane fullerene phenyl-C61-butyrate methyl ester (PCBM) in chlorobenzene and stir at room temperature to obtain a [6,6]-phenyl-C61-butyrate methyl ester solution; spin-coat an electron transport layer onto an ITO conductive glass on which a perovskite light-absorbing layer has been formed by the [6,6]-phenyl-C61-butyrate methyl ester solution; (6) Dissolve 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol and stir at room temperature to obtain a hole blocking layer solution; take the hole blocking layer solution and drop it onto the electron transport layer, then spin-coat to form a hole blocking layer. (7) Transfer the TCO conductive glass, which forms a hole blocking layer, an electron transport layer, an interface modification layer, a perovskite light-absorbing layer, and a hole transport layer, to a vacuum coating instrument. Deposit a silver electrode under vacuum conditions to form a silver electrode on the hole blocking layer, thus obtaining the electrode layer.

[0069] This application provides a photovoltaic module, including a perovskite solar cell as described above or a perovskite solar cell prepared by the method described above.

[0070] In an optional embodiment, the photovoltaic module includes at least one battery string, which includes at least two solar cells as described above.

[0071] The following specific embodiments provide a more detailed description of this application, but should not be construed as limiting the application. Any modifications or substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are within the scope of this application.

[0072]

Preparation Example 1

[0073] A method for preparing a self-assembled single-molecule hole transport material SAM1 includes the following steps: Step 1: 3,6-Dimethylcarbazole (1.08 g, 6.0 mmol), 3,5-dibromoiodobenzene (2.60 g, 7.2 mmol), potassium phosphate (3.82 g, 18.0 mmol), cuprous iodide (114 mg, 0.6 mmol), and dimethylethylenediamine (106 mg, 1.2 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a1 with a weight of 2.10 g, yielding 82%. Step 2: Intermediate a1 (1.29 g, 3.0 mmol) was dissolved in 15 mL of diethyl phosphite (1.24 g, 9.0 mmol), potassium acetate (60 mg, 0.6 mmol), triethylamine (323 mg, 3.6 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (440 mg, 0.6 mmol) and 30 mL of tetrahydrofuran were added. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b1 with a weight of 1.45 g, with a yield of 90%. Step 3: Intermediate b1 (1.45 g, 2.7 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.06 g, 13.5 mmol). The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material SAM1. SAM1 was a light yellow solid, and the weight of the obtained SAM1 was 0.9 g, with a yield of 85%. The NMR spectrum of SAM1 is shown below. Figure 1 The NMR spectrum of SAM1 is 1H NMR (400MHz, DMSO) δ 8.15-8.09 (m, 1H), 7.96-7.79 (m, 4H), 7.28 (d, J=8.7Hz, 2H), 7.04 (dd, J=8.8, 2.5Hz, 2H), 2.48 (s, 6H).

[0074]

Preparation Example 2

[0075] A method for preparing a self-assembled single-molecule hole transport material SAM2 includes the following steps: Step 1: 3,6-bis(4-methoxyphenyl)carbazole (1.14 g, 3.0 mmol), 3,5-dibromoiodobenzene (1.30 g, 3.6 mmol), potassium phosphate (1.91 g, 9.0 mmol), cuprous iodide (57 mg, 0.3 mmol), and dimethylethylenediamine (53 mg, 0.6 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a2 with a weight of 1.56 g, yielding 85%. Step 2: Intermediate a2 (1.50 g, 2.45 mmol) was added to (1.03 g, 7.5 mmol), followed by potassium acetate (30 mg, 0.3 mmol), triethylamine (208 mg, 2.4 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (220 mg, 0.3 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b2 with a weight of 1.66 g, yielding 93%. Step 3: Intermediate b2 (1.66 g, 2.3 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.06 g, 13.5 mmol). The mixture was reacted at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material (SAM2). SAM2 was a white solid, and the weight of the obtained SAM2 was 1.23 g, with a yield of 87%. Mass spectrometry analysis of SAM2 yielded the following mass spectrum: [See attached image]. Figure 2 The mass spectrum of the self-assembled single-molecule hole transport material SAM2 is as follows: MS (m / z, [MH]). - ):614.10.

[0076]

Preparation Example 3

[0077] A method for preparing a self-assembled single-molecule hole transport material SAM3 includes the following steps: Step 1: 9,9-Dimethylacridine (1.05 g, 5.0 mmol), 3,5-dibromoiodobenzene (2.17 g, 6.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), cuprous iodide (95 mg, 0.5 mmol), and dimethylethylenediamine (88 mg, 1.0 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a3 with a weight of 1.60 g, yielding 72%. Step 2: Intermediate a3 (1.50 g, 3.38 mmol) was added to diethyl phosphite (1.40 g, 10.14 mmol), followed by potassium acetate (67 mg, 0.68 mmol), triethylamine (410 mg, 4.05 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (260 mg, 0.34 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b3 with a weight of 1.71 g, yielding 91%. Step 3: Intermediate b3 (1.71 g, 3.07 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.35 g, 15.3 mmol). The mixture was reacted at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, self-assembled single-molecule hole transport material SAM3, which was a white solid. The weight of the obtained self-assembled single-molecule hole transport material SAM3 was 1.12 g, with a yield of 82%. Mass spectrometry analysis of the self-assembled single-molecule hole transport material SAM3 was performed, and the mass spectrum is shown below. Figure 3 The mass spectrum of the self-assembled single-molecule hole transport material SAM3 is as follows: MS (m / z, MH) - ):444.10.

[0078]

Preparation Example 4

[0079] A method for preparing a self-assembled single-molecule hole transport material SAM4 includes the following steps: Step 1: 9,9-Dimethyl-2,7-diphenyl-9,10-dihydroacridine (1.08 g, 3.0 mmol), 3,5-dibromoiodobenzene (1.30 g, 3.6 mmol), potassium phosphate (1.91 g, 9.0 mmol), cuprous iodide (57 mg, 0.3 mmol), and dimethylethylenediamine (53 mg, 0.6 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a4 with a weight of 1.41 g, yielding 79%. Step 2: Intermediate a4 (1.41 g, 2.37 mmol) was added to diethyl phosphite (0.98 g, 7.1 mmol), followed by potassium acetate (30 mg, 0.3 mmol), triethylamine (208 mg, 2.4 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (220 mg, 0.3 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b4 with a weight of 1.50 g, yielding 89%. Step 3: Intermediate b4 (1.50 g, 2.1 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (1.61 g, 10.5 mmol). The mixture was reacted at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material (SAM4). SAM4 was a white solid, and the weight of the obtained SAM4 was 1.03 g, with a yield of 82%. Mass spectrometry analysis of SAM4 yielded the following results: MS (m / z, MH). - ):596.13.

[0080]

Preparation Example 5

[0081] A method for preparing a self-assembled single-molecule hole transport material SAM5 includes the following steps: Step 1: Phenothiazine (1.05 g, 5.0 mmol), 3,5-dibromoiodobenzene (2.17 g, 6.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), cuprous iodide (95 mg, 0.5 mmol), and dimethylethylenediamine (88 mg, 1.0 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a5 with a weight of 1.47 g, yielding 68%. Step 2: Intermediate a5 (1.47 g, 3.40 mmol) was added to diethyl phosphite (1.40 g, 10.2 mmol), followed by potassium acetate (67 mg, 0.68 mmol), triethylamine (410 mg, 4.05 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (260 mg, 0.34 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b5 with a weight of 1.73 g, yielding 93%. Step 3: Intermediate b5 (1.73 g, 3.16 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.42 g, 15.8 mmol). The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material (SAM5). SAM5 was a white solid, and the weight of the obtained SAM5 was 1.18 g, with a yield of 86%. Mass spectrometry analysis of SAM5 yielded the following mass spectrum: [See attached image]. Figure 4 The mass spectrum of the self-assembled single-molecule hole transport material SAM5 is as follows: MS (m / z, MH) - ): 434.20.

[0082]

Preparation Example 6

[0083] A method for preparing a self-assembled single-molecule hole transport material SAM6 includes the following steps: Step 1: 2-Methylthiophenthiazide (1.27 g, 5.0 mmol), 3,5-dibromoiodobenzene (2.17 g, 6.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), cuprous iodide (95 mg, 0.5 mmol), and dimethylethylenediamine (88 mg, 1.0 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a6 with a weight of 1.56 g, yielding 65%. Step 2: Intermediate a6 (1.56 g, 3.25 mmol) was added to diethyl phosphite (1.35 g, 9.75 mmol), followed by potassium acetate (67 mg, 0.68 mmol), triethylamine (410 mg, 4.05 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (260 mg, 0.34 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b6 with a weight of 1.70 g, yielding 88%. Step 3: Intermediate b6 (1.70 g, 2.86 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.30 g, 15 mmol). The mixture was reacted at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material (SAM6), which was a white solid. The weight of SAM6 obtained was 1.08 g, with a yield of 79%. Mass spectrometry analysis of SAM6 yielded the following results: MS (m / z, MH). - ): 480.02.

[0084]

Preparation Example 7

[0085] A method for preparing a self-assembled single-molecule hole transport material SAM7 includes the following steps: Step 1: Phenyrazine (0.92 g, 5.0 mmol), 3,5-dibromoiodobenzene (2.17 g, 6.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), cuprous iodide (95 mg, 0.5 mmol), and dimethylethylenediamine (88 mg, 1.0 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a7 with a weight of 1.60 g, yielding 77%. Step 2: Intermediate a7 (1.60 g, 3.85 mmol) was added to diethyl phosphite (1.60 g, 11.55 mmol), followed by potassium acetate (75 mg, 0.77 mmol), triethylamine (470 mg, 4.60 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (290 mg, 0.38 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b7 with a weight of 1.82 g, yielding 89%. Step 3: Intermediate b7 (1.82 g, 3.42 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.62 g, 17.1 mmol). The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, self-assembled single-molecule hole transport material SAM7, which was a white solid. The weight of SAM7 obtained was 1.12 g, with a yield of 78%. Mass spectrometry analysis of SAM7 yielded the following mass spectrum: [See attached image]. Figure 5 The mass spectrum of the self-assembled single-molecule hole transport material SAM7 is as follows: MS (m / z, MH) - ):418.20.

[0086]

Preparation Example 8

[0087] A method for preparing a self-assembled single-molecule hole transport material SAM8 includes the following steps: Step 1: 2,8-Dichlorophenoxazine (1.26 g, 5.0 mmol), 3,5-dibromoiodobenzene (2.17 g, 6.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), cuprous iodide (95 mg, 0.5 mmol), and dimethylethylenediamine (88 mg, 1.0 mmol) were added to a 100 mL reaction flask. Under nitrogen protection, 30 mL of toluene was added, and the mixture was heated to 100 °C and stirred for 12 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain intermediate a8 with a weight of 2.0 g, yielding 83%. Step 2: Intermediate a8 (2.0 g, 4.15 mmol) was added to diethyl phosphite (1.72 g, 12.45 mmol), followed by potassium acetate (82 mg, 0.83 mmol), triethylamine (500 mg, 4.98 mmol), bis(diphenylphosphine)ferrocene palladium dichloride (320 mg, 0.42 mmol), and 30 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 12 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate b8 with a weight of 2.24 g, yielding 90%. Step 3: Intermediate b8 (2.24 g, 3.73 mmol) was added to 20 mL of dichloromethane, followed by trimethylbromosilane (2.85 g, 18.65 mmol). The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 15 mL of methanol was added, followed by the addition of deionized water until a white solid precipitated. The mixture was filtered to obtain the final product, a self-assembled single-molecule hole transport material (SAM8), which was a white solid with a weight of 1.50 g and a yield of 83%. Mass spectrometry analysis of SAM8 yielded MS (m / z, MH). - ):485.93.

[0088]

Example 1

[0089] The specific fabrication steps for perovskite solar cells are as follows: (1) The TCO conductive glass was ultrasonically cleaned for 15 minutes each with deionized water, acetone and isopropanol, and then dried in a drying oven at 75°C for later use. The dried TCO glass substrate was placed in an ultraviolet ozone machine for 25 minutes to remove organic impurities on its surface and optimize its surface wettability. (2) Disperse 0.5 mg of self-assembled monomolecular hole transport material in 1 mL of ethanol solution; sonicate for 20 min to obtain a hole transport material dispersion; (3) Take 30 μL of the above dispersion and drop it onto the TCO glass. Spin coat it at 5000 rpm for 30 s. Place the TCO glass on a hot plate and heat it at 100°C for annealing for 10 min to obtain the hole transport layer. (4) Dissolve 722.08 mg lead iodide and 238.50 mg methyl iodide solid in 1 mL of N,N-dimethylformamide (DMF) and stir at room temperature until completely dissolved to obtain a perovskite precursor solution; In a nitrogen glove box, take 30 μL of the perovskite precursor solution and drop it onto the ITO conductive glass to form the hole transport layer. First spin coat at 1000 rpm for 10 s, then spin coat at 5000 rpm for 30 s. During this process, add 125 μL of chlorobenzene quickly at 25 s. Then place the TCO glass on a hot stage and heat it at 100 °C for annealing for 40 min to form a perovskite light-absorbing layer of 500 nm. (5) Dissolve 20 mg of methane fullerene phenyl-C61-butyrate methyl ester (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain a [6,6]-phenyl-C61-butyrate methyl ester solution; take 30 μL of the [6,6]-phenyl-C61-butyrate methyl ester solution and spin coat it onto ITO conductive glass with a perovskite light-absorbing layer at 3000 rpm for 60 s to form an electron transport layer of 30 nm. (6) Dissolve 0.5 mg of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in 1 mL of isopropanol and stir at room temperature to obtain a hole blocking layer solution; take 40 μL of hole blocking layer solution and drop it onto the electron transport layer, spin coat at 5000 rpm for 35 s to form a 6 nm hole blocking layer; (7) Transfer the TCO conductive glass, which forms the hole blocking layer, electron transport layer, interface modification layer, perovskite light-absorbing layer, and hole transport layer, to a vacuum coating instrument and wait for its vacuum degree to reach 3×10 -4 Silver electrodes are deposited by vapor deposition at Pa, forming a 100 nm thick silver electrode on the hole blocking layer, thus obtaining the electrode layer.

[0090] The self-assembled single-molecule hole transport material was selected from Preparation Example 1.

[0091]

Example 2

[0092]

Example 3

[0093]

Example 4

[0094]

Example 5

[0095]

Example 6

[0096]

Example 7

[0097]

Example 8

[0098] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the hole transport layer in Comparative Example 1 is made of Ph-4PACz material, and the structure of Ph-4PACz is as follows: .

[0099] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the hole transport layer in Comparative Example 2 is made of MeOCzPhDPA material, and the structure of MeOCzPhDPA is as follows: .

[0100] The performance of the perovskite solar cells provided in Examples 1-8 and Comparative Examples 1-2 of this application was tested under standard test conditions to obtain the open-circuit voltage Voc, fill factor FF, short-circuit current density Jsc, and photoelectric conversion efficiency PCE of the corresponding perovskite solar cells. The test results are shown in Table 1.

[0101] The fill factor (FF) used in this paper refers to the ratio of the actual maximum obtainable power (Pm or Vmp × Jmp) to the theoretical (not actually obtainable) power (Jsc × Voc). Therefore, FF can be determined by the following formula: FF = (Vmp × Jmp) / (Jsc × Voc); Where Jmp and Vmp represent the current density and voltage at the maximum power point (Pm), respectively, this point is obtained by changing the resistance in the circuit until J×V reaches its maximum value; Jsc and Voc represent the short-circuit current and open-circuit voltage, respectively. The fill factor is a key parameter for evaluating solar cells. Commercial solar cells typically have a fill factor of approximately 60% or higher.

[0102] The open-circuit voltage (Voc) used in this paper is the potential difference between the anode and cathode of the device under conditions of no external load connection.

[0103] The short-circuit current (Isc) used in this article is the maximum current flowing through the output terminal of a photovoltaic cell or module when it is short-circuited (voltage V=0) under STC conditions.

[0104] The power conversion efficiency (PCE) of solar cells used in this article refers to the percentage of power converted from absorbed light into electrical energy. The PCE of a solar cell can be measured under standard test conditions (STC) with varying incident light irradiance (...). ) and the surface area of ​​solar cells ( The STC is calculated by dividing by the point of maximum power (Pm). STC typically refers to the value at a temperature of 25°C and an irradiance of 100 ppm. The spectrum of air quality 1.5 (AM1.5).

[0105] Table 1: Test data of perovskite solar cells prepared in Examples 1-8 and Comparative Examples 1-2

[0106] As shown in Table 1, the open-circuit voltage of the perovskite solar cells provided in Examples 1-8 is 1.153-1.163V, while the open-circuit voltage of the perovskite solar cells provided in Comparative Examples 1-2 is 1.148-1.150V. The perovskite solar cells provided in Examples 1-8 have higher open-circuit voltages and can maintain a higher potential difference during charge separation, which is beneficial for improving energy output. Furthermore, the hole transport layer obtained using the self-assembled single-molecule hole transport material specified in this application in Examples 1-8 is even more beneficial for improving... The increased energy output also indicates that the hole transport layer interfaces obtained in Examples 1-8 have better charge transport and defect passivation effects. In Comparative Example 2, the hole transport layer was prepared using MeOCzPhDPA material. Although both MeOCzPhDPA used in Comparative Example 2 and the self-assembled monomolecular hole transport material used in Example 1 are bisphosphonic acid-anchored hole transport layers, the methyl substitution of SAM1 used in Example 1 has a better energy level matching degree than methoxy substitution, and has an advantage in open-circuit voltage, thus outperforming Comparative Example 2.

[0107] As shown in Table 1, the short-circuit current of the perovskite solar cells provided in Examples 1-8 is 25.51-25.63. The short-circuit current of the perovskite solar cells provided in Comparative Examples 1 and 2 was 24.60–24.71 kJ. (less than 25) The perovskite solar cells provided in Examples 1-8 can generate more photogenerated carriers and have better light absorption and charge separation and transport characteristics than the perovskite solar cells provided in Comparative Examples 1-2.

[0108] As shown in Table 1, the fill factor of the perovskite solar cells provided in Examples 1-8 is 0.8216-0.8469%, while the fill factor of the perovskite solar cells provided in Comparative Examples 1-2 is 0.8159-0.8261%. The fill factor of the perovskite solar cells provided in Examples 1-8 is higher. Compared with Comparative Examples 1-2, the perovskite solar cells obtained in Examples 1-8 have lower internal series resistance, higher parallel resistance, lower charge transfer loss, and better circuit output characteristics.

[0109] As shown in Table 1, the photoelectric conversion efficiency of the perovskite solar cells provided in Examples 1-8 is 24.25-25.18%, while the photoelectric conversion efficiency of the perovskite solar cells provided in Comparative Examples 1-2 is 23.18-23.33% (lower than 24%). The photoelectric conversion efficiency of the perovskite solar cells provided in Examples 1-8 is higher than that of the perovskite solar cells provided in Comparative Examples 1-2.

[0110] In summary, the hole transport layers obtained by using the self-assembled single-molecule hole transport material as defined in Examples 1-8, when applied to perovskite solar cells, can improve the light absorption, charge separation and transport effects, reduce charge transport losses, and increase photoelectric conversion efficiency of perovskite solar cells.

[0111] This application embodiment can also provide a photovoltaic module (not shown), which includes the perovskite solar cell described above. The perovskite solar cell can be connected in series and / or in parallel with one or more other solar cells in a predetermined manner. Multiple cells can form a cell string, and adjacent cells can be connected together by string welding.

[0112] This application provides a photovoltaic system including the photovoltaic modules described in any of the above embodiments. The advantages of the aforementioned photovoltaic modules are also present in this photovoltaic system, and will not be repeated here. The application fields of the aforementioned photovoltaic system are wide, not limited to photovoltaic power plants, such as ground-mounted power plants, rooftop power plants, and floating power plants, but also including various devices and apparatuses that utilize solar energy for power generation, such as user solar power supplies, solar streetlights, solar cars, and solar buildings. Of course, it is understood that the application scenarios of the photovoltaic system are not limited to these; that is, the photovoltaic system can be applied in all fields that require solar energy for power generation. Taking a photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a combiner box, and an inverter. The photovoltaic array may be an array combination of multiple photovoltaic modules; for example, multiple photovoltaic modules can form multiple photovoltaic arrays. The photovoltaic array is connected to the combiner box, which can collect the current generated by the photovoltaic array. The collected current flows through the inverter and is converted into AC power required by the mains power grid before being connected to the mains power grid to achieve solar power supply.

[0113] It should be noted that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The directional terms "inner" and "outer" refer to the inside or outside relative to the outline of the component itself. For example, if a device in the drawings is inverted, a device described as "above" or "on top of" other devices or structures will subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0114] It should also be noted that the terms "one embodiment," "another embodiment," and "embodiment" used in this application refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment described in the general description of this application. The appearance of the same expression in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure, or characteristic is described in connection with any embodiment, the intention is to suggest that implementing such a feature, structure, or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0115] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0116] It should also be noted that the above are merely preferred embodiments of this application and do not limit the scope of patent protection of this application. Any equivalent structural or procedural changes made using the content of this application’s specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of this application.

Claims

1. A self-assembling monomolecular hole transporting material, characterized by, The self-assembled monomolecular hole transport material has a structure shown in the following formula I: Formula I In the formula, A1, A2 and A3 are respectively and independently an anchor group or a hydrogen atom; the anchor group is independently selected from a phosphoric acid group; G is selected from a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenothiazine group, and a substituted or unsubstituted phenoxazine group.

2. The self-assembled monomolecular hole transport material according to claim 1, wherein at least two of A1, A2 and A3 are anchor groups, and the anchor groups are phosphoric acid groups.

3. The self-assembled monomolecular hole transport material according to claim 1, wherein the number of carbon atoms of G is limited to 6-30.

4. The self-assembled monomolecular hole transport material according to claim 1, wherein G is selected from one of the following structural formulas:

5. The self-assembled monomolecular hole transport material according to claim 1, wherein the molecule corresponding to G is selected from one of the following structural formulas:

6. The self-assembled monomolecular hole transport material according to claim 1, wherein the self-assembled monomolecular hole transport material is selected from the following structures: The method comprises the following steps: 、 、 、 、 、 、 、 、 、 、 ； wherein X1-X 12 are each and independently selected from one of a hydrogen atom, a methyl group, a methoxy group, a methylthio group, a phenyl group, a methylphenyl group, a methoxyphenyl group, a thienyl group, a furanyl group, an arylamine group; X 13 is selected from one of an oxygen atom, a sulfur atom, a dialkyl-substituted methylene group. Step 1: coupling the molecule corresponding to the end group functional group G with a halogenated aromatic compound to generate an intermediate a; Step 2: substituting the intermediate a in step 1 with a phosphite compound to generate an intermediate b; 。 Step 3: reacting the intermediate b in step 2 with a halogenated silane, and then performing a hydrolysis reaction after the reaction is completed, to obtain the self-assembled monomolecular hole transport material. The self-assembled monomolecular hole transport material is applied to a perovskite solar cell. 、 、 、 、 、 、 、 。 7. A method for preparing a self-assembled single-molecule hole transport material according to any one of claims 1 to 6, characterized in that, The hole transport layer comprises the self-assembled monomolecular hole transport material according to any one of claims 1-6. A hole blocking layer is further arranged between the electron transport layer and the electrode. The method comprises: providing a conductive substrate; 8. Use of a self-assembled monolayer hole transport material according to any one of claims 1 to 6, characterized in that: dispersing the self-assembled monomolecular hole transport material according to any one of claims 1-6 in a solvent to obtain a hole transport material dispersion; 9. A perovskite solar cell, comprising an electrically conductive substrate, a hole transport layer, a perovskite light absorbing layer, an electron transport layer and an electrode which are sequentially stacked, characterized in that: placing the hole transport material dispersion on the upper surface of the conductive substrate, and performing spin coating and heat annealing to obtain a hole transport layer; 10. The perovskite solar cell according to claim 9, characterized in that, forming a perovskite light-absorbing layer on the upper surface of the hole transport layer; 11. A method of producing a perovskite solar cell, characterized by, forming an electron transport layer on the upper surface of the perovskite light-absorbing layer; forming an electrode on the upper surface of the electron transport layer. The solar cell is prepared by the method according to claim 9 or 10 or the method according to claim 11. ​ ​ ​ ​ 12. A photovoltaic module, characterized by ​

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