Self-assembling monomeric compounds, self-assembling monolayers, photovoltaic devices and methods of manufacture

Abstract

The application belongs to the field of photovoltaics, and particularly relates to a self-assembled monolayer compound, a self-assembled monolayer, a photovoltaic device and a preparation method. The self-assembled monolayer compound has a structure of formula I, and definitions of X1, X2, D1, D2, A and L are as described herein. The self-assembled monolayer compound provided by the application contains a disulfide bond or a selenium-sulfur bond, and can realize perfect conformal coverage of a textured structure as a hole transport material, can improve the performance of a large-size perovskite photovoltaic device, and has a very high commercial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of photovoltaics, specifically relating to self-assembled monomolecular compounds, self-assembled monolayers, photovoltaic devices, and preparation methods. Background Technology

[0002] The efficiency of tandem perovskite solar cells has exceeded 30%, and they are at a critical stage of transitioning from the laboratory to GW-level industrialization. Self-assembled monolayers (SAMs) such as MeO-2PACz have become the preferred hole transport material for tandem perovskite solar cells due to their ultrathinness, high light transmittance, and excellent energy level matching. This technology directly targets the high-efficiency photovoltaic module market, especially addressing the requirements for encapsulation and long-term stability of tandem perovskite solar cells in the context of large-size, textured (textured) silicon wafers.

[0003] Currently, the mainstream SAMs used are single-molecule SAMs, such as 2PACz, MeO-2PACz, and Me-4PACz. Most existing molecules are single-point anchored, resulting in uneven coverage on complex surfaces (such as the pyramidal textured surface of silicon wafers), and they are prone to displacement or desorption when heated or subjected to solvent impact. Summary of the Invention

[0004] To address the aforementioned problems in the prior art, this invention proposes a compound of formula I: , In Formula I, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; D1 and D2 are each independently selected from substituted or unsubstituted phenothiazine-2,10-diyl, substituted or unsubstituted phenothiazine-3,10-diyl, substituted or unsubstituted 9H-carbazole-3,9-diyl, substituted or unsubstituted triphenylamine-4,4′-diyl, substituted or unsubstituted triphenylamine-3,4′-diyl, and substituted or unsubstituted triphenylamine-2,4′-diyl; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8.

[0005] In one or more embodiments, the compound of formula I is a compound of formula I-1: , In Formula I-1, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0006] In one or more embodiments, the compound of formula I is a compound of formula I-2: , In Formula I-2, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0007] In one or more embodiments, the compound of formula I-1 is one or two selected from the following compounds: , .

[0008] In one or more embodiments, the I-2 compound is selected from one or more of the following compounds: , , .

[0009] In one or more embodiments, the compound of formula I is a compound of formula I-3: , In Formula I-3, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R5, R6, R7, and R8 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; g, h, i, and j are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0010] In one or more embodiments, the compound of formula I-3 is selected from one or more of the following compounds: , , .

[0011] In one or more embodiments, the compound of formula I is a compound of formula I-4: , In formula I-4, A1 and A2 are each independently selected from phosphate groups, carboxyl groups, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R9 and R10 R 11 R 12 R 13 R 14 Each is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl and hydroxyl groups; k, l, m, n, o, p are each independently selected from 0 to 5; Y1 and Y2 are each independently selected from oxygen atoms or are not present; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8.

[0012] In one or more embodiments, the compound of formula I-4 is .

[0013] Another aspect of the present invention provides a self-assembled monolayer precursor liquid comprising a solvent and a compound of formula I as described in any embodiment of the present invention.

[0014] In one or more embodiments, the solvent is selected from one or more of methanol, ethanol, acetonitrile, chloroform, toluene, N,N-dimethylformamide, and dimethyl sulfoxide.

[0015] In one or more embodiments, the molar concentration of the compound of formula I in the self-assembled monolayer precursor solution is 0.01-2 mmol / mL.

[0016] Another aspect of the present invention provides a self-assembled monolayer comprising a self-assembled monomolecular compound, the self-assembled monomolecular compound comprising a dynamic covalent bridge bond and two identical monomer structures connected by the dynamic covalent bridge bond, the dynamic covalent bridge bond being -SS- or -Se-S-; the monomer structures comprising an anchoring group and a core, the anchoring group being connected to the core via an alkyl chain, the anchoring group being selected from phosphate, carboxyl, and trimethoxysilyl groups, and the core being selected from phenothiazine, carbazole, and C1-C4 alkoxy-substituted triarylamines.

[0017] In one or more embodiments, the alkyl chain is a C2-C12 alkylene chain.

[0018] In one or more embodiments, the self-assembled monomolecular compound is selected from the compounds of Formula I described in any embodiment of the present invention.

[0019] In one or more embodiments, the thickness of the self-assembled monolayer is 0.05-2 nm.

[0020] Another aspect of the present invention provides a method for preparing a self-assembled monolayer, the method comprising coating a self-assembled monolayer precursor solution as described in any embodiment of the present invention, and then annealing to obtain a self-assembled monolayer.

[0021] In one or more embodiments, the annealing method is heat annealing, the annealing temperature is 80-150°C, and the annealing time is 1-30 min.

[0022] In one or more embodiments, the annealing time is 10-20 minutes.

[0023] Another aspect of the present invention provides a photovoltaic device comprising a self-assembled monolayer as described in any embodiment of the present invention; In one or more embodiments, the photovoltaic device sequentially comprises a conductive substrate, a self-assembled monolayer, a perovskite light-absorbing layer, an electron transport layer, and an electrode.

[0024] In one or more embodiments, the photovoltaic device is a perovskite solar cell.

[0025] In one or more embodiments, the perovskite solar cell is a single-junction perovskite cell, a crystalline silicon-perovskite tandem cell, a perovskite-perovskite tandem cell, a perovskite-copper indium gallium selenide tandem cell, or a perovskite-gallium arsenide tandem cell.

[0026] In this invention, the symmetrical long-chain structure and dynamic bridging bonds act as interfacial "springs," absorbing thermal stress during perovskite growth and operation, thus improving peel strength. Utilizing the reversibility of disulfide bonds (-SS-) or selenium-sulfur bonds (-Se-S-), the self-assembled monolayer compound can undergo spatial arrangement fine-tuning during assembly, achieving perfect conformal coverage of the textured structure. Simultaneously, the self-assembled monolayer compound of this invention contains two anchoring groups, significantly enhancing its adhesion to conductive glass (ITO / IZO) and greatly improving its resistance to solvent impact. Furthermore, the core material of this invention preferably uses phenothiazine, carbazole, or triphenylamine; similar core materials can provide faster hole extraction kinetics, reduce interfacial recombination current, and increase the fill factor (FF). Detailed Implementation

[0027] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used herein are explained and defined in general terms below. Unless otherwise specified, all technical and scientific terms used herein have the common meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0028] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0029] In this document, the terms “contains,” “includes,” “containing,” and similar terms encompass the meanings of “basically composed of” and “composed of.” For example, when this document discloses “A contains B and C,” “A is basically composed of B and C” and “A is composed of B and C” should be considered as having been disclosed in this document.

[0030] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0031] Unless otherwise specified, percentages refer to mass percentages and proportions refer to mass ratios in this article.

[0032] In this article, the sum of the percentages of all components in the composition is 100%.

[0033] In this document, when describing embodiments or examples, it should be understood that it is not intended to limit the invention to those embodiments or examples. Rather, all alternatives, modifications, and equivalents of the methods and materials described herein are covered within the scope of this invention.

[0034] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0035] Compound of Formula I: , In Formula I, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; D1 and D2 are each independently selected from substituted or unsubstituted phenothiazine-2,10-diyl, substituted or unsubstituted phenothiazine-3,10-diyl, substituted or unsubstituted 9H-carbazole-3,9-diyl, substituted or unsubstituted triphenylamine-4,4′-diyl, substituted or unsubstituted triphenylamine-3,4′-diyl, and substituted or unsubstituted triphenylamine-2,4′-diyl; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8, for example, 0, 1, 2, 3, 4, 5, 6, 7, and 8.

[0036] In some embodiments, the compound of formula I is a compound of formula I-1: , In Formula I-1, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently integers from 0 to 4 (e.g., 0, 1, 2, 3, 4); Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0037] In some embodiments, in Formula I-1, A1 and A2 are each independently selected from phosphate, carboxyl and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; c, d, e and f are all 0; Y1 and Y2 are absent; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 0.

[0038] In some embodiments, in Formula I-1, A1 and A2 are each independently selected from phosphate, carboxyl and trimethoxysilyl groups; L1 and L2 are each independently selected from C4-C12 alkylene groups; c, d, e and f are all 0; Y1 and Y2 are absent; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 0.

[0039] In some embodiments, the compound of formula I-1 is one or two selected from the following compounds: , .

[0040] In some embodiments, the compound of formula I is a compound of formula I-2: , In Formula I-2, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently integers from 0 to 4 (e.g., 0, 1, 2, 3, 4); Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0041] In some embodiments, in Formula I-2, A1 and A2 are each independently selected from phosphate, carboxyl and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; c, d, e and f are all 0; Y1 and Y2 are absent; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 0.

[0042] In some embodiments, in Formula I-2, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C4-C12 alkylene groups; c, d, e, and f are all 0; Y1 and Y2 are absent; X1 and X2 are each independently selected from sulfur or selenium atoms; and a and b are both 0.

[0043] In some embodiments, the I-2 compound is one or more selected from the following compounds: , , .

[0044] In some embodiments, the compound of formula I is a compound of formula I-3: , In Formula I-3, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R5, R6, R7, and R8 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; g, h, i, and j are each independently integers from 0 to 4 (e.g., 0, 1, 2, 3, 4); Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; and a and b are each independently integers from 0 to 8.

[0045] In some embodiments, in Formula I-3, A1 and A2 are each independently selected from phosphate, carboxyl and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; g, h, i and j are all 0; Y1 and Y2 are not present; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 0.

[0046] In some embodiments, in Formula I-3, A1 and A2 are each independently selected from phosphate, carboxyl and trimethoxysilyl groups; L1 and L2 are each independently selected from C4-C12 alkylene groups; g, h, i and j are all 0; Y1 and Y2 are not present; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 0.

[0047] In some embodiments, the compound of formula I-3 is selected from one or more of the following compounds: , , .

[0048] In some embodiments, the compound of formula I is a compound of formula I-4: , In formula I-4, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R9 and R 10 R 11 R 12 R 13 R 14 Each is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl and hydroxyl groups; k, l, m, n, o, p are each independently an integer from 0 to 5 (e.g. 0, 1, 2, 3, 4, 5); Y1 and Y2 are each independently selected from oxygen atoms or are not present; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently an integer from 0 to 8.

[0049] In some embodiments, in formulas I-4, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R9 and R 10 R 11 R 12 R 13 R 14 Each atom is independently selected from methoxy groups; k, l, m, n, o, and p are each independently 0 or 1; Y1 and Y2 are oxygen atoms; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are both integers between 0 and 2.

[0050] In some embodiments, in formula I-4, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C4 alkylene groups; R9 and R 10 R 11 R 12 R 13 R 14 Each atom is independently selected from methoxy groups; k, l, m, n, o, and p are each independently 0 or 1; Y1 and Y2 are oxygen atoms; X1 and X2 are each independently selected from sulfur or selenium atoms; a and b are both 1.

[0051] In some embodiments, the compound of formula I-4 is .

[0052] Self-assembled monolayer precursor

[0053] The self-assembled monolayer precursor solution of the present invention comprises a solvent and a compound of formula I as described in any embodiment of the present invention.

[0054] Solvents suitable for use in this invention include, but are not limited to, one or more selected from methanol, ethanol, acetonitrile, chloroform, toluene, N,N-dimethylformamide and dimethyl sulfoxide.

[0055] In some embodiments, the molar concentration of compound I in the self-assembled monolayer precursor solution of the present invention is 0.01-2 mmol / mL, for example 0.01 mmol / mL, 0.02 mmol / mL, 0.03 mmol / mL, 0.04 mmol / mL, 0.05 mmol / mL, 0.06 mmol / mL, 0.07 mmol / mL, 0.08 mmol / mL, 0.09 mmol / mL, 0.1 mmol / mL, 0.2 mmol / mL, 0.3 mmol / mL, 0.4 mmol / mL, 0.5 mmol / mL, 0.6 mmol / mL, 0.7 mmol / mL, 0.8 mmol / mL, 0.9 mmol / mL, 1 mmol / mL, 1.1 mmol / mL, 1.2 mmol / mL, 1.3 mmol / mL, 1.4 mmol / mL, 1.5 mmol / mL, 1.6 mmol / mL, 1.7 mmol / mL. mmol / mL, 1.8 mmol / mL, 1.9 mmol / mL, 2 mmol / mL, or any range between two values.

[0056] Self-assembled monolayer

[0057] The self-assembled monolayer of the present invention comprises a self-assembled monomolecular compound, wherein the self-assembled monomolecular compound comprises a dynamic covalent bridge bond and two identical monomer structures connected by the dynamic covalent bridge bond, wherein the dynamic covalent bridge bond is -SS- or -Se-S-; the monomer structure comprises an anchoring group and a parent nucleus, wherein the anchoring group and the parent nucleus are connected by an alkyl chain, wherein the anchoring group is selected from phosphate, carboxyl and trimethoxysilyl groups, and the parent nucleus is selected from phenothiazine, carbazole and C1-C4 alkoxy-substituted triarylamines.

[0058] In some embodiments, the alkyl chain is a C2-C12 alkylene chain.

[0059] In some embodiments, the self-assembled monomolecular compound is selected from the compounds of Formula I described in any embodiment of the present invention.

[0060] In some implementations, the thickness of the self-assembled monolayer is 0.05-2 nm, for example, 0.05 nm, 0.06 nm, 0.07 nm, 0.08 nm, 0.09 nm, 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.2 nm, 1.4 nm, 1.6 nm, 1.8 nm, 2 nm, or any range between two such values.

[0061] Methods for preparing self-assembled monolayers

[0062] The method for preparing a self-assembled monolayer according to the present invention includes coating a self-assembled monolayer precursor solution as described in any embodiment of the present invention, followed by annealing to obtain a self-assembled monolayer.

[0063] In some embodiments, the annealing method is heat annealing, with an annealing temperature of 80-150°C and an annealing time of 1-30 minutes. In some preferred embodiments, the annealing time is 10-20 minutes.

[0064] Photovoltaic devices

[0065] The photovoltaic device of the present invention comprises the self-assembled monolayer described in any embodiment of the present invention.

[0066] In some embodiments, the photovoltaic device of the present invention comprises, in sequence, a conductive substrate, a self-assembled monolayer, a perovskite light-absorbing layer, an electron transport layer, and an electrode.

[0067] In some implementations, the photovoltaic device is a perovskite solar cell.

[0068] In some embodiments, the perovskite solar cell is a single-junction perovskite cell, a crystalline silicon-perovskite tandem cell, a perovskite-perovskite tandem cell, a perovskite-copper indium gallium selenide tandem cell, or a perovskite-gallium arsenide tandem cell.

[0069] The present invention will be described below by way of specific embodiments. It should be understood that these embodiments are merely illustrative and are not intended to limit the scope of the invention. The methods, reagents, and materials used in the embodiments and comparative examples are conventional methods, reagents, and materials in the art, unless otherwise stated. The starting material compounds in the embodiments and comparative examples are all commercially available.

[0070] Synthesis example 1

[0071] Step 1: Synthesize intermediate A1 ( Under nitrogen protection, 4-bromophenol (1.73 g, 10 mmol), 4-methoxyaniline (1.23 g, 10 mmol), cesium carbonate (9.77 g, 30 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (XPhos) (380 mg, 0.8 mmol) were added to 100 mL of toluene. The mixture was heated to 100 °C and stirred for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered to remove inorganic salts, and the solvent was removed by vacuum distillation of the filtrate. Separation was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 5:1, v / v) to give a pale yellow solid intermediate A1 (1.8 g, 85% yield).1 H NMR (400 MHz, DMSO-d6): δ 9.15 (br s, 1H), 8.42 (br s, 1H), 7.05 (d, J = 8.8 Hz, 2H), 6.95 (d, J = 8.8 Hz, 2H), 6.82 (d,J = 8.8 Hz, 2H), 6.70 (d, J = 8.8 Hz, 2H), 3.72 (s, 3H).

[0072] Step 2: Synthesize intermediate B1 ( Under nitrogen protection, intermediate A1 (2.13 g, 10 mmol), 1-bromo-4-(4-(diethoxyphosphoryl)butyl)benzene (3.63 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), XPhos (380 mg, 0.8 mmol), and NaOtBu (1.44 g, 15 mmol) were added to 100 mL of toluene. The mixture was heated to 100 °C and stirred for 12 hours. After cooling, the mixture was quenched with water and extracted with ethyl acetate. The organic phase was dried, concentrated, and purified by column chromatography (petroleum ether / ethyl acetate = 2:1, v / v) to give a colorless oily intermediate B1. 1 HNMR (400 MHz, CDCl3): δ 7.10 (d, J = 8.5 Hz, 2H), 6.82 (d, J = 8.8 Hz, 2H), 6.75 (d, J = 8.8 Hz, 2H), 6.68 (d, J = 8.8 Hz, 2H), 6.62 (d, J = 8.8 Hz, 2H), 6.55 (d, J = 8.5 Hz, 2H), 5.15 (br s, 1H), 4.08 (m, 4H), 3.76 (s, 3H), 2.58(t, J = 7.6 Hz, 2H), 1.85 (m, 2H), 1.65–1.55 (m, 4H), 1.28 (t, J = 7.0 Hz, 6H)

[0073] Step 3: Synthesize intermediate C1 ( Intermediate B1 (2.0 mmol) was dissolved in 50 mL of anhydrous THF, and NaH (60% mineral oil dispersion, purchased from Nanjing Chemical Reagent 100 mg, 2.5 mmol) was added. The mixture was stirred at room temperature for 30 minutes until no more bubbles were generated. Then, bis(bromomethyl)disulfide (0.9 mmol) and KI (catalytic amount) were added. The mixture was heated to 60 °C and stirred for 12 hours. After the reaction was complete, the mixture was cooled, quenched with water, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting solution was purified by column chromatography to give intermediate C1, a pale yellow, viscous oil. 1 H NMR (400 MHz, CDCl3): δ 7.10 (d, J = 8.5 Hz, 4H), 6.98 (d, J = 8.8 Hz, 4H), 6.90 (d, J = 8.8 Hz, 4H), 6.82 (d, J = 8.8 Hz, 4H), 6.75 (d, J = 8.8 Hz, 4H), 6.68(d, J = 8.5 Hz, 4H), 4.25 (t, J = 6.2 Hz, 4H), 4.08 (m, 8H), 3.76 (s, 6H), 2.92 (t, J = 6.2 Hz, 4H), 2.55 (t, J = 7.6 Hz, 4H), 1.82 (m, 4H), 1.65–1.55 (m, 8H), 1.26 (t, J = 7.0 Hz, 12H).

[0074] Step 4: Synthesize compound 1 ( Intermediate C1 (0.5 mmol) was dissolved in 20 mL of anhydrous dichloromethane (DCM), cooled to 0 °C, and trimethylbromosilane (TMSBr, 2.0 mmol) was slowly added. The mixture was heated to room temperature and stirred for 4 hours. Then, methanol (5 mL) was added and stirred for 30 minutes. The solvent was removed under reduced pressure, and the crude product was purified by preparative HPLC (water / acetonitrile gradient elution, containing 0.1% TFA). Lyophilization yielded a white solid powder, which was compound 1 (180 mg, 35% yield). Its MS (ESI) m / z [M-2H] 2- Calculated value: 533.15; Measured value: 533.12; NMR results 1H NMR (400 MHz, DMSO-d6): δ 10.15 (br s, 4H), 7.08 (d, J = 8.6Hz, 4H), 6.92 (d, J = 8.8 Hz, 4H), 6.85 (d, J = 8.8 Hz, 4H), 6.78 (d, J = 8.8Hz, 4H), 6.72 (d, J = 8.6 Hz, 4H), 6.65 (d, J = 8.6 Hz, 4H), 4.12 (t, J = 6.0Hz, 4H), 3.72 (s, 6H), 2.52 (t, J = 7.5 Hz, 4H), 1.78 (m, 4H), 1.58–1.45 (m,8H).

[0075] Synthesis example 2

[0076] Step 1: Synthesis of intermediate A2 (3,3'-dithiobis(9H-carbazole)). Under nitrogen protection, 3-bromocarbazole (4.90 g, 20 mmol), sodium sulfide (Na2S, 1.56 g, 20 mmol), sulfur powder (0.64 g, 20 mmol), Pd2(dba) (368 mg, 0.4 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (Xantphos, 464 mg, 0.8 mmol) were added to 100 mL of toluene. Sodium tert-butoxide (t-BuON, 3.84 g, 40 mmol) was added. The mixture was heated to 100 °C and stirred for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solvent was removed by vacuum distillation of the filtrate. Separation by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 3:1, v / v) yielded a pale yellow solid intermediate A2 (2.1 g, yield 58%).

[0077] Step 2: Synthesis of intermediate B2 (3,3'-dithiobis[9-(4-(diethoxyphosphoryl)butyl)-9H-carbazole]). Under nitrogen protection, intermediate A2 (1.83 g, 5 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.48 g, 12 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution of diethyl 4-bromobutylphosphonate (3.06 g, 12 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by silica gel column chromatography yielded a colorless oily intermediate B2 (2.8 g, 75% yield).

[0078] Step 3: Synthesis of Compound 2. Intermediate B2 (1.5 g, 2.0 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (2.5 mL, 19 mmol) was added. The reaction was stirred at room temperature for 12 hours. Subsequently, methanol (10 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 2 hours to hydrolyze the generated silanol ester. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of methanol / water mixed solvent and purified by preparative HPLC or recrystallization to obtain a white solid powder, which was Compound 2. (1.05 g, yield 78%); its MS (ESI) m / z [MH] - Calculated value: 667.14; Measured value: 667.12; NMR result: 1 H NMR (400 MHz, DMSO-d6): δ 8.15 (d, J = 1.8 Hz, 2H), 7.65 (d, J = 7.8 Hz, 2H), 7.55 (d, J =8.2 Hz, 2H), 7.45 (t, J = 7.8 Hz, 2H), 7.35 (t, J = 7.8 Hz, 2H), 7.25 (d, J =8.2 Hz, 2H), 7.10 (dd, J = 8.2, 1.8 Hz, 2H), 4.25 (t, J = 7.2 Hz, 4H), 1.95-1.85 (m, 4H), 1.75-1.60 (m, 8H).

[0079] Synthesis example 3

[0080] Step 1: Synthesis of intermediate A3 (N-(4-(diethiophosphoryl)butyl)phenazine). Under nitrogen protection, phenothiazine (3.98 g, 20 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.96 g, 24 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution of diethyl 4-bromobutylphosphonate (5.46 g, 120 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 2:1, v / v) to give a pale yellow oily intermediate A3 (6.2 g, 78% yield).

[0081] Step 2: Synthesis of intermediate B3 (3-bromo-N-(4-(diethoxyphosphoryl)butyl)phenthiazide). Under nitrogen protection, intermediate A3 (3.96 g, 10 mmol) was dissolved in 50 mL of anhydrous DCM and cooled to -10 °C. N-bromosuccinimide (NBS, 1.78 g, 10 mmol) was added in portions. After the addition was complete, the mixture was stirred at room temperature for 4 hours. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried and concentrated. The solution was purified by column chromatography to give intermediate B3 (3.2 g, 68% yield) as a white solid.

[0082] Step 3: Synthesis of intermediate C3 (3,3'-dithiobis[N-(4-(diethoxyphosphoryl)butyl)phenthiazine]). Under nitrogen protection, intermediate B3 (2.35 g, 5 mmol), sodium sulfide (Na2S·9H2O, 1.2 g, 5 mmol), and sulfur powder (0.32 g, 10 mmol) were added to 50 mL of DMF. Potassium carbonate (K2CO3, 1.38 g, 10 mmol) and cuprous iodide (CuI, 95 mg, 0.5 mmol) were added as catalysts. The mixture was heated to 110 °C and stirred for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to remove inorganic salts, and the solvent was removed by vacuum distillation of the filtrate. Separation was performed by silica gel column chromatography (eluent: dichloromethane / methanol = 50:1, v / v) to give a yellow solid intermediate C3 (1.5 g, yield 68%).

[0083] Step 4: Synthesis of Compound 3. Intermediate C3 (1.0 g, 1.14 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (2.0 mL, 15 mmol) was added. The reaction was stirred at room temperature for 12 hours. Subsequently, methanol (10 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 2 hours to hydrolyze the generated silanol ester. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of methanol, and diethyl ether was added to precipitate the precipitate. The precipitate was filtered and dried to obtain a white solid powder, which was compound 3. (0.75 g, yield 85%); its MS (ESI) m / z [M-2H] 2- Calculated value: 731.08; Measured value: 731.10; NMR results 1H NMR (400 MHz, DMSO-d6): δ 7.45 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 1.5 Hz, 2H), 7.20 (dd, J = 8.0,1.5 Hz, 2H), 7.15-7.05 (m, 6H), 7.00 (d, J = 7.5 Hz, 2H), 4.10 (t, J = 7.0Hz, 4H), 2.00-1.80 (m, 4H), 1.70-1.50 (m, 8H).

[0084] Synthesis example 4

[0085] Step 1: Synthesize intermediate A4 ( Under nitrogen protection, phenothiazine (3.98 g, 20 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.96 g, 24 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Subsequently, a DMF solution of diethyl 4-bromobutylphosphonate (5.46 g, 20 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 3:1, v / v) to give a pale yellow oily intermediate A4 (6.5 g, 82% yield). 1 H NMR (400 MHz, CDCl3): δ 7.12 (dd, J = 7.6, 1.2 Hz, 4H), 6.95 (td, J = 7.6, 1.2 Hz, 4H), 4.12 (dq, J= 7.0, 6.8 Hz, 4H), 3.90 (t, J = 7.2 Hz, 2H), 1.92 (quin, J = 7.2 Hz, 2H), 1.75 (m, 2H), 1.62 (m, 2H), 1.30 (t, J = 7.0 Hz, 6H).

[0086] Step 2: Synthesize intermediate B4 ( Under nitrogen protection, intermediate A4 (3.96 g, 10 mmol) was dissolved in 50 mL of anhydrous DCM and cooled to -10 °C. N-bromosuccinimide (NBS, 1.78 g, 10 mmol) was added in portions. After addition, the mixture was brought to room temperature and stirred for 4 hours. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried and concentrated. Purification by column chromatography yielded a white solid intermediate B4 (3.5 g, 74% yield). 1H NMR (400MHz, CDCl3): δ 7.42 (d, J = 2.0 Hz, 1H), 7.28 (dd, J = 8.4, 2.0 Hz, 1H), 7.15 (d, J = 8.4 Hz, 1H), 7.08–6.92 (m, 4H), 4.15 (dq, J = 7.0, 6.5 Hz, 4H), 3.92(t, J = 7.2 Hz, 2H), 1.95 (quin, J = 7.2 Hz, 2H), 1.78 (m, 2H), 1.65–1.55 (m,2H), 1.32 (t, J = 7.0 Hz, 6H).

[0087] Step 3: Synthesize intermediate C4 ( Under nitrogen protection, intermediate B4 (2.36 g, 5 mmol) and potassium cyanide (KCN, 0.65 g, 10 mmol) were dissolved in 30 mL of ethanol / water (1:1) mixture. Selenium powder (0.40 g, 5 mmol) and sodium borohydride (NaBH4, 0.38 g, 10 mmol) were added. The mixture was heated under reflux for 4 hours. After the reaction was complete, the mixture was cooled and extracted with ethyl acetate. The organic phase was dried, concentrated, and purified by column chromatography to give a pale yellow solid intermediate C4 (2.0 g, 80% yield). 1 H NMR (400 MHz, CDCl3): δ 7.42 (d, J = 2.0 Hz, 1H), 7.28 (dd, J = 8.4, 2.0 Hz, 1H), 7.15 (d, J = 8.4 Hz, 1H), 7.08–6.92 (m, 4H), 4.15(dq, J = 7.0, 6.5 Hz, 4H), 3.92 (t, J = 7.2 Hz, 2H), 1.95 (quin, J = 7.2 Hz, 2H), 1.78 (m, 2H), 1.65–1.55 (m, 2H), 1.32 (t, J = 7.0 Hz, 6H).

[0088] Step 4: Synthesize intermediate D4 ( Under nitrogen protection, intermediate B4 (2.36 g, 5 mmol) and thiourea (0.38 g, 5 mmol) were dissolved in 30 mL of ethanol. The mixture was heated under reflux for 6 hours to form isothiourea salt. After cooling, 2 M NaOH solution (20 mL) was added, and the mixture was heated under reflux for 2 hours for hydrolysis. The pH was adjusted to 6-7 with dilute hydrochloric acid, and a solid precipitated. The solid was filtered, washed with water, and dried to give a white solid intermediate D4 (1.7 g, 85% yield). 1 HNMR (400 MHz, CDCl3): δ 7.28 (d, J=2.0 Hz, 1H), 7.20 (dd, J=8.4, 2.0 Hz, 1H), 7.08 (d, J=8.4 Hz, 1H), 7.02–6.92 (m, 4H), 4.14 (dq, J=7.0, 6.5 Hz, 4H), 3.90 (t, J=7.2 Hz, 2H), 3.45 (br s, 1H), 1.94 (quin, J=7.2 Hz, 2H), 1.76 (m, 2H), 1.60 (m, 2H), 1.30 (t, J=7.0 Hz, 6H).

[0089] Step 5: Synthesize intermediate E4 ( Intermediate C4 (1.0 mmol, providing the -SeCN group) and intermediate D4 (1.0 mmol, providing the -SH group) were dissolved in 20 mL of anhydrous ethanol. Triethylamine (Et3N, 0.5 mL) was added as a base. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the solvent was removed under reduced pressure. The solution was purified by silica gel column chromatography (eluent: dichloromethane / methanol = 50:1, v / v) to give a yellow solid intermediate E4 (1.2 g, 65% yield). 1 H NMR (400 MHz, CDCl3): δ 7.35–6.90 (m, 14H), 4.16–4.08 (m, 8H), 3.94–3.86 (m, 4H), 2.02–1.52 (m, 12H), 1.32–1.26 (m, 12H).

[0090] Step 6: Synthesis of Compound 4. Intermediate E4 (1.0 g, 1.1 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (2.0 mL, 15 mmol) was added. The reaction was stirred at room temperature for 12 hours. Then, methanol (10 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 2 hours to hydrolyze the generated silanol ester. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of methanol, and diethyl ether was added to precipitate the precipitate. The precipitate was filtered and dried under vacuum to obtain a pale yellow solid powder, which was Compound 4. (0.78 g, yield 86%); its MS (ESI) m / z [MH] - Calculated value: 810.98; Measured value: 811.05; NMR results 1 H NMR (400 MHz, DMSO-d6): δ 10.20(br s, 4H), 7.42 (d, J = 2.0 Hz, 1H), 7.38 (d, J = 2.0 Hz, 1H), 7.26 (dd, J =8.5, 2.0 Hz, 1H), 7.21 (dd, J = 8.5, 2.0 Hz, 1H), 7.13 (d, J = 8.5 Hz, 1H), 7.09 (d, J = 8.5 Hz, 1H), 7.05–6.90 (m, 8H), 3.92 (t, J = 7.2 Hz, 2H), 3.88(t, J = 7.2 Hz, 2H), 1.96 (quin, J = 7.2 Hz, 2H), 1.91 (quin, J = 7.2 Hz,2H), 1.68–1.52 (m, 4H), 1.48 (m, 4H, 2 JPH ≈ 18 Hz.

[0091] Synthesis example 5

[0092] Step 1: Synthesis of intermediate A5 (10-(3-(diethoxyphosphoryl)-2-methylpropyl)-10H-phenthiazine). Under nitrogen protection, phenthiazine (3.98 g, 20 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.96 g, 24 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution of 1-bromo-3-(diethoxyphosphoryl)-2-methylpropane (6.02 g, 20 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 3:1, v / v) to give a pale yellow oily intermediate A5 (6.8 g, 80% yield).

[0093] Step 2: Synthesis of intermediate B5 (3-bromo-10-(3-(diethoxyphosphoryl)-2-methylpropyl)-10H-phenthiazine). Under nitrogen protection, intermediate A5 (4.24 g, 10 mmol) was dissolved in 50 mL of anhydrous DCM and cooled to -10 °C. N-bromosuccinimide (NBS, 1.78 g, 10 mmol) was added in portions. After the addition was complete, the mixture was stirred at room temperature for 4 hours. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried and concentrated. Purified by column chromatography, intermediate B5 (3.6 g, 72% yield) was obtained as a white solid.

[0094] Step 3: Synthesis of intermediate C5 (3,3'-dithiobis[10-(3-(diethoxyphosphoryl)-2-methylpropyl)-10H-phenthiazine]). Under nitrogen protection, intermediate B5 (2.50 g, 5 mmol), sodium sulfide (Na2S·9H2O, 1.2 g, 5 mmol), and sulfur powder (0.32 g, 10 mmol) were added to 50 mL of DMF. Potassium carbonate (K2CO3, 1.38 g, 10 mmol) and cuprous iodide (CuI, 95 mg, 0.5 mmol) were added as catalysts. The mixture was heated to 110 °C and stirred for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to remove inorganic salts, and the solvent was removed by vacuum distillation of the filtrate. Separation was performed by silica gel column chromatography (eluent: dichloromethane / methanol = 50:1, v / v) to give a yellow solid intermediate C5 (1.6 g, yield 66%).

[0095] Step 4: Synthesis of Compound 5. Intermediate C5 (1.2 g, 1.3 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (2.5 mL, 19 mmol) was added. The reaction was stirred at room temperature for 12 hours. Subsequently, methanol (10 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 2 hours to hydrolyze the generated silanol ester. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of methanol, and diethyl ether was added to precipitate the precipitate. The precipitate was filtered and dried under vacuum to obtain a white solid powder, which was Compound 5. (0.85 g, yield 82%); its MS (ESI) m / z [MH] - Calculated value: 763.14; Measured value: 763.18; NMR results 1H NMR (400 MHz, DMSO-d6): δ 7.50 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 1.5 Hz, 2H), 7.25 (dd, J =8.0, 1.5 Hz, 2H), 7.15-7.05 (m, 6H), 7.00 (d, J = 7.5 Hz, 2H), 4.05 (d, J =7.0 Hz, 4H), 2.10-1.90 (m, 2H), 1.80-1.60 (m, 4H), 1.05 (d, J = 7.0 Hz, 6H).

[0096] Synthesis example 6

[0097] Step 1: Synthesis of the side-chain precursor A6 (1-bromo-3,7-diethyl-10-methyl-11-(diethoxyphosphoryl)undecane). Under nitrogen protection, diethyl malonate (10.0 g, 62.5 mmol) was dissolved in 80 mL of anhydrous THF and cooled to 0°C in an ice bath. Sodium hydride (3.0 g, 75 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Subsequently, anhydrous THF solutions of 1-bromo-3-ethylhexane (13.2 g, 68.8 mmol) and 2-bromo-3-methylbutane (10.5 g, 68.8 mmol) were added dropwise. After the addition was complete, the mixture was heated to 60°C and refluxed for 18 hours. The reaction solution was concentrated under reduced pressure to remove THF, and triethyl phosphite (12.5 g, 75 mmol) was added directly. The mixture was stirred in an oil bath at 130°C for 20 hours. After cooling to 0°C, an anhydrous THF suspension of lithium aluminum hydride (2.4 g, 63 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 4 hours. The mixture was carefully quenched with ice water and 15% NaOH solution, filtered to remove inorganic salts, and the filtrate was concentrated to obtain crude alcohol. The crude alcohol was dissolved in 50 mL of anhydrous DCM, and phosphorus tribromide (5.1 g, 18.8 mmol) was added dropwise at 0°C, followed by stirring at room temperature for 3 hours. After the reaction was complete, the mixture was poured into a saturated NaHCO3 aqueous solution and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give a pale yellow oily intermediate A6 (15.2 g, 48% yield).

[0098] Step 2: Synthesis of intermediate B6 (10-(3,7-diethyl-10-methyl-11-(diethoxyphosphoryl)undecyl)-10H-phenthiazine). Under nitrogen protection, phenthiazine (3.98 g, 20 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.96 g, 24 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution of intermediate A6 (12.0 g, 22 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 5:1, v / v) to give a pale yellow oily intermediate B6 (8.5 g, 70% yield).

[0099] Step 3: Synthesis of intermediate C6 (3-bromo-10-(3,7-diethyl-10-methyl-11-(diethoxyphosphoryl)undecyl)-10H-phenthiazine). Under nitrogen protection, intermediate B6 (6.0 g, 10 mmol) was dissolved in 50 mL of anhydrous DCM and cooled to -10 °C. N-bromosuccinimide (NBS, 1.78 g, 10 mmol) was added in portions. After the addition was complete, the mixture was stirred at room temperature for 4 hours. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried and concentrated. Purified by column chromatography, intermediate C6 (5.2 g, 76% yield) was obtained as a white solid.

[0100] Step 4: Synthesis of intermediate D6. Under nitrogen protection, intermediate C6 (3.43 g, 5 mmol), sodium sulfide (Na₂S·9H₂O, 1.2 g, 5 mmol), and sulfur powder (0.32 g, 10 mmol) were added to 50 mL of DMF. Potassium carbonate (K₂CO₃, 1.38 g, 10 mmol) and cuprous iodide (CuI, 95 mg, 0.5 mmol) were added. The mixture was heated to 110 °C and stirred for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered to remove inorganic salts, and the solvent was removed by vacuum distillation of the filtrate. Separation was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 2:1, v / v) to give a yellow, viscous oily / solid intermediate D6 (2.8 g, 85% yield).

[0101] Step 5: Synthesis of Compound 6. Intermediate D6 (2.0 g, 1.5 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (TMSBr, 3.0 mL, 22 mmol) was added. The reaction was stirred at room temperature for 12 hours. Subsequently, methanol (15 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 4 hours. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of methanol, and n-hexane was added to precipitate the product. The precipitate was filtered and dried under vacuum to obtain a white waxy solid, which was Compound 6. (1.5 g, 80% yield). Its MS (ESI) m / z [MH] - Calculated value: 1235.45; Measured value: 1235.50; NMR results 1 H NMR (400 MHz, DMSO-d6): δ10.15 (br s, 4H), 7.32 (d, J = 2.0 Hz, 2H), 7.24 (dd, J = 8.4, 2.0 Hz, 2H), 7.10 (d, J = 8.4 Hz, 2H), 7.00–6.90 (m, 8H), 3.86 (t, J = 7.2 Hz, 4H), 1.80–1.60 (m, 14H), 1.55–1.35 (m, 13H), 1.28–1.15 (m, 4H), 0.89 (t, J = 7.4 Hz,9H), 0.85 (d, J = 6.8 Hz, 6H).

[0102] Synthesis Example 7

[0103] Step 1: Synthesis of intermediate A7 (10-(12-(diethoxyphosphoryl)dodecyl)-10H-phenthiazine). Under nitrogen protection, phenthiazine (3.98 g, 20 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.96 g, 24 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Subsequently, a DMF solution of diethyl 12-bromododecylphosphonate (7.58 g, 22 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1, v / v) to give a pale yellow oily intermediate A7 (7.5 g, 75% yield).

[0104] Step 2: Synthesis of intermediate B7 (3-bromo-10-(12-(diethoxyphosphoryl)dodecyl)-10H-phenthiazine). Under nitrogen protection, intermediate A7 (5.0 g, 10 mmol) was dissolved in 50 mL of anhydrous DCM and cooled to -10 °C. N-bromosuccinimide (NBS, 1.78 g, 10 mmol) was added in portions. After the addition was complete, the mixture was stirred at room temperature for 4 hours. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried and concentrated. Purified by column chromatography, intermediate B7 (4.2 g, 73% yield) was obtained as a white solid.

[0105] Step 3: Synthesis of intermediate C7 (dimer). Under nitrogen protection, intermediate B7 (2.87 g, 5 mmol), sodium sulfide (Na₂S·9H₂O, 1.2 g, 5 mmol), and sulfur powder (0.32 g, 10 mmol) were added to 50 mL of DMF. Potassium carbonate (K₂CO₃, 1.38 g, 10 mmol) and cuprous iodide (CuI, 95 mg, 0.5 mmol) were added. The mixture was heated to 110 °C and stirred for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered to remove inorganic salts, and the solvent was removed by vacuum distillation of the filtrate. Separation was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 2:1, v / v) to obtain a yellow, waxy, oily intermediate C7 (2.2 g, 80% yield).

[0106] Step 4: Synthesis of Compound 7. Intermediate C7 (1.5 g, 1.35 mmol) was dissolved in 30 mL of anhydrous DCM. Trimethylbromosilane (3.0 mL, 22 mmol) was added. The reaction was stirred at room temperature for 24 hours. Subsequently, methanol (15 mL) was added to quench the reaction, and the mixture was stirred at room temperature for 4 hours to completely hydrolyze the silanol. The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of hot methanol, cooled to precipitate a white solid, filtered, and dried under vacuum to obtain a white powder, which was Compound 7. (1.1 g, yield 82%); its MS (ESI) m / z [MH] - Calculated value: 957.35; Measured value: 957.40; NMR results 1H NMR (400 MHz, DMSO-d6): δ7.55 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 1.5 Hz, 2H), 7.25 (dd, J = 8.0, 1.5Hz, 2H), 7.15-7.05 (m, 6H), 7.00 (d, J = 7.5 Hz, 2H), δ 4.10 (t, J = 7.0 Hz, 4H), δ 1.90 (m, 4H), δ 1.60-1.20 (m, 40H).

[0107] Synthesis example 8

[0108] Step 1: Prepare a pale yellow solid intermediate A2 according to Step 1 of Synthesis Example 2. 1 H NMR (400 MHz, CDCl3): δ 8.12 (d, J = 1.8 Hz, 2H), 7.68 (d, J = 7.8 Hz, 2H), 7.58 (d, J = 8.2Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 7.38 (t, J = 7.8 Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 7.12 (dd, J = 8.2, 1.8 Hz, 2H), 8.05 (br s, 2H).

[0109] Step 2: Synthesize intermediate B8 ( Under nitrogen protection, intermediate A2 (1.98 g, 5 mmol) was dissolved in 50 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.24 g, 6 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution (10 mL) of diethyl 4-bromobutylphosphonate (1.53 g, 5 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 2:1, v / v) to give a pale yellow oily intermediate B8 (1.65 g, 55% yield). 1H NMR (400 MHz, CDCl3): δ 8.15 (d, J = 1.8 Hz, 1H), 8.08 (d, J = 1.8 Hz, 1H), 8.02 (br s, 1H), 7.70–7.05 (m, 12H), 4.28 (t, J = 7.2 Hz, 2H), 4.12 (dq, J = 7.0, 6.5 Hz, 4H), 1.90 (m, 2H), 1.68–1.55 (m, 6H), 1.28 (t, J = 7.0 Hz, 4H).

[0110] Step 3: Synthesize intermediate C8 ( Under nitrogen protection, intermediate B8 (1.50 g, 2.5 mmol) was dissolved in 40 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.12 g, 3 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution (5 mL) of ethyl 5-bromopentanoate (0.63 g, 3 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give a colorless oily intermediate C8 (1.42 g, 82% yield). 1 H NMR (400MHz, CDCl3): δ 8.18 (d, J = 1.8 Hz, 1H), 8.14 (d, J = 1.8 Hz, 1H), 7.72–7.08(m, 12H), 4.30 (t, J = 7.2 Hz, 2H), 4.24 (t, J = 7.2 Hz, 2H), 4.14 (m, 6H), 2.32 (t, J = 7.4 Hz, 2H), 1.92 (m, 2H), 1.75–1.50 (m, 8H), 1.29 (t, J = 7.0Hz, 6H), 1.26 (t, J = 7.1 Hz, 3H).

[0111] Step 3: Synthesize compound 8 ( Intermediate C8 (1.20 g, 1.7 mmol) was dissolved in 30 mL of anhydrous DCM, cooled to 0 °C, and trimethylbromosilane (2.2 mL, 17 mmol) was slowly added. The mixture was then stirred at room temperature for 12 hours. Subsequently, methanol (10 mL) was added and stirred for 2 hours to hydrolyze the generated silyl ester. The solvent was removed under reduced pressure, and the crude product was purified by preparative HPLC (water / acetonitrile gradient elution, containing 0.1% TFA). Lyophilization yielded a white solid powder, which was compound 8 (0.85 g, 76% yield). Its MS (ESI) m / z [MH] - Calculated value: 667.14; Measured value: 667.12; NMR result: 1 H NMR (400 MHz, DMSO-d6): δ 12.35 (br s, 1H), 10.90 (br s, 2H), 8.16 (d, J = 1.8 Hz, 1H), 8.14 (d, J = 1.8 Hz, 1H), 7.66 (d,J = 7.8 Hz, 1H), 7.64 (d, J = 7.8 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.54 (d,J = 8.2 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 7.44 (t, J = 7.8 Hz, 1H), 7.36 (t,J = 7.8 Hz, 1H), 7.34 (t,J = 7.8 Hz, 1H), 7.26 (d, J = 8.2 Hz, 1H), 7.24 (d,J = 8.2 Hz, 1H), 7.11 (dd, J = 8.2, 1.8 Hz, 1H), 7.09 (dd, J = 8.2, 1.8 Hz,1H), 4.26 (t, J = 7.2 Hz, 2H), 4.24 (t, J = 7.2 Hz, 2H), 2.32 (t, J = 7.4 Hz, 2H), 1.96-1.86 (m, 2H), 1.78-1.55 (m, 8H).

[0112] Synthesis example 9

[0113] Step 1: Prepare a pale yellow solid intermediate A2 according to Step 1 of Synthesis Example 2.

[0114] Step 2: Prepare a pale yellow oily intermediate B8 according to step 2 of Synthesis Example 8.

[0115] Step 3: Synthesize intermediate C9 ( Under nitrogen protection, intermediate B8 (1.50 g, 2.5 mmol) was dissolved in 40 mL of anhydrous DMF and cooled to 0°C in an ice bath. Sodium hydride (0.12 g, 3 mmol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 30 minutes. Then, a DMF solution (5 mL) of 4-bromobutyltrimethoxysilane (0.72 g, 3 mmol) was added dropwise. After the addition was complete, the mixture was heated to 80°C and stirred for 12 hours. After the reaction was complete, the mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification was achieved by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give a colorless oily intermediate C9 (1.58 g, 85% yield). 1 H NMR (400MHz, CDCl3): δ 8.18 (d, J = 1.8 Hz, 1H), 8.14 (d, J = 1.8 Hz, 1H), 7.72–7.08(m, 12H), 4.30 (t, J = 7.2 Hz, 2H), 4.22 (t, J = 7.2 Hz, 2H), 4.14 (dq, J =7.0, 6.5 Hz, 4H), 3.58 (s, 9H), 1.92 (m, 2H), 1.75–1.50 (m, 8H), 1.29 (t, J =7.0 Hz, 6H), 0.62 (t, J = 7.8 Hz, 2H).

[0116] Step 4: Synthesize compound 9 ( Intermediate C9 (1.30 g, 1.8 mmol) was dissolved in 30 mL of anhydrous DCM and cooled to 0 °C. Trimethylbromosilane (2.0 mL, 15 mmol) was slowly added. The mixture was stirred at room temperature for 4 hours (time was strictly controlled to avoid silane hydrolysis). Then, pre-cooled anhydrous methanol (5 mL) was added and the mixture was stirred at 0 °C for 30 minutes. The solvent was removed under reduced pressure, and the crude product was purified by preparative HPLC (water / ethyl acetate gradient elution, containing 0.1% TFA). Lyophilization yielded a white solid powder, which was compound 9 (0.92 g, 78% yield). Its MS (ESI) m / z [MH] - Calculated value: 703.18; Measured value: 703.16; NMR result: 1H NMR (400 MHz, DMSO-d6): δ 10.10(br s, 2H), 8.18 (d, J = 1.8 Hz, 1H), 8.15 (d, J = 1.8 Hz, 1H), 7.70–7.05 (m,12H), 4.26 (t, J = 7.2 Hz, 2H), 4.18 (t, J = 7.2 Hz, 2H), 3.55 (s, 9H), 1.82(m, 2H), 1.65–1.45 (m, 8H), 0.58 (t, J = 7.8 Hz, 2H).

[0117] Example 1

[0118] This embodiment provides a perovskite / crystalline silicon tandem solar cell module, and the specific fabrication steps are as follows: (1) Preparation of bottom battery Plasma-enhanced chemical vapor deposition (PECVD) was used to deposit intrinsic amorphous silicon layers (a-Si(i)) on both sides of the intrinsic silicon layer (c-Si(n)) at 200℃ to form an amorphous silicon passivation layer. Then, n-type microcrystalline silicon layers and p-type microcrystalline silicon layers were deposited on both sides of the amorphous silicon passivation layer to form an electron transport layer (nc-Si(n)) and a hole transport layer (nc-Si(p)) respectively, resulting in a bottom cell with a thickness of 160 μm. (2) Fabrication of back electrode and tunneling layer ITO was deposited on the surface of a p-type microcrystalline silicon layer using magnetron sputtering to form a transparent conductive layer with a thickness of 80 nm. Silver paste was then printed on the surface of the transparent conductive layer using screen printing to form silver gate electrodes with a height of 10 μm and a width of 80 μm. The transparent conductive layer ITO and the silver gate electrodes together form the back electrode. IZO was deposited on the surface of an n-type microcrystalline silicon layer using radio frequency sputtering to form a tunneling layer with a thickness of 15 nm. (3) Preparation of hole transport layer Compound 1 was dissolved in anhydrous ethanol to prepare a 0.2 mmol / mL solution of compound 1. 50 μL of the compound 1 solution was dropped onto the surface of the tunneling layer IZO and then spin-coated at 4000 rpm for 30 s. After spin-coating, it was transferred to a heating plate at 100 °C and annealed for 10 min. Then it was removed to obtain a hole transport layer with a thickness of 1.5 nm. (4) Preparation of perovskite light-absorbing layer Using a mixture of DMF and dimethyl sulfoxide (DMSO) at a volume ratio of 4:1 as a solvent, and PbI2, PbBr2, FAI, MABr, and CsI as raw materials, a 1.4 mol / L solution with the following composition was prepared: 0.05 MA 0.08FA 0.87 Pb(I 0.80 Br 0.20 )3 perovskite precursor solution; Perovskite thin film layer was prepared by anti-solvent method: 60 μL of perovskite precursor liquid was dropped onto the surface of hole transport layer prepared in step (3) in nitrogen glove box. In the first stage, spin coating was performed at 1500 r.pm for 5 s. In the second stage, spin coating was performed at 4000 r.pm for 25 s. In the 10th s of spin coating at 4000 r.pm in the second stage, 200 µL of chlorobenzene anti-solvent was dropped onto its surface. After spin coating, it was annealed on a hot stage at 110℃ for 15 min to obtain a perovskite light-absorbing layer with a thickness of 500 nm. (5) Preparation of perovskite passivation layer (perovskite interface passivation) Phenylacetium iodide (PEAI) was dissolved in isopropanol (IPA) to prepare a 1.0 mg / mL solution. The solution was then spin-coated onto the surface of the perovskite light-absorbing layer in a nitrogen glove box at a speed of 3500 rpm for 30 s. The solution was then annealed on a hot stage at 90 °C for 5 min to obtain a perovskite passivation layer with a thickness of 8 nm. (6) Fabrication of electron transport layer Fullerene (C60) was deposited on the surface of the perovskite passivation layer using a thermal evaporation method (evaporation source temperature of 400℃ and evaporation rate of 0.8A / s) to obtain a fullerene layer with a thickness of 20nm; tin dioxide (SnO2) was deposited on the surface of the fullerene layer using an atomic layer deposition method to obtain a tin dioxide layer with a thickness of 15nm. The fullerene layer and the tin dioxide layer together constitute the electron transport layer. (7) Preparation of transparent conductive layer A 100 nm thick transparent conductive layer IZO was prepared on the surface of the electron transport layer using reactive plasma deposition (RPD). (8) Preparation of metal electrodes Silver was deposited on the surface of a transparent conductive layer using a thermal evaporation method, resulting in a layer with a height of 400 nm and an effective area of ​​1.0 cm². 2 The silver electrode was used; MgF2 was deposited on the surface of the transparent conductive layer by thermal evaporation to obtain an antireflection layer with a thickness of 120 nm; at the same time, a perovskite / crystalline silicon tandem solar cell module was obtained.

[0119] Example 2

[0120] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 2.

[0121] Example 3

[0122] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 3.

[0123] Example 4

[0124] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 4.

[0125] Example 5

[0126] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 5.

[0127] Example 6

[0128] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 6.

[0129] Example 7

[0130] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 7.

[0131] Example 8

[0132] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 8.

[0133] Example 9

[0134] The other conditions in this embodiment are the same as in embodiment 1, except that in step (3) of this embodiment, compound 1 is replaced with an equimolar amount of compound 9.

[0135] Comparative Example 1

[0136] The other conditions of this comparative example are the same as those of Example 1, except that in step (3) of this example, compound 1 is replaced with an equimolar amount of [4-(9H-carbazole-9-yl)ethyl]phosphoric acid (4PACz, Merck, CNPZ40).

[0137] Test case

[0138] At 25 ℃, AM1.5 standard solar spectrum, and irradiance of 1000 W / m 2Under the conditions of -0.1 to 2.00V, the performance (open-circuit voltage, short-circuit current density, fill factor and photoelectric conversion efficiency) of the perovskite / crystalline silicon tandem solar cell modules in each embodiment and comparative example was measured using a solar simulator. The specific test results are shown in Table 1.

[0139] (1) Open circuit voltage (Voc): The voltage value when the current is zero.

[0140] (2) Short-circuit current density (Jsc): The current value when the voltage is zero is the short-circuit current (Isc), and the current on a unit cell surface area is the short-circuit current density.

[0141] (3) Fill factor (FF): The ratio of the battery’s maximum output power (Pmax) to the product of the open-circuit voltage and the short-circuit current. The formula is (Pmax / Voc×Isc), where the maximum power point is the point where the battery’s output power reaches its maximum value.

[0142] (4) Photoelectric conversion efficiency (PCE): Photoelectric conversion efficiency refers to the ratio of maximum output power to incident light power (Pin), and the calculation formula is (Pmax / Pin)×100%.

[0143] Table 1: Photovoltaic performance test results of perovskite solar cells in each embodiment and comparative example

Claims

1. Compound of Formula I: ， In Formula I, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; D1 and D2 are each independently selected from substituted or unsubstituted phenothiazine-2,10-diyl, substituted or unsubstituted phenothiazine-3,10-diyl, substituted or unsubstituted 9H-carbazole-3,9-diyl, substituted or unsubstituted triphenylamine-4,4′-diyl, substituted or unsubstituted triphenylamine-3,4′-diyl, and substituted or unsubstituted triphenylamine-2,4′-diyl; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8.

2. The compound of formula I as claimed in claim 1, characterized in that, The compound of formula I is the compound of formula I-1: ， In Formula I-1, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8. Alternatively, the compound of formula I is a compound of formula I-2: ， In Formula I-2, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R1, R2, R3, and R4 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; c, d, e, and f are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8. Preferably, the compound of formula I-1 is selected from one or two of the following compounds: 、 ； Preferably, the I-2 compound is one or more selected from the following compounds: 、 、 。 3. The compound of formula I as claimed in claim 1, characterized in that, The compound of formula I is a compound of formula I-3: ， In Formula I-3, A1 and A2 are each independently selected from phosphate, carboxyl, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R5, R6, R7, and R8 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl, and hydroxyl groups; g, h, i, and j are each independently selected from 0 to 4; Y1 and Y2 are each independently selected from oxygen atoms or are absent; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8. Preferably, the compound of formula I-3 is selected from one or more of the following compounds: , , .

4. The compound of formula I as claimed in claim 1, characterized in that, The compound of formula I is a compound of formula I-4: ， In formula I-4, A1 and A2 are each independently selected from phosphate groups, carboxyl groups, and trimethoxysilyl groups; L1 and L2 are each independently selected from C2-C12 alkylene groups; R9 and R 10 R 11 R 12 R 13 R 14 Each is independently selected from C1-C8 alkyl, C1-C8 alkoxy, halogen, phenyl and hydroxyl groups; k, l, m, n, o, p are each independently selected from 0 to 5; Y1 and Y2 are each independently selected from oxygen atoms or are not present; X1 and X2 are each independently selected from sulfur atoms or selenium atoms; a and b are each independently integers from 0 to 8. Preferably, the compound of formula I-4 is .

5. A self-assembled monolayer precursor solution, characterized in that, The self-assembled monolayer precursor liquid comprises a solvent and a compound of formula I according to any one of claims 1-4; Preferably, the solvent is selected from one or more of methanol, ethanol, acetonitrile, chloroform, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; In the self-assembled monolayer precursor solution, the molar concentration of the compound of formula I is 0.01-2 mmol / mL.

6. A self-assembled monolayer, characterized in that, The self-assembled monolayer comprises a self-assembled monomolecular compound, which includes a dynamic covalent bridge bond and two identical monomer structures connected by the dynamic covalent bridge bond, wherein the dynamic covalent bridge bond is -SS- or -Se-S-; the monomer structure includes an anchoring group and a core, wherein the anchoring group and the core are connected by an alkyl chain, wherein the anchoring group is selected from phosphate, carboxyl, and trimethoxysilyl groups, and the core is selected from phenothiazine, carbazole, and C1-C4 alkoxy-substituted triarylamines; preferably, the alkyl chain is a C2-C12 alkylene group; More preferably, the self-assembled monomolecular compound is selected from the compound of formula I according to any one of claims 1-5; More preferably, the thickness of the self-assembled monolayer is 0.05-2 nm.

7. A method for preparing a self-assembled monolayer, characterized in that, The method includes coating the self-assembled monolayer precursor liquid of claim 5, and then annealing to obtain a self-assembled monolayer; preferably, the annealing method is heating annealing, the annealing temperature is 80-150℃, and the annealing time is 1-30 min, preferably 10-20 min.

8. A photovoltaic device, characterized in that, The photovoltaic device comprises the self-assembled monolayer as described in claim 6.

9. The photovoltaic device as described in claim 8, characterized in that, The photovoltaic device comprises, in sequence, a conductive substrate, a self-assembled monolayer, a perovskite light-absorbing layer, an electron transport layer, and electrodes.

10. The photovoltaic device as described in claim 8, characterized in that, The photovoltaic device is a perovskite solar cell; preferably, the perovskite solar cell is a single-junction perovskite cell, a crystalline silicon-perovskite tandem cell, a perovskite-perovskite tandem cell, a perovskite-copper indium gallium selenide tandem cell, or a perovskite-gallium arsenide tandem cell.

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