Oxygen / sulfur / selenium-containing heterocyclic self-assembled material, preparation method and application thereof

Abstract

This invention belongs to the field of perovskite solar cells, specifically disclosing a self-assembled material containing oxygen / sulfur / selenium heterocycles, its preparation method, and applications. By introducing furan, thiophene, or selenophene heterocycles into a carbazole or dibenzocarbazole core, high stability, large molecular dipoles, strong intermolecular interactions, and excellent interfacial passivation properties are achieved. The inverted perovskite solar cell prepared using the self-assembled material of this invention achieves an optimal photoelectric conversion efficiency of 26.85%, an open-circuit voltage of 1.194V, and a short-circuit current density of 25.95mA / cm². 2 The fill factor is 86.67%. After being stored in an atmospheric environment for 3000 hours, the device retains an efficiency of over 95%.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cells, and in particular to a self-assembled material containing oxygen / sulfur / selenium heterocycles, its preparation method, and its application. Background Technology

[0002] Perovskite solar cells (PSCs), as a novel type of photovoltaic device, possess advantages such as low cost, low production energy consumption, and high photoelectric conversion efficiency, and have developed rapidly in recent years, with laboratory efficiencies exceeding 27%. Hole transport materials are one of the key factors determining the efficiency and stability of perovskite solar cells. Self-assembled monolayers (SAMs), as hole transport materials, have attracted considerable attention due to their simple preparation, low material consumption, and tunable energy levels.

[0003] SAMs based on the carbazole-phosphonic acid structure, such as [4-(9H-carbazole-9-yl)butyl]phosphonic acid (4PACz) and (2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl)phosphonic acid (MeO-2PACz), have been extensively studied and some progress has been made. However, existing SAM materials have the following main drawbacks: First, the design of traditional SAM molecules focuses excessively on the modulation of electronic properties, neglecting their dual function as perovskite crystallization templates and buried interface passivators. Studies have shown that unpassivated buried interfaces contain a large number of uncoordinated Pb²⁺ defects, leading to severe nonradiative recombination and limiting the open-circuit voltage and fill factor of the device.

[0004] Secondly, to introduce passivation capabilities, researchers have attempted to introduce electron-donating groups such as methoxy or thiomethyl groups into the carbazole framework. However, these groups are themselves electron-rich and are highly susceptible to degradation under oxidative or photosensitive conditions, resulting in poor material stability and failing to meet the long-term operational requirements for commercial applications.

[0005] Third, the molecular design of high-performance SAMs requires simultaneously satisfying the dual requirements of strong intermolecular interactions (to form a dense and ordered monolayer) and macromolecular dipoles (to effectively adjust the electrode work function). Currently reported SAM materials struggle to achieve both of these simultaneously, resulting in low efficiency and poor stability of the fabricated perovskite solar cells, which severely hinders the further development of this technology.

[0006] Therefore, there is an urgent need to develop a novel self-assembled hole transport material that combines high stability, strong interface passivation capability, macromolecular dipoles, and good intermolecular stacking. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a self-assembled material containing oxygen / sulfur / selenium heterocycles, its preparation method, and its applications.

[0008] To achieve the above objectives, the present invention is implemented according to the following technical solution: The first technical solution provided by this invention is a self-assembled material containing oxygen / sulfur / selenium heterocycles, having the structure shown in formula (1), formula (2), formula (3) or formula (4): ; ; Equation (1) Equation (2) ; ; Equation (3) Equation (4) Among them, R1-R 12 Individually derived from hydrogen, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidine, hydrazine, hydrazone, C1-C 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl group, C1-C 10 Alkoxy, C3-C 10 cycloalkyl, C1-C 10 Hybrid Garden Base, C3-C 10 Cycloalkenyl, C1-C 10 Heterocyclic alkenyl, C6-C 30 Aryl, C1-C 30 One of heteroaryl, monovalent non-aromatic condensed polycyclic, monovalent non-aromatic condensed heterocyclic, biphenyl and terphenyl; L is selected from one of alkylene with 1-8 carbon atoms, aryl with 6-20 cyclic carbon atoms and heteroaryl with 5-12 cyclic atoms; X is selected from one of oxygen, sulfur and selenium.

[0009] The second technical solution provided by this invention is a method for preparing a self-assembled material containing oxygen / sulfur / selenium heterocycles as described in claim 1, comprising the following steps: S1. The compound shown in formula (I), formula (II), formula (III) or formula (IV) is subjected to a carbon-nitrogen coupling reaction with the compound shown in formula (V) to obtain the compound shown in formula (VI), formula (VII), formula (VIII) or formula (IX); The structural formulas of the compounds represented by formulas (I), (II), (III), and (IV) are as follows: ; Formula (I) Formula (II) Formula (III) Formula (IV) The structural formula of the compound represented by formula (V) is: Y1—L—Y2 Formula (V); Y1 and Y2 are halogens, and L is selected from one of alkylene with 1-8 carbon atoms, arylene with 6-20 cyclic carbon atoms, and heteroarylene with 5-12 cyclic carbon atoms; The structural formulas of the compounds shown in formulas (VI), (VII), (VIII), and (IX) are as follows: ; Formula (VI) Formula (VII) Formula (VIII) Formula (IX) S2. The compound shown in formula (VI), (VII), (VIII) or (IX) is subjected to a carbon-phosphorus coupling reaction with the compound shown in formula (X) to obtain the compound shown in formula (XI), (XII), (XIII) or (XIV). The structural formula of the compound represented by formula (X) is: or ; Z is selected from C1-C4 alkyl groups; The structural formulas of the compounds of formula (XI), formula (XII), formula (XIII), and formula (XIV) are as follows: ; Formula (XI) Formula (XII) Formula (XIII) Formula (XIV); S3. The compound represented by formula (XI), formula (XII), formula (XIII) or (XIV) is subjected to a hydrolysis reaction to obtain a self-assembled material containing oxygen / sulfur / selenium heterocycles represented by formula (1), formula (2), formula (3) or formula (4).

[0010] Further, in step S1, when L is selected from alkylene groups having 1-8 carbon atoms, the carbon-nitrogen coupling reaction specifically includes: taking the compound shown in formula (I), formula (II), formula (III) or formula (IV) and the compound shown in formula (V) in a molar ratio of 1:(2-40), mixing them with a base, a phase transfer catalyst and a solvent, and carrying out the carbon-nitrogen coupling reaction at 20-120°C for 12-48 h to obtain the compound shown in formula (VI), formula (VII), formula (VIII) or formula (IX); the base is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide; the phase transfer catalyst is tetrabutylammonium bromide (TBAB); the solvent is an organic solvent or water.

[0011] Further, in step S1, when L is selected from arylene groups with 6-20 carbon atoms or heteroarylene groups with 5-12 ring atoms, the carbon-nitrogen coupling reaction specifically includes: taking compounds of formula (I), (II), (III), or (IV) and compound (V) in a molar ratio of 1:(1-4), mixing them with a base, catalyst, catalyst ligand, and solvent, and carrying out the carbon-nitrogen coupling reaction at 20-150°C for 12-48 minutes. h, to obtain the compound shown in formula (VI), (VII), (VIII), or (IX); the base is selected from at least one of potassium carbonate, sodium carbonate, potassium phosphate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide; the catalyst is selected from at least one of copper powder, cuprous oxide, cuprous iodide, cuprous bromide, and cuprous chloride; the catalyst ligand is selected from at least one of L-proline, 18-crown ether-6, 1,2-cyclohexanediamine, 1,10-phenanthroline, and oxalyldiamine ligands; the solvent is an organic solvent; and when L is phenyl, Y1 is F or Cl, and Y2 is Br or I, no catalyst is needed, and the compound shown in formula (VI), (VII), (VIII), or (IX) can be obtained by electrophilic substitution reaction under the action of the base alone.

[0012] Further, step S2 specifically includes: mixing the compound represented by formula (VI), formula (VII), formula (VIII) or formula (IX) with an excess of the compound represented by formula (X), and carrying out a carbon-phosphorus coupling reaction at 100-160°C for 12-48 h to obtain the compound represented by formula (XI), formula (XII), formula (XIII) or (XIV).

[0013] Further, step S2 specifically includes: taking the compound represented by formula (VI), formula (VII), formula (VIII) or formula (IX) and an excess of the compound represented by formula (X) in a molar ratio of 1:(0.9~1.5), and mixing it with a base, catalyst, catalyst ligand, additive and solvent, and carrying out a carbon-phosphorus coupling reaction at 40-120℃ for 12-48 h to obtain the compound represented by formula (XI), formula (XII), formula (XIII) or (XIV); the base is selected from at least one of triethylamine, tripropylamine, and N-methyldicyclohexylamine; the catalyst is selected from at least one of palladium acetate, palladium on carbon, tetra(triphenylphosphine)palladium, and palladium chloride; the catalyst ligand is selected from at least one of triphenylphosphine and 1,1′-bis(diphenylphosphine)ferrocene; the additive is selected from at least one of potassium acetate and sodium acetate; and the solvent is an organic solvent.

[0014] Further, step S4 specifically includes: Take the compound shown in formula (XI), (XII), (XIII) or (XIV) and trimethylbromosilane or hydrochloric acid in a molar ratio of 1:(2-50). Mix the compound shown in formula (XI), (XII), (XIII) or (XIV) with an organic solvent, and then add trimethylbromosilane or hydrochloric acid. Perform a hydrolysis reaction at 0-60℃ for 24-48 h to obtain the self-assembled material containing oxygen / sulfur / selenium heterocycles shown in formula (1), (2), (3) or (4).

[0015] Preferably, the organic solvent is at least one selected from toluene, tetrahydrofuran, and dichloromethane.

[0016] The third technical solution provided by the present invention is the application of the above-mentioned self-assembled material containing oxygen / sulfur / selenium heterocycles in the preparation of perovskite solar cell devices, wherein the hole transport layer of the solar cell device is made of the self-assembled material containing oxygen / sulfur / selenium heterocycles.

[0017] Preferably, the perovskite solar cell is an inverted perovskite solar cell.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) Significantly improved stability: By introducing oxygen-containing / sulfur-containing / selenium heterocycles into the carbazole or dibenzocarbazole skeleton, the present invention utilizes the electron delocalization effect to reduce the local electron density of heteroatoms, thereby inhibiting oxidation or photodegradation. Compared with carbazole materials modified with methoxy or thiomethyl, the materials of the present invention have higher electrochemical and photochemical stability.

[0019] (2) Enhanced molecular dipole moment and tunable energy level: The non-centrosymmetric molecular framework of this invention endows the material with a larger molecular dipole moment (DFT calculated value 2.3~2.9 Debye), which can effectively adjust the work function of transparent conductive electrodes such as ITO, form cascaded energy level matching, and improve the open circuit voltage and fill factor. At the same time, the type of heteroatom and the substitution position can be flexibly controlled to adjust the HOMO / LUMO energy level.

[0020] (3) Enhanced intermolecular interactions: The heterocycles of the material of the present invention provide abundant dipole-dipole interactions including CH···π, O···π, S···π, Se···π and heteroatoms, which promote the pre-aggregation of molecules in solution and dense and ordered self-assembly on the substrate, forming a hole transport layer with high coverage and low defects.

[0021] (4) Excellent passivation ability of buried interface: The oxygen, sulfur and selenium atoms on the heterocycle of the material of the present invention serve as Lewis base sites, which interact with the uncoordinated Pb in the perovskite. 2+ It forms strong coordination, significantly reduces the density of interface defect states, and suppresses nonradiative recombination.

[0022] (5) Excellent optoelectronic device performance: The inverted perovskite solar cell prepared using the self-assembled material of this invention achieves an optimal photoelectric conversion efficiency of 26.85%, an open-circuit voltage of 1.194V, and a short-circuit current density of 25.95mA / cm². 2 The fill factor is 86.67%. After being stored in an atmospheric environment for 3000 hours, the device retains an efficiency of over 95%. Attached Figure Description

[0023] Figure 1 The 1H NMR spectrum of the intermediate compound 10-(4-bromobutyl)-10H-benzo[4,5]thieno[3,2-b]indole is shown.

[0024] Figure 2 The 1H NMR spectrum of the intermediate compound diethyl(4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonate.

[0025] Figure 3 The 1H NMR spectrum of compound (4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonic acid (JJ23) is shown.

[0026] Figure 4 This is a schematic diagram of the structure of the inverted planar heterojunction perovskite solar cell of the present invention, wherein: 1. a transparent conductive substrate ITO; 2. a monomolecular self-assembled layer; 3. a perovskite light-absorbing layer; 4. an electron transport layer (C 60 5. Copper or silver electrodes.

[0027] Figure 5 The JV curve and photovoltaic parameter diagram are shown for JJ23-based perovskite solar cells.

[0028] Figure 6 The JV curve and photovoltaic parameter diagram are shown for JJ29-based perovskite solar cells.

[0029] Figure 7 The 1H NMR spectrum of the intermediate compound 7-(4-bromobutyl)-7H-benzo[c]benzofuran[2,3-g]carbazole.

[0030] Figure 8 The 1H NMR spectrum of the intermediate compound diethyl(4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonate.

[0031] Figure 9 The 1H NMR spectrum of compound (4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ88) is shown.

[0032] Figure 10 The JV curve and photovoltaic parameter diagram are shown for JJ88-based perovskite solar cells.

[0033] Figure 11 The 1H NMR spectrum of the intermediate compound 7-(4-bromobutyl)-7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole.

[0034] Figure 12 The 1H NMR spectrum of the intermediate compound diethyl(4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonate.

[0035] Figure 13 The 1H NMR spectrum of compound (4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ89) is shown.

[0036] Figure 14 The JV curve and photovoltaic parameter diagram are shown for the JJ89-based perovskite solar cell. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention.

[0038] The following examples use several typical self-assembled materials containing oxygen / sulfur / selenium heterocycles, namely compounds JJ23, JJ29, JJ88, and JJ89, as examples to illustrate the present invention.

[0039] Example 1: Preparation of compound JJ23 and its application in perovskite solar cells The synthetic route for compound JJ23 is as follows: ;

[0040] The preparation process of this embodiment is described in detail based on the above route, as follows: (1) Synthesis of 10-(4-bromobutyl)-10H-benzo[4,5]thieno[3,2-b]indole 10H-benzo[4,5]thieno[3,2-b]indole (0.5 g, 2.24 mmol) was dissolved in 1,4-dibromobutane (6.8 mL, 44.8 mmol), followed by the sequential addition of tetrabutylammonium bromide (0.07 g, 0.15 equivalents) and 50% KOH aqueous solution (5 equivalents). The reaction was stirred overnight at 60°C. After the reaction was complete, the mixture was extracted with dichloromethane. The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: hexane: dichloromethane = 9:1 → 4:1, v / v) to give 0.7 g of white crystalline solid, yield 87%. The 1H NMR spectrum of compound 10-(4-bromobutyl)-10H-benzo[4,5]thieno[3,2-b]indole is shown below. Figure 1 As shown.

[0041] 1 H NMR (400 MHz, chloroform- d ) δ 7.92 (ddt, J = 18.7, 8.1, 1.0 Hz,2H), 7.76 (dt, J = 7.8, 1.0 Hz, 1H), 7.47 – 7.39 (m, 2H), 7.33 (dddd, J =8.3, 7.0, 3.7, 1.2 Hz, 2H), 7.25 – 7.16 (m, 1H), 4.56 (t, J = 7.0 Hz, 2H), 3.34 (t, J = 6.4 Hz, 2H), 2.20 – 1.82 (m, 4H).

[0042] (2) Synthesis of diethyl(4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonate 10-(4-bromobutyl)-10H-benzo[4,5]thieno[3,2-b]indole (0.7 g, 2.00 mmol) was dissolved in triethyl phosphite (20 equivalents, 6.66 g, 6.87 mL, 40 mmol), and the reaction mixture was heated overnight at 150°C. After the reaction was complete (TLC monitoring, dichloromethane:ethyl acetate = 5:1, v / v), the solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: dichloromethane:ethyl acetate = 5:1, v / v) to give 0.81 g of a colorless oil, 97% yield. The 1H NMR spectrum of the compound diethyl(4-(10H-benzo[4,5]thieno[3,2-b]indole-10-yl)butyl)phosphonate is shown below. Figure 2 As shown.

[0043] 1 H NMR (400 MHz, chloroform- d ) δ 8.01 – 7.89 (m, 2H), 7.77 (d, J =7.9 Hz, 1H), 7.51 – 7.42 (m, 2H), 7.35 (dddd, J = 8.3, 7.0, 4.1, 1.2 Hz, 2H),7.21 (ddd, J = 7.9, 7.1, 1.0 Hz, 1H), 4.60 (t, J = 7.2 Hz, 2H), 4.07 – 3.93(m, 4H), 2.14 – 1.66 (m, 6H), 1.23 (t, J = 7.1 Hz, 6H).

[0044] (3) Synthesis of (4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonic acid (JJ23) Diethyl(4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonate (0.81 g, 1.94 mmol) was dissolved in anhydrous dichloromethane (15 mL) under an argon atmosphere, followed by the dropwise addition of trimethylbromosilane (10 equivalents, 2.97 g, 2.56 mL, 19.4 mmol). The reaction was stirred at room temperature under an argon atmosphere for 12 hours. The solvent was then partially evaporated under reduced pressure, and the remaining liquid residue was dissolved in methanol (5 mL). Distilled water (40 mL) was then added dropwise until the solution became cloudy. The product was collected by filtration and washed with water to give 0.61 g of a white solid, in 88% yield. The 1H NMR spectrum of compound (4-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)butyl)phosphonic acid (JJ23) is as follows: Figure 3 As shown.

[0045] 1 H NMR (400 MHz, DMSO- d 6) δ 8.19 (d, J = 7.8 Hz, 1H), 8.10 – 8.03 (m,1H), 7.83 – 7.67 (m, 2H), 7.52 (ddd, J= 8.2, 7.2, 1.1 Hz, 1H), 7.42 (ddd, J = 8.2, 7.1, 1.1 Hz, 2H), 7.34 (ddd, J = 8.3, 7.0, 1.2 Hz, 2H), 7.18 (ddd, J =8.0, 7.0, 0.9 Hz, 1H), 4.69 (t, J = 7.1 Hz, 2H), 2.15 – 1.18 (m, 6H).

[0046] The solar cells involved in this embodiment include perovskite solar cells and organic solar cells, specifically taking an inverted planar heterojunction perovskite solar cell as an example. Figure 4 This is a schematic diagram of the structure of the inverted planar heterojunction perovskite solar cell involved in this invention. From bottom to top, it includes: a transparent conductive substrate ITO1, a single-molecule self-assembled layer (SAM) or hole transport layer 2 of JJ23, a perovskite light-absorbing layer 3, and an electron transport layer (C 60 4. And copper or silver electrodes 5. Refer to Figure 4 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate ITO: The etched transparent conductive substrate ITO was ultrasonically treated in cleaning agent, deionized water, anhydrous ethanol, acetone and isopropanol for 15 minutes in sequence. After being removed, it was dried with clean air and placed in an oven to dry at 120°C for 8 hours, followed by UV / ozone treatment for 30 minutes.

[0047] 2) Preparation of self-assembled monolayers (SAMs): Prepare a JJ23 solution; spin-coat the solution onto a transparent conductive substrate ITO at 4000 rpm for 40 s; anneal the resulting film at 100 °C for 10 minutes in nitrogen. 3) Preparation of perovskite light-absorbing layer: All ABX3 films have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0048] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 Deposited on the surface of perovskite.

[0049] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0050] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 5 As shown, by Figure 5 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.194V, and the short-circuit current density is 25.95mA / cm². 2 The fill factor is 86.67%, and the photoelectric conversion efficiency is 26.85%. After being stored in an atmospheric environment for 3000 hours, the device retains more than 95% of its initial efficiency.

[0051] Example 2: Preparation of compound JJ29 and its application in perovskite solar cells The synthetic route for compound JJ29 is as follows: ;

[0052] The preparation process of this embodiment is described in detail based on the above route, as follows: (1) Synthesis of 10-(4-bromobutyl)-10H-benzo[4,5]seleno[3,2-b]indole 10H-benzo[4,5]seleno[3,2-b]indole (1.2 g, 4.44 mmol) was dissolved in excess 1,4-dibromobutane (15 mL), followed by the sequential addition of tetrabutylammonium bromide (0.15 equivalents, 0.211 g, 0.66 mmol) and 50% KOH aqueous solution (5 equivalents, 22.2 mmol, 1.78 mL). The reaction was stirred overnight at 60°C. After the reaction was complete, the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: hexane: dichloromethane = 4:1, v / v) to give 1.65 g of gray powder, yield 92%.

[0053] 1 H NMR (400 MHz, Chloroform- d ) δ 8.09 (t, J = 7.5 Hz, 2H), 7.76 (d, J= 8.0 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.30 (t, J= 7.5 Hz, 1H), 7.25 (t, J = 7.0 Hz, 1H), 7.13 (t, J = 7.5 Hz, 1H), 4.57 (t, J = 7.1 Hz, 2H), 3.38 (t, J = 6.5 Hz, 2H), 2.15 (m, 7.1 Hz, 2H), 1.95 (m, 2H). (2) Synthesis of diethyl(4-(10H-benzo[4,5]seleno[3,2-b]indol-10-yl)butyl)phosphonate 10-(4-bromobutyl)-10H-benzo[4,5]seleno[3,2-b]indole (1.5 g, 3.7 mmol) was dissolved in triethyl phosphite (20 equivalents, 12.3 g, 12.7 mL, 74 mmol), and the reaction mixture was heated at 150°C overnight. After the reaction was complete (TLC monitoring, dichloromethane:ethyl acetate = 4:1, v / v), the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: dichloromethane:ethyl acetate = 4:1, v / v) to give 1.71 g of colorless oil, 95% yield.

[0054] 1 H NMR (400 MHz, chloroform- d ) δ 8.12 (m, 2H), 7.81 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.46 ( m, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.29(t, J = 7.0 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), , 4.61 (t, J = 7.2 Hz, 2H),4.08 – 3.93 (m, 4H), 2.14 – 1.66 (m, 6H), 1.23 (t, J = 7.1 Hz, 6H). (3) Synthesis of (4-(10H-benzo[4,5]seleno[3,2-b]indol-10-yl)butyl)phosphonic acid (JJ29) Diethyl(4-(10H-benzo[4,5]seleno[3,2-b]indol-10-yl)butyl)phosphonate (1.6 g, 3.46 mmol) was dissolved in anhydrous dichloromethane (24 mL) under an argon atmosphere, followed by the dropwise addition of trimethylbromosilane (10 equivalents, 5.3 g, 4.57 mL, 34.6 mmol). The reaction was stirred at room temperature under an argon atmosphere for 12 hours. The solvent was then partially evaporated under reduced pressure, and the remaining liquid residue was dissolved in methanol (8 mL). Distilled water (50 mL) was then added dropwise until the solution became cloudy. The product was collected by filtration and washed with water to give 1.3 g of off-white solid, in 92% yield.

[0055] 1 H NMR (400 MHz, DMSO- d 6) δ 8.13 (m, 2H), 7.74 (d, J = 8.0 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.23 (t, J = 7.0 Hz, 1H), 7.10 (t, J = 7.5 Hz, 1H), 4.69 (t, J = 7.1 Hz, 2H),2.15 – 1.18 (m, 6H). Referring to the method in Example 1, compound JJ29 was used instead of compound JJ23 as the hole transport layer material, and the remaining steps were the same. The test results are shown below. Figure 6 As shown, by Figure 6 The optimal photoelectric conversion efficiency parameters of the inverted planar heterojunction perovskite solar cell prepared in this embodiment are: open-circuit voltage 1.192 V, short-circuit current density 25.91 mA / cm2, fill factor 85.09%, and conversion efficiency 26.28%. After being stored in an atmospheric environment for 3000 hours, the device still maintains more than 92% of its initial efficiency.

[0056] Example 3: Preparation of compound JJ88 and its application in perovskite solar cells The synthetic route for compound JJ88 is as follows: ;

[0057] The preparation process of this embodiment is described in detail based on the above route, as follows: (1) Synthesis of 7-(4-bromobutyl)-7H-benzo[c]benzofuran[2,3-g]carbazole 0.6 g (2 mmol) of 7H-benzo[c]benzofuran[2,3-g]carbazole was dissolved in excess 1,4-dibromobutane (10 mL), followed by the sequential addition of tetrabutylammonium bromide (0.15 equivalents, 0.095 g, 0.3 mmol) and 50% KOH aqueous solution (5 equivalents, 10 mmol, 0.8 mL). The reaction was stirred overnight at 60°C. After the reaction was complete, the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: hexane: dichloromethane = 4:1, v / v) to give 0.77 g of white powder, yield 89%. The 1H NMR spectrum of compound 7-(4-bromobutyl)-7H-benzo[c]benzofuran[2,3-g]carbazole is shown below. Figure 7 As shown.

[0058] 1 H NMR (400 MHz, Chloroform- d ) δ 10.01 (dt, J = 8.4, 0.9 Hz, 1H),8.07 – 8.00 (m, 3H), 7.97 (d, J = 8.9 Hz, 1H), 7.89 – 7.83 (m, 2H), 7.68 (d, J = 8.9 Hz, 1H), 7.58 – 7.40 (m, 4H), 4.57 (t, J = 7.1 Hz, 2H), 3.38 (t, J =6.5 Hz, 2H), 2.15 (m, 7.1 Hz, 2H), 1.95 (m, 2H). (2) Synthesis of diethyl(4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonate 0.7 g (1.58 mmol) of 7-(4-bromobutyl)-7H-benzo[c]benzofuran[2,3-g]carbazole was dissolved in excess triethyl phosphite (10 mL), and the reaction mixture was heated at 145°C overnight. After the reaction was complete, the solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: dichloromethane: ethyl acetate = 3:1, v / v) to give 0.72 g of a colorless oil, 91% yield. The 1H NMR spectrum of the compound diethyl(4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonate is shown below. Figure 8 As shown.

[0059] 1 H NMR (400 MHz, Chloroform- d ) δ 10.00 (d, J = 8.4 Hz, 1H), 8.03 (dd, J = 8.2, 1.7 Hz, 3H), 7.96 (d, J = 8.8 Hz, 1H), 7.89 – 7.83 (m, 2H), 7.69 (d, J = 8.9 Hz, 1H), 7.58 – 7.39 (m, 4H), 4.55 (t, J = 7.2 Hz, 2H), 4.06 – 3.96(m, 4H), 2.08 (m, 2H), 1.81 – 1.66 (m, 4H), 1.22 (t, J = 7.1 Hz, 6H). (3) Synthesis of (4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ88) Under an argon atmosphere, diethyl(4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonate (0.6 g, 1.2 mmol) was dissolved in anhydrous dichloromethane (15 mL), followed by the dropwise addition of trimethylbromosilane (10 equivalents, 1.84 g, 12 mmol). The reaction was stirred at room temperature under an argon atmosphere for 12 hours. Afterward, the solvent was partially evaporated under reduced pressure, and the remaining liquid residue was dissolved in methanol (4 mL). Then, distilled water (30 mL) was added dropwise until the solution became cloudy. The product was collected by filtration and washed with water to give 0.49 g of an off-white solid, with a yield of 92%. The 1H NMR spectrum of compound (4-(7H-benzo[c]benzofuran[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ88) is shown below. Figure 9 As shown.

[0060] 1 H NMR (400 MHz, DMSO- d 6) δ 9.86 (d, J = 8.4 Hz, 1H), 8.25 – 8.17 (m,2H), 8.14 – 8.09 (m, 1H), 8.06 (d, J = 2.1 Hz, 2H), 7.98 (d, J= 8.1 Hz, 1H),7.90 – 7.83 (m, 2H), 7.59 – 7.43 (m, 3H), 4.70 (t, J = 7.1 Hz, 2H), 1.95 (m,2H), 1.67 – 1.53 (m, 4H). Referring to the method in Example 1, compound JJ88 was used instead of compound JJ23 as the hole transport layer material, and the remaining steps were the same. The test results are shown below. Figure 10 As shown, by Figure 10 It can be seen that the optimal photoelectric conversion efficiency parameters of the inverted planar heterojunction perovskite solar cell prepared in this embodiment are: open-circuit voltage 1.193 V, short-circuit current density 26.08 mA / cm². 2 The fill factor is 85.68%, and the conversion efficiency is 26.65%. After being stored in an atmospheric environment for 3000 hours, the device still maintains more than 93% of its initial efficiency.

[0061] Example 4: Preparation of compound JJ89 and its application in perovskite solar cells The synthetic route for compound JJ89 is as follows: ;

[0062] The preparation process of this embodiment is described in detail based on the above route, as follows: (1) Synthesis of 7-(4-bromobutyl)-7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole 7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole (0.9 g, 2.78 mmol) was dissolved in excess 1,4-dibromobutane (15 mL), followed by the sequential addition of tetrabutylammonium bromide (0.15 equivalents, 0.134 g, 0.42 mmol) and 50% KOH aqueous solution (5 equivalents, 14 mmol, 1.1 mL). The reaction was stirred overnight at 60°C. After the reaction was complete, the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: hexane: dichloromethane = 4:1, v / v) to give 1.17 g of white powder, 92% yield. The 1H NMR spectrum of compound 7-(4-bromobutyl)-7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole is shown below. Figure 11 As shown.

[0063] 1 H NMR (400 MHz, Chloroform- d ) δ 9.76 (d, J= 8.5 Hz, 1H), 8.26 (dd, J = 22.5, 8.3 Hz, 2H), 8.08 – 7.94 (m, 3H), 7.84 (ddd, J = 8.4, 6.8, 1.4 Hz,1H), 7.68 (m, 2H), 7.59 – 7.45 (m, 3H), 4.60 (t, J = 6.9 Hz, 2H), 3.39 (t, J = 6.5 Hz, 2H), 2.16 (m, 2H), 1.95 (m, 2H). (2) Synthesis of diethyl(4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonate 1 g (2.18 mmol) of 7-(4-bromobutyl)-7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole was dissolved in excess triethyl phosphite (15 mL), and the reaction mixture was heated overnight at 145°C. After the reaction was complete, the solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: dichloromethane: ethyl acetate = 3:1, v / v) to give 1.06 g of a colorless oil, 94% yield. The 1H NMR spectrum of the compound diethyl(4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonate is shown below. Figure 12 As shown.

[0064] 1 H NMR (400 MHz, Chloroform- d ) δ 9.75 (dd, J = 8.5, 1.1 Hz, 1H), 8.29– 8.19 (m, 2H), 8.02 (td, J = 8.5, 1.4 Hz, 2H), 7.95 (d, J = 8.9 Hz, 1H), 7.83 (ddd, J = 8.4, 6.9, 1.5 Hz, 1H), 7.71 – 7.61 (m, 2H), 7.58 – 7.45 (m,3H), 4.55 (t, J = 7.2 Hz, 2H), 4.06 – 3.95 (m, 4H), 2.07 (p, J= 7.3 Hz, 2H), 1.79 – 1.68 (m, 4H), 1.22 (m, 6H). (3) Synthesis of (4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ89) Under an argon atmosphere, diethyl(4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonate (0.8 g, 1.55 mmol) was dissolved in anhydrous dichloromethane (20 mL), followed by the dropwise addition of trimethylbromosilane (10 equivalents, 2.38 g, 15.5 mmol). The reaction was stirred at room temperature under an argon atmosphere for 12 hours. Afterward, the solvent was partially evaporated under reduced pressure, and the remaining liquid residue was dissolved in methanol (6 mL). Then, distilled water (40 mL) was added dropwise until the solution became cloudy. The product was collected by filtration and washed with water to give 0.65 g of an off-white solid, with a yield of 91%. The 1H NMR spectrum of compound (4-(7H-benzo[c]benzo[4,5]thieno[2,3-g]carbazole-7-yl)butyl)phosphonic acid (JJ89) is shown below. Figure 13 As shown.

[0065] 1 H NMR (400 MHz, DMSO- d 6) δ 9.63 (d, J = 8.4 Hz, 1H), 8.49 – 8.39 (m,2H), 8.20 – 8.11 (m, 2H), 8.06 (s, 2H), 7.98 (dd, J = 8.8, 1.8 Hz, 1H), 7.83(ddd, J = 8.3, 6.8, 1.4 Hz, 1H), 7.58 – 7.49 (m, 3H), 4.70 (t, J = 7.1 Hz,2H), 1.94 (m, 2H), 1.61 (m, 4H). Referring to the method in Example 1, compound JJ89 was used instead of compound JJ23 as the hole transport layer material, and the remaining steps were the same. The test results are shown below. Figure 14 As shown, by Figure 14 The optimal photoelectric conversion efficiency parameters of the inverted planar heterojunction perovskite solar cell prepared in this embodiment are: open-circuit voltage 1.196 V, short-circuit current density 26.38 mA / cm2, fill factor 84.91%, and conversion efficiency 26.80%. After being stored in an atmospheric environment for 3000 hours, the device still maintains more than 98% of its initial efficiency.

[0066] The above embodiments demonstrate that the fused carbazole / dibenzocarbazole-phosphonic acid self-assembled material with oxygen-, sulfur-, and selenium heterocycles provided by the present invention possesses high stability, macromolecular dipoles, strong intermolecular interactions, and excellent buried interface passivation capabilities, which can significantly improve the efficiency and stability of perovskite solar cells, and has outstanding technical effects and industrial application value.

[0067] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A self-assembled material containing oxygen / sulfur / selenium heterocycles, characterized in that, It has the structure shown in equation (1), equation (2), equation (3) or equation (4): ； Equation (1) Equation (2) ； Equation (3) Equation (4) Among them, R1-R 12 Individually derived from hydrogen, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidine, hydrazine, hydrazone, C1-C 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl group, C1-C 10 Alkoxy, C3-C 10 cycloalkyl, C1-C 10 Hybrid Garden Base, C3-C 10 Cycloalkenyl, C1-C 10 Heterocyclic alkenyl, C6-C 30 Aryl, C1-C 30 One of heteroaryl, monovalent non-aromatic condensed polycyclic, monovalent non-aromatic condensed heterocyclic, biphenyl and terphenyl; L is selected from one of alkylene with 1-8 carbon atoms, aryl with 6-20 cyclic carbon atoms and heteroaryl with 5-12 cyclic atoms; X is selected from one of oxygen, sulfur and selenium.

2. A method for preparing a self-assembled material containing oxygen / sulfur / selenium heterocycles as described in claim 1, characterized in that, Includes the following steps: S1. The compound shown in formula (I), formula (II), formula (III) or formula (IV) is subjected to a carbon-nitrogen coupling reaction with the compound shown in formula (V) to obtain the compound shown in formula (VI), formula (VII), formula (VIII) or formula (IX); The structural formulas of the compounds represented by formulas (I), (II), (III), and (IV) are as follows: ； Formula (I) Formula (II) Formula (III) Formula (IV) The structural formula of the compound represented by formula (V) is: Y1—L—Y2 Formula (V); Y1 and Y2 are halogens, and L is selected from one of alkylene with 1-8 carbon atoms, arylene with 6-20 cyclic carbon atoms, and heteroarylene with 5-12 cyclic carbon atoms; The structural formulas of the compounds shown in formulas (VI), (VII), (VIII), and (IX) are as follows: ； Formula (VI) Formula (VII) Formula (VIII) Formula (IX) S2. The compound shown in formula (VI), (VII), (VIII) or (IX) is subjected to a carbon-phosphorus coupling reaction with the compound shown in formula (X) to obtain the compound shown in formula (XI), (XII), (XIII) or (XIV). The structural formula of the compound represented by formula (X) is: or ; Z is selected from C1-C4 alkyl groups; The structural formulas of the compounds of formula (XI), formula (XII), formula (XIII), and formula (XIV) are as follows: ； Formula (XI) Formula (XII) Formula (XIII) Formula (XIV); S3. The compound represented by formula (XI), formula (XII), formula (XIII) or (XIV) is subjected to a hydrolysis reaction to obtain a self-assembled material containing oxygen / sulfur / selenium heterocycles represented by formula (1), formula (2), formula (3) or formula (4).

3. The method for preparing the self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 2, characterized in that, In step S1, when L is selected from alkylene groups having 1-8 carbon atoms, the carbon-nitrogen coupling reaction specifically includes: taking the compound shown in formula (I), formula (II), formula (III) or formula (IV) and the compound shown in formula (V) in a molar ratio of 1:(2-40), mixing them with a base, a phase transfer catalyst and a solvent, and carrying out the carbon-nitrogen coupling reaction at 20-120°C for 12-48 h to obtain the compound shown in formula (VI), formula (VII), formula (VIII) or formula (IX); the base is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide; the phase transfer catalyst is tetrabutylammonium bromide (TBAB); the solvent is an organic solvent or water.

4. The method for preparing the self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 2, characterized in that, In step S1, when L is selected from arylene groups with 6-20 carbon atoms or heteroarylene groups with 5-12 ring atoms, the carbon-nitrogen coupling reaction specifically includes: taking compounds of formula (I), (II), (III), or (IV) and compound (V) in a molar ratio of 1:(1-4), mixing them with a base, catalyst, catalyst ligand, and solvent, and carrying out the carbon-nitrogen coupling reaction at 20-150°C for 12-48 minutes. h, to obtain a compound represented by formula (VI), (VII), (VIII), or (IX); the base is selected from at least one of potassium carbonate, sodium carbonate, potassium phosphate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide; the catalyst is selected from at least one of copper powder, cuprous oxide, cuprous iodide, cuprous bromide, and cuprous chloride; the catalyst ligand is selected from at least one of L-proline, 18-crown ether-6, 1,2-cyclohexanediamine, 1,10-phenanthroline, and oxalyldiamine ligands; the solvent is an organic solvent.

5. The method for preparing the self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 3, characterized in that, Step S2 specifically includes: mixing the compound represented by formula (VI), formula (VII), formula (VIII) or formula (IX) with an excess of the compound represented by formula (X), and carrying out a carbon-phosphorus coupling reaction at 100-160°C for 12-48 h to obtain the compound represented by formula (XI), formula (XII), formula (XIII) or (XIV).

6. The method for preparing the self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 4, characterized in that, Step S2 specifically includes: taking the compound represented by formula (VI), (VII), (VIII), or (IX) and an excess of the compound represented by formula (X) in a molar ratio of 1:(0.9-1.5), and mixing it with a base, catalyst, catalyst ligand, additive, and solvent, and carrying out a carbon-phosphorus coupling reaction at 40-120°C for 12-48 h to obtain the compound represented by formula (XI), (XII), (XIII), or (XIV); the base is selected from at least one of triethylamine, tripropylamine, and N-methyldicyclohexylamine; the catalyst is selected from at least one of palladium acetate, palladium on carbon, tetra(triphenylphosphine)palladium, and palladium chloride; the catalyst ligand is selected from at least one of triphenylphosphine and 1,1′-bis(diphenylphosphine)ferrocene; the additive is selected from at least one of potassium acetate and sodium acetate; and the solvent is an organic solvent.

7. The method for preparing the self-assembled material of oxygen / sulfur / selenium heterocycles according to claim 5 or 6, characterized in that, Step S4 specifically includes: Take the compound shown in formula (XI), (XII), (XIII) or (XIV) and trimethylbromosilane or hydrochloric acid in a molar ratio of 1:(2-50). Mix the compound shown in formula (XI), (XII), (XIII) or (XIV) with an organic solvent, and then add trimethylbromosilane or hydrochloric acid. Perform a hydrolysis reaction at 0-60℃ for 24-48 h to obtain the self-assembled material containing oxygen / sulfur / selenium heterocycles shown in formula (1), (2), (3) or (4).

8. The method for preparing a self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 3, 4, 6, or 7, characterized in that, The organic solvent is at least one of toluene, tetrahydrofuran, and dichloromethane.

9. The application of a self-assembled material containing oxygen / sulfur / selenium heterocycles as described in claim 1 in the fabrication of perovskite solar cell devices, characterized in that, The hole transport layer of the solar cell device is made of a self-assembled material containing oxygen / sulfur / selenium heterocycles as described in claim 1.

10. The application of the self-assembled material containing oxygen / sulfur / selenium heterocycles according to claim 9 in the fabrication of perovskite solar cell devices, characterized in that, The perovskite solar cell is an inverted perovskite solar cell.

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