Acridine compound, hole transport material, perovskite solar cell and device

Abstract

The invention discloses an acridine compound, a hole transport material, a perovskite solar cell and a perovskite solar device, and the chemical structural formula of the acridine compound is as shown in the formula I. According to the invention, R1 and R2 with large steric hindrance conjugated structures are introduced on the basis of a basic structure of 9, 10-dihydroacridine, so that the acridine compound has the characteristic of asymmetric steric hindrance; meanwhile, R3 is used as an anchoring group. Therefore, when the acridine compound is applied to solar cell devices such as perovskite solar cells as a hole transport material, asymmetric steric hindrance, molecular aggregation inhibition and multi-dimensional ordered charge transport channel construction are realized by performing steric hindrance modification on the acridine derivative; the efficiency and the stability of the perovskite device can be remarkably improved, and the application is wide.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of solar cells, and particularly relates to an acridine compound, a hole transport material, a perovskite solar cell and a device. BACKGROUND

[0002] Perovskite solar cells (PSC) have been widely used in the field of photovoltaic power generation due to their high photoelectric conversion efficiency, excellent adjustment flexibility and low preparation cost, and have shown great commercial application prospects. In particular, the inverted (p-i-n) structure perovskite solar cell has become an ideal structure choice for commercialized cells due to its excellent power conversion efficiency (PCE), good compatibility with the laminated structure and excellent performance under weak light conditions, and has become a leader in the next generation of photovoltaic technology field.

[0003] In the inverted (reverse) structure perovskite solar cell, the hole transport layer (HTL) is the first prepared functional layer, which mainly functions to block electrons and transport holes. At the same time, the application of hole transport material can effectively adjust the interface energy level arrangement and improve the contact condition between the perovskite layer and the anode. Therefore, the selection of HTL material plays a crucial decisive role in the performance of perovskite solar cell device. Self-assembled monolayer material (SAMs) has promoted the revolutionary development of inverted perovskite solar cell due to its incomparable advantages in energy level adjustability, cost-effectiveness and reduction of parasitic absorption.

[0004] However, the current self-assembled monolayer material has the problem of excessive aggregation in solution or thin film state due to its amphiphilic nature, which ultimately affects the power conversion efficiency and stability of the perovskite solar cell device, thereby further hindering its more widespread application in the field of perovskite solar cells. SUMMARY

[0005] The present application aims to at least solve one of the problems in the related art. To this end, the present application aims to provide an acridine compound, a hole transport material, a perovskite solar cell, and a device. The present application introduces R1 and R2 with large steric hindrance conjugated structure on the basis of the basic structure of 9,10-dihydroacridine, which gives the acridine compound asymmetric steric hindrance characteristics; at the same time, R3 is used as an anchor group. Therefore, when the acridine compound is used as a hole transport material in a solar cell device such as a perovskite solar cell, by modifying the steric hindrance of the acridine derivative, asymmetric steric hindrance, molecular aggregation inhibition, and multi-dimensional ordered charge transport channel construction are realized, which can significantly improve the efficiency and stability of the perovskite device, and has a wide range of applications.

[0006] The present application provides an acridine compound. According to an embodiment of the present application, the chemical structural formula of the acridine compound is shown as formula I; The formula I is: ; Wherein, R1 and R2 are each independently selected from substituted methyl, substituted aryl or substituted heteroaryl, R3 is a phosphoric acid group, a carboxylic acid group or a sulfonic acid group, and n is any natural number from 1 to 10.

[0007] The acridine compound of the above-mentioned embodiments of the present application introduces R1 and R2 with large steric hindrance conjugated structure on the basis of the basic structure of 9,10-dihydroacridine, which gives the acridine compound asymmetric steric hindrance characteristics; at the same time, R3 is used as an anchor group. Therefore, when the acridine compound is used as a hole transport material in a solar cell device such as a perovskite solar cell, by modifying the steric hindrance of the acridine derivative, asymmetric steric hindrance, molecular aggregation inhibition, and multi-dimensional ordered charge transport channel construction are realized, which can significantly improve the efficiency and stability of the perovskite device, and has a wide range of applications.

[0008] In addition, the acridine compound according to the above-mentioned embodiments of the present application can also have the following additional technical features: In some embodiments of the present application, R1 and R2 are each independently selected from a methyl group substituted with an electron-withdrawing group, an aryl group substituted with an electron-withdrawing group, or a heteroaryl group substituted with an electron-withdrawing group, and the electron-withdrawing group includes a fluorine group, a trifluoromethyl group, or a cyano group.

[0009] In some embodiments of the present application, R1 and R2 are each independently selected from any of the following substituents: .

[0010] In some embodiments of the present application, n is any natural number from 2 to 6; And / or, R3 is a phosphoric acid group; and / or, the R1 and the R2 are different in group type.

[0011] In some embodiments of the present application, the compounds include any one of the following chemical structural formulae: , , , or .

[0012] A second aspect of the present application provides a hole transport material. According to embodiments of the present application, the hole transport material includes the acridine compound of the first aspect. Thus, when the hole transport material is applied to a solar cell device such as a perovskite solar cell, by means of spatial steric hindrance modification of the acridine derivative, asymmetric spatial steric hindrance and molecular aggregation inhibition and multi-dimensional ordered charge transport channel construction can be achieved, which can significantly improve the efficiency and stability of the perovskite device, etc.

[0013] A third aspect of the present application provides a perovskite solar cell. According to embodiments of the present application, the perovskite solar cell includes a conductive substrate layer, a hole transport layer, a perovskite light-absorbing layer, an interface modification layer, an electron transport layer and a top electrode layer which are sequentially stacked; the hole transport layer is the hole transport material of the second aspect. Thus, the power conversion efficiency and stability of the perovskite solar cell are significantly improved.

[0014] In addition, the perovskite solar cell according to the above-mentioned embodiments of the present application can also have the following additional technical features: In some embodiments of the present application, the conductive substrate includes at least one of glass, a steel plate, a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a polyimide substrate, an indium tin oxide substrate, an aluminum-doped zinc oxide substrate and a fluorine-doped tin oxide substrate; and / or, the perovskite light-absorbing layer includes an ABX3 type material; wherein A includes at least one of Rb + , Cs + , CH3NH3 + , CH3CH2NH3 + , CH3(CH2)2NH3 + , CH3(CH2)3NH3 + and HC(NH2)2 + , B includes at least one of Pb 2+ , Sn 2+ , Cu 2+ and Ge 2+ , and X includes Cl - , Br - , I- SCN - BF4 - and PF6 - ; and / or, the interface modification layer comprises at least one of phenethylammonium iodide, phenethylammonium chloride, phenyldimethylammonium iodide and oleylamine iodide; and / or, the electron transport layer comprises at least one of TiO2, SnO2, ZnO, phenyl-C61-butyric acid methyl ester, phenyl-C71-butyric acid methyl ester, 2,4,6-triisopropylphenyl diimine, bis[1-(3-methoxycarbonyl)propyl]-1,4-phenyl bisimine, C 60 and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and / or, the top electrode layer comprises at least one of a metal material and a transparent oxide material, the metal material comprises at least one of gold, silver, copper and aluminum, and the transparent oxide material comprises at least one of indium tin oxide and indium zinc oxide.

[0015] In some embodiments of the present application, the thickness of the hole transport layer is 1-20 nm; and / or, the thickness of the perovskite light absorption layer is 300-600 nm; and / or, the thickness of the interface modification layer is 1-20 nm; and / or, the thickness of the electron transport layer is 5-40 nm; and / or, the thickness of the top electrode layer is 50-200 nm.

[0016] A fourth aspect of the present application provides a device. According to embodiments of the present application, the device comprises the hole transport material of the second aspect or the perovskite solar cell of the third aspect. Thus, the electrical performance and service life and other performances of the device are significantly improved.

[0017] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0018] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings. Figure 1 A perovskite solar cell structure diagram provided for embodiments of the present application.

[0019] Figure 2 A perovskite solar cell electrical performance test result diagram provided for embodiments of the present application.

[0020] Reference signs: Figure 1 Fig. 1: 1 - conductive substrate layer, 2 - hole transport layer, 3 - perovskite light absorption layer, 4 - interface modification layer, 5 - electron transport layer, 6 - top electrode layer. DETAILED DESCRIPTION

[0021] The embodiments of the present application are described below in detail by way of example, which are intended to explain the present application and cannot be understood as a limitation of the present application.

[0022] The first aspect of the present application proposes an acridine compound. According to the embodiments of the present application, the chemical structural formula of the acridine compound is shown as formula I; The formula I: ; Wherein, R1 and R2 are each independently selected from substituted methyl, substituted aryl or substituted heteroaryl, R3 is a phosphoric acid group, a carboxylic acid group or a sulfonic acid group, and n is any natural number from 1 to 10.

[0023] The acridine compound of the above-mentioned embodiments of the present application introduces R1 and R2 with large steric hindance conjugated structure on the basis of the basic structure of 9,10-dihydroacridine, which gives the acridine compound asymmetric steric hindance characteristics; at the same time, R3 is used as an anchor group. Therefore, when the acridine compound is used as a hole transport material in solar cell devices such as perovskite solar cells, by modifying the acridine derivative with steric hindance, asymmetric steric hindance and molecular aggregation inhibition are achieved, and a multi-dimensional ordered charge transport channel is constructed, which can significantly improve the efficiency and stability of perovskite devices, and has wide application. Specifically: 1. As shown in formula II, R1 and R2 with large steric hindance conjugated structure are introduced on the basis of the basic structure of 9,10-dihydroacridine, which has a central sp 3 Hybrid carbon atom in its chemical structure, which presents a tetrahedral geometry; at the same time, the chemical structure of 9,10-dihydroacridine itself has suitable electron-donating ability and ideal energy level arrangement, which provides a perfect basis for creating asymmetric space environment of SAM molecules.

[0024] Formula II: .

[0025] 2. The introduction of conjugated large steric hindance substituents, the interaction between the substituents, leads to a greater degree of torsion angle and enhanced multi-molecular interaction, which can make the SAM molecules form a larger steric volume, which is conducive to inhibiting the aggregation between molecules and improving the uniformity of the thin film; the conjugated steric hindance can enhance the CH-π interaction between molecules, increase the hole transport path and improve the molecular transport performance; the conjugated structure makes the molecule form a weak D-A structure inside, which enhances the optical and electrical stability of the molecule, etc.

[0026] According to some embodiments of the present application, R1 and R2 are each independently selected from a methyl group substituted with an electron-withdrawing group, an aryl group substituted with an electron-withdrawing group, or a heteroaryl group substituted with an electron-withdrawing group, and the electron-withdrawing group includes a fluoro group, a trifluoromethyl group, or a cyano group. In this way, the D-A effect and the optical and electrical stability of the acridine compound can be further enhanced by the electron-withdrawing structures such as cyano, fluoro, trifluoromethyl, etc., thereby further improving the stability of the perovskite solar cell, etc.

[0027] According to some embodiments of the present application, R1 and R2 are each independently selected from any one of the following substituents: .

[0028] It should be noted that “----” in the chemical structure of the above substituent only represents the connection or disconnection of the chemical bond at this point, and is not part of the substituent.

[0029] According to some embodiments of the present application, n is any natural number from 2 to 6, for example, can be 2, 3, 4, 5, 6; and / or, R3 is a phosphoric acid group; and / or, the types of R1 and R2 are different.

[0030] According to some embodiments of the present application, the following compounds are included: 、 、 、 or .

[0031] It should be noted that the acridine compounds provided in the present application can be prepared by referring to the existing acridine compounds, and only the type of 9,10-dihydroacridine raw material with a substituent group is adjusted. Specifically, when R3 is a phosphoric acid group, the preparation method of the acridine compound provided in the present application includes the following steps: 9,10-dihydroacridine with a substituent group, NaH under N2 atmosphere, add DMF (N,N-dimethylformamide) and keep stirring until completely dissolved. At 0°C, (4-bromobutyl) diethyl phosphonate is added dropwise to the solution, and the reaction is slowly warmed to room temperature and stirred overnight. After the reaction is completed, the mixture is quenched with ice water and extracted with dichloromethane, then the organic layer is washed with water three times, and finally the organic solvent is removed by reduced pressure distillation, and the crude product is purified by column chromatography to obtain the target product.

[0032] The second aspect of the present application provides a hole transport material. According to embodiments of the present application, the hole transport material comprises the acridine compound of the first aspect. Thus, when the hole transport material is applied to a solar cell device such as a perovskite solar cell (for example, the acridine compound is applied to a hole transport layer material of an inverted (p-i-n) structure perovskite solar cell (PSC)), by means of steric hindrance modification of the acridine derivative, asymmetric steric hindrance and molecular aggregation inhibition are achieved, and a multi-dimensional ordered charge transport channel is constructed, which can significantly improve the efficiency and stability of the perovskite device.

[0033] The third aspect of the present application provides a perovskite solar cell. According to embodiments of the present application, as shown in Figure 1 , the perovskite solar cell comprises a conductive substrate layer 1, a hole transport layer 2, a perovskite light-absorbing layer 3, an interface modification layer 4, an electron transport layer 5 and a top electrode layer 6 which are sequentially stacked; the hole transport layer 2 is the hole transport material of the second aspect. Thus, the power conversion efficiency and stability of the perovskite solar cell are significantly improved. Specifically, an efficiency of 25.34% can be achieved, and the stability is improved, which can retain about 85% of the initial efficiency after being stored in an air environment with a relative humidity (RH) of 45%±10% for 3026 hours, and can retain 94% of the initial efficiency after 500 hours of maximum power point tracking under 1 sun irradiation in an air environment with a temperature of 45±5°C and a RH of 70%±10%.

[0034] In addition, the perovskite solar cell according to the above embodiments of the present application can have the following additional technical features: In some embodiments of the present application, the conductive substrate comprises at least one of glass, a steel plate, a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a polyimide substrate, an indium tin oxide substrate, an aluminum-doped zinc oxide substrate and a fluorine-doped tin oxide substrate.

[0035] In some embodiments of the present application, the perovskite light-absorbing layer comprises an ABX3 type material; wherein A comprises at least one of Rb + , Cs + , FA + (carbamido ion), MA + (methylammonium ion), CH3NH3 + , CH3CH2NH3 + , CH3(CH2)2NH3 + , CH3(CH2)3NH3 + and HC(NH2)2 + , B comprises Pb 2+ , Sn 2+ , Cu2+ and Ge 2+ X includes at least one of Cl - , Br - , I - , SCN - , BF4 - and PF6 - .

[0036] In some embodiments of the present application, the interface modification layer is a low-dimensional perovskite material, for example including at least one of PEAI (phenethylammonium iodide), PEACL (phenethylammonium chloride), PDADI (phenyldimethylammonium iodide) and OAmI (oleylamine iodide).

[0037] In some embodiments of the present application, the electron transport layer includes TiO2, SnO2, ZnO, PC 61 BM (phenyl-C61-butyric acid methyl ester), PC 71 BM (phenyl-C71-butyric acid methyl ester), TIPD (2,4,6-triisopropylphenyl diimine), ICBA (bis[1-(3-methoxycarbonyl)propyl]-1,4-phenyl bisimine), C 60 and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline).

[0038] In some embodiments of the present application, the top electrode layer includes a metal material and a transparent oxide material, etc., the metal material generally uses a material with a high work function, such as gold, silver, copper, aluminum and the like, and the transparent oxide material can be ITO, IZO (indium zinc oxide) and the like, and can use existing film preparation methods in the art, such as evaporation, vacuum evaporation, magnetron sputtering, multi-arc ion plating and the like.

[0039] In some embodiments of the present application, the thickness of the hole transport layer is 1-20 nm, for example, can be 3 nm, 5 nm, 20 nm and the like.

[0040] In some embodiments of the present application, the thickness of the perovskite light absorption layer is 300-600 nm, for example, can be 400 nm, 450 nm, 500 nm and the like.

[0041] In some embodiments of the present application, the thickness of the interface modification layer is 1-20 nm, for example, can be 3 nm, 5 nm, 15 nm and the like.

[0042] In some embodiments of the present application, the thickness of the electron transport layer is 5-40 nm, for example, can be 8 nm, 10 nm, 30 nm and the like.

[0043] In some embodiments of the present application, the thickness of the top electrode layer is 50-200 nm, for example, it can be 80 nm, 100 nm, 160 nm, etc.

[0044] It should be noted that the above-mentioned preparation method of the perovskite solar cell provided in the present application can be performed according to the preparation process of the perovskite solar cell reported in the prior art such as CN120224911A, and specifically can include the following steps: (1) On the conductive substrate, an acridine compound provided in the present application is used as a hole transport material to prepare a hole transport layer; (2) A perovskite precursor solution is coated on the hole transport layer, and a perovskite light-absorbing layer is formed by annealing under conditions such as a temperature of 80-150°C (specifically, 120°C, etc.) and a time of 5-10 min (specifically, 8 min, etc.); (3) An interface modification layer material is coated on the perovskite light-absorbing layer; (4) An electron transport layer is sequentially evaporated on the interface modification layer; (5) An opaque metal electrode or a transparent oxide electrode is prepared on the electron transport layer.

[0045] (6) A perovskite solar cell is obtained.

[0046] In addition, when different electron transport layers are selected, a buffer layer can be appropriately added according to the prior art reported in CN120224911A, etc. For example, if C60 is selected as the electron transport layer, BCP is generally added as the buffer layer, and if tin oxide is selected as the electron transport layer, no buffer layer is needed.

[0047] The fourth aspect of the present application provides a device. According to embodiments of the present application, the device includes the hole transport material of the second aspect or the perovskite solar cell of the third aspect. Thus, the electrical performance and service life of the device are significantly improved.

[0048] The embodiments of the present application are described in detail below. It should be noted that the embodiments described below are exemplary and are used to explain the present application, and cannot be understood as a limitation of the present application. In addition, if not specifically stated, all reagents used in the following examples are commercially available or can be synthesized according to the methods described herein or known methods, and the reaction conditions not listed are also easily obtained by those skilled in the art.

[0049] Example 1 The present embodiment provides an acridine compound, and the chemical structural formula of the acridine compound is as follows (i.e., in formula I, R1 and R2 are both benzyl, R3 is a phosphate group, and n is 4): .

[0050] The preparation method of the above-mentioned acridine compounds includes the following steps: Step 1: Dissolve the starting material in anhydrous tetrahydrofuran. Slowly add 4-methylphenyl magnesium chloride (2.5 times the molar amount of the starting material) at 0°C. Stir for 1 hour, then move to room temperature and react overnight. After the reaction is complete, extract with ethyl acetate. Concentrate the organic phase and dissolve it in acetic acid. Add 4 mL of hydrochloric acid under nitrogen protection and stir overnight at 70°C. Post-treatment: Filter and wash the filter cake with ethanol. The filter cake is intermediate 1 (its NMR characterization data are shown below). 1 H NMR (500 MHz, DMSO) δ 9.09 (s, 1H), 7.29 – 7.23 (m, 4H), 7.20 (t, J = 6.8 Hz, 2H), 6.92 (d, J =7.8 Hz, 2H), 6.88 – 6.83 (m, 4H), 6.80 (t, J = 7.5 Hz, 2H), 6.64 (d, J = 7.7 Hz,2H), 2.20 (s, 6H).).

[0051] Step 2: Add intermediate 1 obtained in Step 1 and sodium hydride to a reaction flask. Add DMF under nitrogen protection, stir for half an hour, then add an equivalent amount of 4-bromobutyl phosphate. Stir overnight at room temperature. Extract with dichloromethane, wash with water, and then perform column chromatography to obtain intermediate 2 (its NMR characterization data are shown below). 1 H NMR (500 MHz, DMSO) δ7.29 – 7.19 (m, 8H), 6.89 (t, J = 7.4 Hz, 2H), 6.77 (d, J = 6.4 Hz, 4H), 6.71 –6.65 (m, 2H), 4.00 – 3.90 (m, 4H), 3.90 – 3.81 (m, 2H), 2.20 (s, 6H), 1.66 –1.53 (m, 4H), 1.31 (dt, J = 14.5, 7.8 Hz, 2H), 1.23 – 1.14 (m, 6H). Step 3: Dissolve intermediate 2 obtained in step 2 in anhydrous dichloromethane, then add 10 equivalents of trimethylbromosilane under nitrogen protection, and stir overnight at room temperature. After rotary evaporation to concentrate the reaction solution, dissolve it in methanol, then add deionized water to precipitate it, and finally filter to obtain the filter cake, which is the target product.

[0052] The NMR characterization data of the above acridine compound obtained in this example are as follows: 1 H NMR (500 MHz, DMSO) δ 7.30 - 7.19 (m, 8H), 6.89 (t, J = 7.4 Hz, 2H), 6.80 - 6.74 (m, 4H), 6.69 (d, J = 7.7 Hz, 2H), 3.92 - 3.73 (m, 2H), 2.20 (s, 6H), 1.59 (d, J = 6.2 Hz, 2H), 1.40 (ddt, J = 21.7, 14.4, 7.2 Hz, 4H).

[0053] Example 2 This example provides an acridine compound, the chemical structural formula of which is as follows (i.e. in formula I, R1and R2are both , R3is a phosphate group, and n is 2): .

[0054] The preparation method of the above acridine compound is similar to that in Example 1, except that the corresponding substituent group in 4-methylphenylmagnesium chloride is adjusted to serve as a raw material.

[0055] The NMR characterization data of the above acridine compound obtained in this example are as follows: 1 H NMR (500 MHz, DMSO) δ 8.07-8.03 (m, 4H), δ 7.88-7.39 (m, 8H), 6.89 (t, J = 7.4 Hz, 2H), 6.80 - 6.74 (m, 4H), 6.69 (d, J = 7.7 Hz, 2H), 3.92 - 3.73 (m, 2H), 1.59 (d, J = 6.2 Hz, 2H).

[0056] Example 3 This example provides an acridine compound, the chemical structural formula of which is as follows (i.e. in formula I, R1and R2are both , R3is a phosphate group, and n is 2): .

[0057] The preparation method of the above acridine compound is similar to that of Example 1, except that the corresponding substituent group in 4-methylphenylmagnesium chloride is adjusted as a raw material.

[0058] The nuclear magnetic characterization data of the above acridine compound obtained in this example are as follows: 1 H NMR (500 MHz, DMSO) δ 7.80-7.63 (m, 4H), 7.38-7.26 (m, 4H), δ 6.89 (t, J = 7.4 Hz, 2H), 6.80– 6.74 (m, 4H), 6.69 (d, J = 7.7 Hz, 2H), 3.92 – 3.73 (m, 2H), 2.37 (s, 6H),1.59 (d, J = 6.2 Hz, 2H)。

[0059] Example 4 This example provides an acridine compound, the chemical structural formula of which is shown as formula I, wherein R1 and R2 are both , R3 is a phosphate group, and n is 2).

[0060] The preparation method of the above acridine compound is similar to that of Example 1, except that the corresponding substituent group in 4-methylphenylmagnesium chloride is adjusted as a raw material.

[0061] The nuclear magnetic characterization data of the above acridine compound obtained in this example are as follows: 1 H NMR (500 MHz, DMSO) δ 8.38 (m, 2H), δ 7.93-7.68 (m,10H), 6.89 (t, J = 7.4 Hz, 2H), 6.80– 6.74 (m, 4H), 6.69 (d, J = 7.7 Hz, 2H), 3.92 – 3.73 (m, 2H), 1.59 (d, J = 6.2 Hz,2H)。

[0062] Example 5 This example provides an acridine compound, the chemical structural formula of which is shown as formula I, wherein R1 is methyl, R2 is phenyl, R3 is a phosphate group, and n is 4) The preparation method of the above acridine compound includes the following steps:

[0063] Step one: Diphenylamine (1 eq) and bis(trifluoromethylsulfonimide) 5% eq, alkynyl arene 1.5 eq, 1,1,1,3,3,3-hexafluoro-2-propanol as solvent, the reaction mixture was stirred in an oil bath at 80 °C for 16 hours. Work-up: pour the reaction system into water, adjust the PH, extract with ethyl acetate, then concentrate the organic phase and purify by column chromatography to obtain the intermediate product (its NMR characterization data are as follows: 1 H NMR (500MHz, CDCl3): δ 8.08 (s, 1H), δ 7.20-7.09 (m,4H), 6.99-6.94 (m, 2H), 6.72-6.62 (m, 6H), 1.75 (s, 3H))。

[0064] The subsequent steps are the same as steps two and three of Example 1.

[0065] The NMR characterization data of the acridine compound obtained in this example are as follows: 1 H NMR (500MHz, CDCl3): δ 7.20-7.09 (m, 4H), 6.99-6.94 (m, 2H), 6.72-6.62 (m, 6H), 3.92 –3.73 (m, 2H), 1.75 (s, 3H), 1.59 (d, J = 6.2 Hz, 2H), 1.40 (ddt, J = 21.7, 14.4,7.2 Hz, 4H)。

[0066] Example 6 This example provides an acridine compound, the chemical structural formula of which is shown as formula I, wherein R1 is phenyl, R2 is methylphenyl, R3 is a phosphate group, and n is 4. The preparation method of the acridine compound includes the following steps:

[0067] Step one: Diphenylamine (1 eq) and p-toluenesulfonic acid monohydrate (2% eq) were placed in a reaction bottle and heated to 140 °C, then 4-methylbenzophenone was added after the solution was formed, and the temperature was continued to be heated to 200 °C for 1 h; Work-up: dissolved with dichloromethane, washed with water twice, concentrated the organic phase, and then purified by column chromatography to obtain the intermediate product (its NMR characterization data are as follows: 1 HNMR (500 MHz, DMSO) δ 9.09 (s, 1H), 7.29 – 7.23 (m, 5H), 7.20 (t, J= 7.8 Hz, 2H), 6.88 – 6.83 (m, 4H), 6.80 (t, J = 7.5 Hz, 2H),6.64 (d, J = 7.7 Hz, 2H), 2.20 (s, 3H).)。 J = 7.7 Hz, 2H), 2.20 (s, 3H).)。

[0068] The subsequent steps are the same as steps two and three of Example 1.

[0069] The nuclear magnetic characterization data of the above acridine compound obtained in this example are as follows: 1 H NMR (500 MHz,DMSO) δ 7.30 – 7.19 (m, 9H), 6.89 (t, J = 7.4 Hz, 2H), 6.80 – 6.74 (m, 4H),6.69 (d, J = 7.7 Hz, 2H), 3.92 – 3.73 (m, 2H), 2.20 (s, 3H), 1.59 (d, J = 6.2 Hz,2H), 1.40 (ddt, J = 21.7, 14.4, 7.2 Hz, 4H)。

[0070] Example 7 The present example provides a perovskite solar cell, comprising a conductive substrate layer, a hole transport layer, a perovskite light absorption layer, an interface modification layer, an electron transport layer and a top electrode layer which are sequentially stacked; The conductive substrate layer is an ITO flexible substrate (specifically, a PET film is used as the substrate, and indium tin oxide (ITO) is deposited on the surface as a transparent conductive layer), and the sheet resistance is 20 Ω / D; The hole transport layer is the acridine compound provided in Example 1 as a hole transport material, and the thickness is 5 nm; The perovskite light absorption layer is specifically FA 0.95 Cs 0.05 PbI3, and the thickness is 450 nm; The interface modification layer is specifically phenethylammonium chloride, and the thickness is 5 nm; The electron transport layer is specifically tin oxide, and the thickness is 20 nm; The top electrode layer is specifically copper, and the thickness is 100 nm.

[0071] The preparation method of the above perovskite solar cell comprises the following steps: (1) The ITO flexible substrate is cleaned and ozone treated, and the acridine compound provided in Example 1 is used as a hole transport material and spin-coated onto the ITO flexible substrate to form a hole transport layer after annealing; (2) A perovskite precursor solution (FA 0.95 Cs 0.05 PbI3) is coated on the hole transport layer to form a perovskite light-absorbing layer after annealing; (3) Phenethylammonium chloride is spin-coated on the perovskite light-absorbing layer to obtain an interface modification layer; (4) Tin oxide is deposited on the interface modification layer by atomic layer deposition to prepare an electron transport layer; (5) Copper is evaporated on the electron transport layer to prepare a top electrode layer.

[0072] (6) A perovskite solar cell is obtained.

[0073] Example 8 The present example provides a perovskite solar cell and a preparation method thereof, which differs from Example 7 in that: (1) The hole transport layer is an acridine compound provided in Example 2 as a hole transport material.

[0074] Example 9 The present example provides a perovskite solar cell and a preparation method thereof, which differs from Example 7 in that: (1) The hole transport layer is an acridine compound provided in Example 3 as a hole transport material.

[0075] Example 10 The present example provides a perovskite solar cell and a preparation method thereof, which differs from Example 7 in that: (1) The hole transport layer is an acridine compound provided in Example 4 as a hole transport material.

[0076] Example 11 The present example provides a perovskite solar cell and a preparation method thereof, which differs from Example 7 in that: (1) The hole transport layer is an acridine compound provided in Example 5 as a hole transport material.

[0077] Example 12 The present example provides a perovskite solar cell and a preparation method thereof, which differs from Example 7 in that: (1) The hole transport layer is an acridine compound provided in Example 6 as a hole transport material.

[0078] Comparative Example 1 This comparative example provides a prior art hole transport material, specifically Me-2PACz (specifically (2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl)phosphonic acid, CAS No. 2996161-30-7).

[0079] Comparative Example 2 This comparative example provides a prior art hole transport material, specifically 4PADBC (specifically [4-(7H-dibenzo[c, h]carbazol-7-yl)butyl]phosphonic acid, CAS No. 2882156-63-8).

[0080] Comparative Example 3 This comparative example provides a perovskite solar cell and a method for preparing the same, which is different from Example 5 in that: (1) the hole transport layer is the hole transport material provided in Comparative Example 1.

[0081] Comparative Example 4 This comparative example provides a perovskite solar cell and a method for preparing the same, which is different from Example 5 in that: (1) the hole transport layer is the hole transport material provided in Comparative Example 2.

[0082] Test Example This test example tests the performance of the perovskite solar cells provided in Examples 5-8 and Comparative Examples 3-4 above.

[0083] The test standards and methods are as follows: 1) PCE test: In a nitrogen-filled glove box at room temperature, the current density-voltage (J-V) characteristics of the perovskite solar cells (PSCs) were measured using a Keithley 2400 source meter, with a solar simulator (ENLITECH SSX 100 R) simulating AM 1.5G illumination at an intensity of 100 mW / cm 2 . The light intensity was calibrated using a standard silicon reference cell (LCR-KG 5-015). The device area was 0.0625 cm 2 .

[0084] 2) Stability test: The stability test was performed according to ISOS-D-1 test standard: humidity = 45% ± 10%, air; and according to ISOS-L-3 test standard: 45 ± 5°C, RH = 70% ± 10%.

[0085] The test results are shown in Table 1 and Figure 2 ( Figure 2 . Jsc, Voc, FF and PCE are shown as positive scan test data, i.e. from short circuit voltage to open circuit voltage, Jsc, Voc, FF and PCE are shown as reverse scan test data, i.e. from open circuit voltage to short circuit voltage).

[0086] Table 1

[0087] As can be seen from Table 1, compared with Comparative Example 3 and Comparative Example 4, the power conversion efficiency and stability of the perovskite solar cell using the acridine compound provided by the embodiment of the present application as the hole transport material are both better. Especially, when R1 and R2 in the acridine derivative provided by the embodiment of the present application contain electron-withdrawing groups, the stability of the obtained perovskite solar cell is most significantly improved, which can retain about 85% of the initial efficiency after being stored in an air environment with a relative humidity (RH) of 45%±10% for 3026 hours, and can retain 94% of the initial efficiency after 500 hours of maximum power point tracking under 1 sun irradiation in an air environment with a temperature of 45±5℃ and a relative humidity of 70%±10%.

[0088] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, organosilicon materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, organosilicon materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0089] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. An acridine compound, characterized in that, The chemical structural formula of the acridine compounds is shown in Formula I; Equation I: ; R1 and R2 are each independently selected from substituted methyl, substituted methyl, substituted aryl or substituted heteroaryl, R3 is a phosphate group, carboxylic acid group or sulfonic acid group, and n is any natural number from 1 to 10.

2. The acridine compound according to claim 1, characterized in that, R1 and R2 are each independently selected from methyl groups substituted with electron-withdrawing groups, aryl groups substituted with electron-withdrawing groups, or heteroaryl groups substituted with electron-withdrawing groups, wherein the electron-withdrawing groups include fluoro, trifluoromethyl, or cyano groups.

3. The acridine compound according to claim 1, characterized in that, R1 and R2 are each independently selected from any of the following substituents: 。 4. The acridine compound according to claim 1, characterized in that, n is any natural number from 2 to 6; And / or, the R3 is a phosphate group; And / or, the group types of R1 and R2 are different.

5. The acridine compound according to claim 1, characterized in that, Including compounds represented by any of the following chemical structural formulas: 、 、 、 or .

6. A hole transport material, characterized in that, The hole transport material includes any one of the acridine compounds according to claims 1 to 5.

7. A perovskite solar cell, characterized in that, It includes a conductive substrate layer, a hole transport layer, a perovskite light-absorbing layer, an interface modification layer, an electron transport layer, and a top electrode layer stacked sequentially. The hole transport layer is the hole transport material described in claim 6.

8. The perovskite solar cell according to claim 7, characterized in that, The conductive substrate includes at least one of glass, steel plate, polyethylene terephthalate substrate, polyethylene naphthalate substrate, polyimide substrate, indium tin oxide substrate, aluminum-doped zinc oxide substrate, and fluorine-doped tin oxide substrate; And / or, the perovskite light-absorbing layer comprises an ABX3 type material; wherein, A comprises Rb + Cs + CH3NH3 + CH3CH2NH3 + CH3(CH2)2NH3 + CH3(CH2)3NH3 + and HC(NH2)2 + At least one of them, B includes Pb 2+ Sn 2+ Cu 2+ and Ge 2+ At least one of them, X includes Cl - ,Br - I - SCN - BF4 - and PF6 - At least one of them; And / or, the interface modification layer includes at least one of phenylethyl ammonium iodide, phenylethyl ammonium chloride, phenyl dimethyl ammonium iodide and oleylamine iodide; And / or, the electron transport layer comprises TiO2, SnO2, ZnO, methyl phenyl-C61-butyrate, methyl phenyl-C71-butyrate, 2,4,6-triisopropylphenyldiimide, bis[1-(3-methoxycarbonyl)propyl]-1,4-phenyldiimide, C 60 At least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; And / or, the top electrode layer comprises at least one of a metallic material and a transparent oxide material, wherein the metallic material comprises at least one of gold, silver, copper and aluminum, and the transparent oxide material comprises at least one of indium tin oxide and indium zinc oxide.

9. The perovskite solar cell according to claim 7, characterized in that, The thickness of the hole transport layer is 1-20 nm; And / or, the thickness of the perovskite light-absorbing layer is 300~600nm; And / or, the thickness of the interface modification layer is 1~20nm; And / or, the thickness of the electron transport layer is 5~40 nm; And / or, the thickness of the top electrode layer is 50~200nm.

10. A device, characterized in that, The device includes the hole transport material of claim 6 or the perovskite solar cell of any one of claims 7 to 9.

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