An acid-containing organic compound, application thereof, and a perovskite solar cell

Abstract

This invention relates to the field of solar cell technology, and discloses an acid-containing organic compound, its applications, and a perovskite solar cell. The compound has the structure shown in formula (I). The organic compound provided by this invention has suitable energy levels and is a high-performance organic semiconductor material capable of improving the efficiency of perovskite solar cell devices.

Description

Technical Field

[0001] This invention relates to the field of solar cell technology, specifically to an acid-containing organic compound and its applications, and a perovskite solar cell. Background Technology

[0002] The development of new energy sources can provide important guarantees for the sustainable development of human civilization, and solar photovoltaic is one of the most promising solutions. Since its inception, all-solid-state organic-inorganic hybrid perovskite solar cells (PSCs) have achieved a peak photoelectric conversion efficiency of 25.7% in just ten years, demonstrating excellent photoelectric conversion efficiency and broad application prospects.

[0003] A perovskite solar cell consists of a conductive glass substrate, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode. The working principle of a perovskite solar cell is as follows: When the perovskite layer absorbs sunlight and is excited, it generates a pair of free electrons and holes. The free electrons excited to the perovskite conduction band diffuse to the perovskite / electron transport layer interface and are injected into the conduction band of the electron transport layer. The electrons then travel through the electron transport layer to the conductive glass electrode, and then flow through the external circuit to the metal electrode. Simultaneously, while free electrons are excited to the perovskite conduction band, holes also travel through the perovskite valence band and diffuse to the perovskite / hole transport layer interface, then are injected into the valence band of the hole transport layer. The holes then travel through the hole transport layer and return to the metal electrode, where they recombine with the free electrons to form a complete circuit.

[0004] The commercialization of perovskite solar cells still requires high efficiency and good long-term environmental stability. The key to further developing better-performing perovskite solar cells remains energy level matching between the hole transport material and the perovskite, as well as hole transport itself.

[0005] Therefore, developing a new type of hole transport material is of great significance. Summary of the Invention

[0006] The purpose of this invention is to maintain the excellent hole transport performance and improve the photoelectric performance of perovskite solar cells.

[0007] To achieve the above objectives, the present invention provides an acid-containing organic compound having the structure shown in formula (I).

[0008]

[0009] In equation (I), n is an integer from 0 to 20;

[0010] A is an acid-containing group;

[0011] L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-30 The aromatic compound is formed by removing at least one of the following: a linking group consisting of any two H atoms that can leave the compound; -S-; -O-; -NH-; -COO-; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 20; the heteroatoms of type A include at least one of N, O, and S;

[0012] Combination A contains C. 1-20 Alkyl and amino groups.

[0013] The second aspect of this invention provides the application of the acid-containing organic compound described in the first aspect in perovskite solar cells.

[0014] A third aspect of the present invention provides a perovskite solar cell, which includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode.

[0015] The perovskite solar cell contains the acidic organic compound described in the first aspect.

[0016] Through the above technical solution, the present invention has at least the following beneficial effects:

[0017] 1. The present invention provides an organic compound with a suitable energy level, which is a high-performance organic semiconductor material that can improve the efficiency of perovskite solar cell devices;

[0018] 2. The method for synthesizing organic compounds provided by this invention is simple and has a well-defined structure. Compared with structures with symmetrical substituents, it has a lower cost, but its performance is basically the same as that of structures with symmetrical substituents. It has high application value in optoelectronic fields such as solar cells.

[0019] 3. The organic compound provided by the present invention contains a carbazole structure and an asymmetric amino structure. The bonding mode between the carbazole structure and the amino structure enables the organic compound to effectively interact weakly with toxic lead, preventing lead leakage. At the same time, it promotes the interaction with the top perovskite to passivate interface defects, ensuring efficient hole selection and transport, thereby improving the safety and service life of perovskite solar cells.

[0020] 4. The acid-containing groups in the organic compounds provided by this invention can be arranged in an orderly manner, which on the one hand can firmly adhere to the ITO surface and form a dense and uniform interface; on the other hand, it can effectively extract charge carriers from the perovskite to the substrate electrode through charge tunneling, thereby improving device performance.

[0021] 5. The organic compounds provided by this invention have good solubility, which is beneficial for dissolving and forming films during device fabrication. Detailed Implementation

[0022] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0024] In this invention, "aromatic compound" and "aromatic group" are interpreted broadly to refer to cyclic compounds or groups that contain at least one delocalized bond and are thus "aromatic".

[0025] "C containing or not containing type A heteroatoms" 3-30 The aromatic compound is described as having at least one of the following linkage groups formed by the departure of any two H atoms: 3-30 carbon atoms (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms). The aromatic compound may or may not contain heteroatoms. The linkage group may also be selected from C atoms containing or not containing type A heteroatoms. 3-30 Aromatic compounds can form two or more linking groups by removing any two H atoms that can leave their bonds. For example, naphthalene and benzene both remove two H atoms and bond with each other to form linking groups.

[0026] “C 1-20 "Alkyl" refers to a straight-chain or branched alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. 1-10 Alkyl" "C" 1～8 Alkyl", C 1～6 Alkyl", C 1～3 Alkyl groups have similar definitions, differing only in the total number of carbon atoms.

[0027] Unless otherwise specified, when the groups of the compounds of the present invention contain substituents, there are no particular requirements on the specific substitution position of the substituents, and they can be any position that can be substituted.

[0028] As previously described, a first aspect of the present invention provides an acidic organic compound having the structure shown in formula (I).

[0029]

[0030] In equation (I), n is an integer from 0 to 20;

[0031] A is an acid-containing group;

[0032] L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-30 The aromatic compound is formed by removing at least one of the following: a linking group consisting of any two H atoms that can leave the compound; -S-; -O-; -NH-; -COO-; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 20; the heteroatoms of type A include at least one of N, O, and S;

[0033] Combination A contains C. 1-20 Alkyl and amino groups.

[0034] For example, n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0035] For example, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0036] In the preferred case, in equation (I),

[0037] n is an integer between 0 and 16;

[0038] A is an acidic group containing at least one element selected from P, S, C, and Si;

[0039] L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-24 The aromatic compound is separated from at least one of the following: a linking group formed by any two H atoms capable of leaving; -S-; -O-; -NH-; -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 12; the heteroatoms of type A include at least one of N, O, and S;

[0040] Combination A contains C.1-16 Alkyl and amino groups.

[0041] More preferably, in equation (I),

[0042] n is an integer between 0 and 10;

[0043] A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3;

[0044] L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-16 The aromatic compound is separated from at least one of the following: a linking group formed by any two H atoms capable of leaving; -S-; -O-; -NH-; -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 10; the A-type heteroatoms include at least one of N, O, and S;

[0045] Combination A contains C. 1-12 Alkyl and amino groups.

[0046] According to a preferred embodiment, in formula (I),

[0047] n is an integer between 0 and 10;

[0048] A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3;

[0049] L stands for -(CH2) m - At least one of the following: a linking group formed by benzene leaving any two H atoms; a linking group formed by biphenyl leaving any two H atoms; a linking group formed by naphthalene leaving any two H atoms; a linking group formed by anthracene leaving any two H atoms; a linking group formed by phenanthrene leaving any two H atoms; a linking group formed by pyridine leaving any two H atoms; a linking group formed by dibenzothiophene leaving any two H atoms; a linking group formed by dibenzofuran leaving any two H atoms; -S-, -O-, -NH-, -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 10;

[0050] Combination A contains C. 1-8 Alkyl and amino groups.

[0051] According to another particularly preferred embodiment (hereinafter referred to as preferred embodiment 1), in formula (I),

[0052] n is an integer between 0 and 10;

[0053] A is -P(O)(OH)2;

[0054] L stands for -(CH2) m -; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 10;

[0055] Combination A contains C. 1-4 Alkyl and amino groups.

[0056] In the preferred embodiment 1, more preferably, the acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

[0057]

[0058]

[0059] According to another particularly preferred embodiment (hereinafter referred to as preferred embodiment 2), in formula (I),

[0060] n is an integer between 0 and 10;

[0061] A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3;

[0062] L stands for -(CH2) m At least one of -, -S-, -O-, -NH-, -COO-; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 10;

[0063] Combination A contains C. 1-8 Alkyl and amino groups.

[0064] In the preferred embodiment 2, more preferably, the acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

[0065]

[0066]

[0067]

[0068] According to another preferred embodiment, the acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

[0069]

[0070]

[0071]

[0072]

[0073] This invention does not impose any particular limitations on the specific methods for preparing the aforementioned compounds. Those skilled in the art can obtain the aforementioned compounds of this invention by combining the specific structural formulas provided by this invention with known knowledge in the field of organic synthesis. Furthermore, several examples are exemplarily provided below to illustrate the preparation methods of the compounds of this invention. Those skilled in the art can also obtain specific preparation methods for all other compounds by substituting the types of raw materials according to the preparation methods of the compounds described below. This invention will not elaborate on the preparation methods of all compounds, and this should not be construed as a limitation of the invention.

[0074] As previously stated, the second aspect of the present invention provides the application of the acid-containing organic compounds described in the first aspect in perovskite solar cells.

[0075] The perovskite solar cell described in this invention refers to a type of solar cell that uses perovskite-type organometal halide semiconductors as light-absorbing materials.

[0076] As previously described, a third aspect of the present invention provides a perovskite solar cell comprising a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode; the perovskite solar cell contains the acid-containing organic compound described in the first aspect.

[0077] Preferably, the acidic organic compound is present in the hole transport layer.

[0078] Preferably, the perovskite solar cell of the present invention comprises, from bottom to top, a conductive glass substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer, and a metal electrode, wherein the acid-containing organic compound is present in the hole transport layer of the perovskite solar cell.

[0079] Preferably, the conductive glass substrate includes a conductive layer, and the conductive layer is selected from at least one of an indium tin oxide layer, an aluminum-doped zinc oxide layer, and a fluorine-doped tin oxide layer.

[0080] In a preferred embodiment, the metal electrode comprises a metal cathode, and the material forming the metal cathode is selected from at least one of Al, Ag, Au, Mg, Cu, Mo and Cr.

[0081] Preferably, the material forming the electron transport layer is a metal oxide electron transport material and / or an organic small molecule electron transport material.

[0082] Particularly preferably, the organic small molecule electron transport material is selected from at least one of fullerenes and their derivatives.

[0083] More preferably, the metal oxide electron transport material is selected from at least one of TiO2, ZnO or SnO2.

[0084] Preferably, the perovskite light-absorbing layer contains at least one of the perovskite materials ABY3; wherein A is NH2CH=NH2. + CH3NH3 + or Cs + At least one of them; B is Pb 2+ or Sn 2+ At least one of them; Y is I - Cl - or Br - At least one of them.

[0085] This invention does not impose any particular requirements on the specific fabrication process of the perovskite solar cell. Those skilled in the art can use known fabrication processes for perovskite solar cells. In order to illustrate the beneficial effects of the presence of the acid-containing organic compound provided by this invention in the perovskite solar cell, a specific fabrication process and specific parameters for a perovskite solar cell are exemplarily described in the device embodiment section. Those skilled in the art should not understand this as a limitation of the invention.

[0086] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available products. Unless otherwise specified, room temperature as mentioned below refers to 25±1℃.

[0087] Preparation Example 1: Synthesis of Compound 2

[0088]

[0089] Synthesis of intermediate 2-1: 0.1 mol of 3-chloro-9H-carbazole was dissolved in 250 mL of toluene, and 0.1 mol of diethyl 3-bromopropylphosphonate, 0.25 mol of sodium tert-butoxide, 3 mmol of tris(dibenzylacetone)dipalladium, and 3 mmol of tritert-butylphosphine were added. The mixture was stirred under nitrogen and heated to reflux. After 4 h, the reaction was confirmed to be complete. The reaction solution was evaporated to dryness under reduced pressure and intermediate 2-1 was obtained by column chromatography (yield: 67.1%).

[0090] Synthesis of intermediate 2-2: 0.06 mol of intermediate 2-1 was dissolved in 220 mL of 1,4-dioxane solvent and stirred under nitrogen purging. 0.06 mol of pinacol diborate, 0.15 mol of potassium acetate, and 1.8 mmol of ferrocene palladium dichloride were added sequentially. The mixture was heated to reflux and reacted. After 4 h, HPLC analysis showed that the reactants had basically reacted completely. The reaction was stopped, and the reaction solution was evaporated to dryness under reduced pressure. The residue was then subjected to column chromatography to obtain intermediate 2-2 (yield: 76.9%).

[0091] Synthesis of intermediate 2-3: 0.04 mol of 3-(4-chlorophenyl)prop-1-amine was dissolved in 180 mL of toluene solvent, and nitrogen gas was introduced and stirred. 0.04 mol of intermediate 2-2, 0.1 mol of potassium carbonate, and 1.2 mmol of tetra(triphenylphosphine)palladium were added sequentially. The mixture was heated to reflux. After 6 h, HPLC analysis showed that the starting material was basically completely reacted. The reaction was stopped, cooled, and filtered to obtain the crude product. The crude product was completely dissolved in toluene, and the filtrate was evaporated to dryness under reduced pressure. The residue was subjected to column chromatography to obtain intermediate 2-3 (yield: 79.2%).

[0092] Synthesis of compound 2: 0.01 mol of intermediate 2-3 was dissolved in 400 mL of dichloromethane, cooled to 0 °C, and 0.07 mol of boron tribromide was added. The mixture was stirred at 0 °C for 12 h. After the reaction was completed, sodium bicarbonate aqueous solution was added to quench the reaction, and then the mixture was extracted three times with dichloromethane. After drying with anhydrous magnesium sulfate, the reaction solution was evaporated to dryness under reduced pressure and compound 2 was obtained by column chromatography (yield: 90.2%).

[0093] Mass spectrometry: C24H27N2O3P, theoretical value: 422.18, measured value: 422.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.19~1.23(2H, s), 1.59~1.73(2H, m), 2.00~2.16(4H, m), 2.59~2.72(4H, m), 4.12~4.20(2H, m), 7.10~7.18(1H,m), 7.25~7.31(2H,m), 7.37~7.45(2H,m), 7.45~7.51(1H,d), 7.59~7.6 5(2H,m), 7.74~7.80(2H,m), 7.89~7.92(1H,d), 7.93~7.99(1H,m), 8.31~8.37(1H,m).

[0094] Preparation Example 2: Synthesis of Compound 14

[0095]

[0096] Synthesis of intermediate 14-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 14-1 (yield: 68.2%).

[0097] Synthesis of intermediate 14-2: The synthesis method is the same as that of intermediate 2-2, yielding intermediate 14-2 (yield: 76.3%).

[0098] Synthesis of intermediate 14-3: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 14-3 (yield: 78.8%).

[0099] Synthesis of compound 14: The synthesis method was the same as that for compound 2, yielding compound 14 (yield: 91.3%).

[0100] Mass spectrometry: C15H17N2O3P, theoretical value: 304.10, measured value: 304.11. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.39~1.44 (2H, s), 1.90~2.00 (2H, m), 4.07~4.11 (2H, s), 4.32~4.38 (2H, m), 4.44~4.50 (1H, m), 7.08~7.14 (1H, m), 7.29~7.37 (1H, m), 7.50~7.58 (2H, m), 7.61~7.72 (2H, m), 8.13~8.20 (2H, m).

[0101] Preparation Example 3: Synthesis of Compound 20

[0102]

[0103] Synthesis of intermediate 20-1: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 20-1 (yield: 77.9%).

[0104] Synthesis of compound 20: The synthesis method was the same as that for compound 2, yielding compound 20 (yield: 90.6%).

[0105] Mass spectrometry: C16H19N2O3P, theoretical value: 318.11, measured value: 318.10. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.21~1.25 (4H, s), 1.88~2.02 (2H, m), 2.79~2.87 (2H, m), 3.01~3.10 (2H, m), 4.37~4.46 (2H, m), 7.00~7.06 (1H, m), 7.29~7.37 (1H, m), 7.50~7.58 (1H, m), 7.61~7.69 (2H, m), 8.05~8.09 (1H, d), 8.14~8.20 (1H, m).

[0106] Preparation Example 4: Synthesis of Compound 23

[0107]

[0108] Synthesis of intermediate 23-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 23-1 (yield: 68.5%).

[0109] Synthesis of intermediate 23-2: The synthesis method is the same as that for intermediate 2-2, yielding intermediate 23-2 (yield: 76.7%).

[0110] Synthesis of intermediate 23-3: The synthesis method is the same as that for intermediate 2-3, yielding intermediate 23-3 (yield: 78.3%).

[0111] Synthesis of compound 23: The synthesis method was the same as that for compound 2, yielding compound 23 (yield: 91.1%).

[0112] Mass spectrometry: C20H27N2O3P, theoretical value: 374.18, measured value: 374.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.18~1.42(9H, m), 1.60~1.81(4H, m), 2.79~2.87(2H, m), 3.01~3.09(2H, m), 4.12~4.20(2H, m), 7.00~7.06(1H, m), 7.29~7.37(2H, m), 7.50~7.58(1H, m), 7.61~7.69(2H, m), 8.05~8.08(1H, d), 8.14~8.20(1H, m).

[0113] Preparation Example 5: Synthesis of Compound 26

[0114]

[0115] Synthesis of intermediate 26-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 26-1 (yield: 67.9%).

[0116] Synthesis of intermediate 26-2: The synthesis method is the same as that for intermediate 2-2, yielding intermediate 26-2 (yield: 77.0%).

[0117] Synthesis of intermediate 26-3: The synthesis method is the same as that for intermediate 2-3, yielding intermediate 26-3 (yield: 78.1%).

[0118] Synthesis of compound 26: The synthesis method was the same as that for compound 2, yielding compound 26 (yield: 90.4%).

[0119] Mass spectrometry: C19H25N2O3P, theoretical value: 360.16, measured value: 360.15. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.19~1.33(4H, m), 1.59~1.80(4H, m), 2.03~2.15(2H, m), 2.60~2.72(4H, m), 4.12~4.20(3H, m), 7.00~7.06(1H, m), 7.29~7.37(2H, m), 7.50~7.58(1H, m), 7.61~7.69(2H, m), 8.05~8.09(1H, d), 8.14~8.20(1H, m).

[0120] Preparation Example 6: Synthesis of Compound 37

[0121]

[0122] Synthesis of intermediate 37-1: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 37-1 (yield: 78.8%).

[0123] Synthesis of compound 37: The synthesis method was the same as that for compound 2, yielding compound 37 (yield: 91.3%).

[0124] Mass spectrometry: C16H20N3O3P, theoretical value: 333.12, measured value: 333.11. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.33~1.40(2H, d), 1.44~1.49(2H, s), 1.88~2.02(2H, m), 2.78~2.87(2H, m), 2.97~3.06(2H,m), 4.36~4.51(2H,m), 7.00~7.06(1H,m), 7.29~7.37(1H,m), 7.50~7.58(2H,m), 7.61~7.69(2H,m), 8.05~8.09(1H,d), 8.14~8.20(1H,m).

[0125] Preparation Example 7: Synthesis of Compound 41

[0126]

[0127] Synthesis of intermediate 41-1: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 41-1 (yield: 77.2%).

[0128] Synthesis of compound 41: The synthesis method was the same as that of compound 2, yielding compound 41 (yield: 89.9%).

[0129] Mass spectrometry: C19H23N2O5P, theoretical value: 390.13, measured value: 390.14. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.20~1.32(2H, m), 1.60~1.80(4H, m), 2.93~2.99(2H, m), 4.13~4.19(2H, m), 4.40~4.51(4H, m), 7.00~7.06(2H, m), 7.29~7.37(1H, m), 7.50~7.58(2H, m), 7.61~7.69(2H, m), 8.05~8.09(1H, d), 8.14~8.20(1H, m).

[0130] Preparation Example 8: Synthesis of Compound 42

[0131]

[0132] Synthesis of intermediate 42-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 42-1 (yield: 68.2%).

[0133] Synthesis of intermediate 42-2: The synthesis method is the same as that of intermediate 2-2, yielding intermediate 42-2 (yield: 76.3%).

[0134] Synthesis of intermediate 42-3: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 42-3 (yield: 78.4%).

[0135] Synthesis of compound 42: The synthesis method was the same as that for compound 2, yielding compound 42 (yield: 91.5%).

[0136] Mass spectrometry: C15H16N2O3S, theoretical value: 304.09, measured value: 304.10. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.39~1.44 (2H, s), 3.26~3.34 (2H, m), 4.07~4.11 (2H, s), 4.53~4.61 (2H, m), 6.66~6.69 (1H, s), 7.08~7.13 (1H, m), 7.29~7.37 (1H, m), 7.50~7.58 (1H, m), 7.61~7.71 (2H, m), 8.13~8.20 (2H, m).

[0137] Preparation Example 9: Synthesis of Compound 55

[0138]

[0139] Synthesis of intermediate 55-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 55-1 (yield: 69.4%).

[0140] Synthesis of intermediate 55-2: The synthesis method is the same as that for intermediate 2-2, yielding intermediate 55-2 (yield: 77.5%).

[0141] Synthesis of intermediate 55-3: The synthesis method is the same as that for intermediate 2-3, yielding intermediate 55-3 (yield: 79.2%).

[0142] Synthesis of compound 55: The synthesis method was the same as that for compound 2, yielding compound 55 (yield: 90.6%).

[0143] Mass spectrometry: C16H16N2O2, theoretical value: 268.12, measured value: 268.15. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.39~1.43 (2H, s), 2.68~2.77 (2H, m), 4.08~4.12 (2H, s), 4.37~4.46 (3H, m), 7.08~7.13 (1H, m), 7.29~7.37 (1H, m), 7.50~7.58 (1H, m), 7.61~7.72 (2H, m), 8.13~8.20 (2H, m).

[0144] Preparation Example 10: Synthesis of Compound 67

[0145]

[0146] Synthesis of intermediate 67-1: The synthesis method is the same as that of intermediate 2-1, yielding intermediate 67-1 (yield: 67.7%).

[0147] Synthesis of intermediate 67-2: The synthesis method is the same as that for intermediate 2-2, yielding intermediate 67-2 (yield: 77.6%).

[0148] Synthesis of intermediate 67-3: The synthesis method is the same as that of intermediate 2-3, yielding intermediate 67-3 (yield: 78.2%).

[0149] Synthesis of compound 67: The synthesis method was the same as that for compound 2, yielding compound 67 (yield: 90.4%).

[0150] Mass spectrometry: C16H20N2O3Si, theoretical value: 316.12, measured value: 316.10. 1H-NMR (400MHz, CDCl3) (ppm) δ=0.85~0.94(2H, m), 1.21~1.25(2H, s), 2.79~2.87(2H, m), 3.01~3.10(2H, m), 3.76~3.86(2H, m), 4.62~4.66(3H, s), 7.00~7.05(1H, m), 7.29~7.37(1H, m), 7.50~7.58(1H, m), 7.62~7.68(2H, m), 8.05~8.08(1H, d), 8.15~8.19(1H, m).

[0151] Device Example 1

[0152] The indium tin oxide (ITO) conductive glass was ultrasonically cleaned for 15 minutes each with deionized water, acetone and isoacetone, and then dried in a drying oven at 75°C for later use. The dried ITO glass substrate was then treated in an ozone machine or plasma surface cleaner for 10 minutes to remove organic impurities from its surface.

[0153] Compound 2 was dissolved in chlorobenzene to prepare a solution with a concentration of 2 mg / ml. The solution was then spin-coated onto ITO at 4000 rpm for 30 s and annealed at 100 °C for 10 min to prepare a hole transport layer.

[0154] 599.31 mg lead iodide and 206.66 mg methyl iodide solid were dissolved in 1 ml of chlorobenzene and stirred at room temperature until completely dissolved to obtain a perovskite precursor solution. Before preparing the perovskite layer, the PTAA film surface was rinsed with DMF solution. The prepared perovskite precursor solution was spin-coated onto the hole transport layer at 5000 rpm for 25 s, followed by the addition of 200 μL of anisole antisolvent over 10 s. The mixture was then annealed at 100 °C for 30 min to prepare the perovskite layer.

[0155] TiO2 was dissolved in toluene to prepare a solution with a total concentration of 15 mg / ml. The solution was then spin-coated at 3000 rpm for 30 s to prepare an electron transport layer.

[0156] BCP was dissolved in isopropanol to prepare a solution with a total concentration of 0.5 mg / ml. The solution was then spin-coated at 6000 rpm for 30 minutes and annealed at 80°C for 10 minutes to prepare the BCP layer.

[0157] In 2×10 -4 A 100 nm silver electrode was deposited under Pa conditions to complete the fabrication of a perovskite solar cell.

[0158] The remaining device embodiments of the present invention are prepared using a method similar to that of device embodiment 1, except that compound 2 in the hole transport layer of device embodiment 1 is replaced with the corresponding compound in Table 1.

[0159] Device Comparison Examples 1 to 4

[0160] Each comparative device was prepared using a method similar to that of Device Example 1, except that compound 2 in the hole transport layer of Device Example 1 was replaced with compounds Ref-1, Ref-2, Ref-3, and Ref-4.

[0161]

[0162] Test case

[0163] The device's current density-voltage (JV) curves were obtained from a source meter (Keithley 2400) on an ABET Sun 3000 solar simulator at AM1.5G (100mW cm⁻¹). -2 Obtained under illumination, battery area 0.08 cm² 2 Before testing, the light intensity was calibrated using a standard silicon cell. The scan rate was 10 mV / s, and the scan direction was forward and reverse scan (-0.2V to 1.2V). The photovoltaic parameters of each device embodiment and device comparison example are shown in Table 1.

[0164] Table 1

[0165]

[0166]

[0167] In summary, the compounds provided by this invention, when used as hole transport layer materials, can effectively extract and transport holes, which is beneficial to improving current and fill factor. When applied to perovskite solar cells, they exhibit high photoelectric conversion efficiency and have good application prospects. In addition, the compounds of this invention have good solubility and can be directly spin-coated from solution, making the preparation process convenient.

[0168] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An acid-containing organic compound, characterized in that, The compound has the structure shown in formula (I). In equation (I), n is an integer from 0 to 20; A is an acid-containing group; L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-30 The aromatic compound is formed by removing at least one of the following: a linking group consisting of any two H atoms that can leave the compound; -S-; -O-; -NH-; -COO-; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 20; the heteroatoms of type A include at least one of N, O, and S; Combination A contains C. 1-20 Alkyl and amino groups.

2. The acid-containing organic compound according to claim 1, characterized in that, In equation (I), n is an integer between 0 and 16; A is an acidic group containing at least one element selected from P, S, C, and Si; L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-24 The aromatic compound is separated from at least one of the following: a linking group formed by any two H atoms capable of leaving; -S-; -O-; -NH-; -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 12; the heteroatoms of type A include at least one of N, O, and S; Combination A contains C. 1-16 Alkyl and amino groups.

3. The acid-containing organic compound according to claim 2, characterized in that, In equation (I), n is an integer between 0 and 10; A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3; L stands for -(CH2) m - Composed of C with or without type A heteroatoms 3-16 The aromatic compound is separated from at least one of the following: a linking group formed by any two H atoms capable of leaving; -S-; -O-; -NH-; -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 10; the A-type heteroatoms include at least one of N, O, and S; Combination A contains C. 1-12 Alkyl, amino groups; Preferably, in formula (I), n is an integer between 0 and 10; A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3; L stands for -(CH2) m - At least one of the following: a linking group formed by benzene leaving any two H atoms; a linking group formed by biphenyl leaving any two H atoms; a linking group formed by naphthalene leaving any two H atoms; a linking group formed by anthracene leaving any two H atoms; a linking group formed by phenanthrene leaving any two H atoms; a linking group formed by pyridine leaving any two H atoms; a linking group formed by dibenzothiophene leaving any two H atoms; a linking group formed by dibenzofuran leaving any two H atoms; -S-, -O-, -NH-, -COO-; and the L group optionally contains at least one group from combination A; m is an integer from 1 to 10; Combination A contains C. 1-8 Alkyl and amino groups.

4. The acid-containing organic compound according to any one of claims 1-3, characterized in that, In equation (I), n is an integer between 0 and 10; A is -P(O)(OH)2; L stands for -(CH2) m -; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 10; Combination A contains C. 1-4 Alkyl, amino groups; Preferably, the acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

5. The acid-containing organic compound according to any one of claims 1-3, characterized in that, In equation (I), n is an integer between 0 and 10; A is -P(O)(OH)2, -S(O)2(OH), -COOH, or -Si(OH)3; L stands for -(CH2) m At least one of -, -S-, -O-, -NH-, -COO-; and the L group may optionally contain at least one group from combination A; m is an integer from 1 to 10; Combination A contains C. 1-8 Alkyl, amino groups; Preferably, the acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

6. The acid-containing organic compound according to any one of claims 1-3, characterized in that, The acidic organic compound with the structure shown in formula (I) is selected from any one of the following:

7. The use of the acid-containing organic compound according to any one of claims 1-6 in perovskite solar cells.

8. A perovskite solar cell, characterized in that, The perovskite solar cell includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode. The perovskite solar cell contains the acid-containing organic compound as described in any one of claims 1-6.

9. The perovskite solar cell according to claim 8, characterized in that, The acidic organic compound is present in the hole transport layer.

10. The perovskite solar cell according to claim 8, characterized in that, The metal electrode includes a metal cathode, and the material forming the metal cathode is selected from at least one of Al, Ag, Au, Mg, Cu, Mo and Cr.

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