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

Abstract

The application relates to the technical field of solar cells, and discloses an amine group-containing organic compound, application of the organic compound and a perovskite solar cell. The organic compound has a structure shown in formula (I). The organic compound provided by the application can have excellent hole transport performance and can improve photoelectric performance.

Description

Technical Field

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

[0002] The development of new energy sources provides an important guarantee 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 (PSCs) 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 issues. Self-assembled monolayers (SAMs) can improve the performance of pin PSCs, but ultrathin SAMs may exhibit thermal instability, thus affecting the photoelectric performance of perovskite solar cells. Therefore, developing SAM materials with thermal stability is crucial. Summary of the Invention

[0005] The purpose of this invention is to develop a hole transport material that, when applied to perovskite solar cells, exhibits excellent hole transport performance and improves photoelectric performance.

[0006] To achieve the above objectives, a first aspect of the present invention provides an amine-containing organic compound having the structure shown in formula (I):

[0007]

[0008] In equation (I),

[0009] Y does not exist; or, Y is selected from O, S, -C(R) x )2-、N(R y ); R x and R y C 1-6 alkyl, C 6-20 Any one of the aromatic groups;

[0010] R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-20 alkyl, C 1-20 alkoxy, halogen, C 6-30 Any of the aromatic groups; m is an integer from 0 to 16;

[0011] R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3;

[0012] L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-20 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-12 alkyl, C 1-12 The alkoxy group is composed of n; n is an integer from 1 to 16.

[0013] A second aspect of the invention provides the use of the organic compounds described in the first aspect in perovskite solar cells.

[0014] A third aspect of the present invention provides a perovskite solar cell containing at least one of the organic compounds described in the first aspect.

[0015] The present invention has at least the following specific advantages:

[0016] 1. This invention provides an organic compound that introduces two nitrogen-containing groups to further increase hole transport performance, reduce defects at the interface with the perovskite layer, reduce hole trapping and carrier recombination at that point, reduce the hysteresis effect of the cell, and improve the efficiency of perovskite solar cell devices.

[0017] 2. The method for synthesizing organic compounds provided by this invention is simple, has a clear structure, is low in cost, and has excellent performance, making it highly valuable for application in optoelectronic fields such as solar cells.

[0018] 3. The organic compounds provided by this invention simultaneously increase the molecular weight, improve the thermal stability of the material, extend the service life of the component, and improve the weather resistance of perovskite solar cells;

[0019] 4. The organic compounds provided by this invention anchor metal oxides with specific oxygen-containing groups, forming a monolayer on the surface and passivating surface defects, thereby improving the stability of perovskite solar cells. Detailed Implementation

[0020] 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.

[0021] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0022] The absence of Y indicates that the two benzene ring structures are directly connected by chemical bonds, forming a carbazole structure.

[0023] C 1-20 The alkyl group refers to a straight-chain or branched alkyl group with a total number of carbon atoms of 1-20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20). Exemplarily, it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc. "C" 1-12 Alkyl", C 1-8 Alkyl", C 1-6 Alkyl groups have similar definitions, differing only in the total number of carbon atoms.

[0024] C 1-20 The alkoxy group refers to a straight-chain or branched-chain alkoxy group with a total number of carbon atoms of 1-20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20). Exemplarily, it can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, etc. "C" 1-12 Alkoxy" "C" 1-8 Alkoxy, C 1-6 "Alkoxy" and similar terms have similar definitions, differing only in the total number of carbon atoms.

[0025] Halogens include: fluorine, chlorine, bromine, and iodine.

[0026] 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".

[0027] C 6-30 The aromatic group indicates that the total number of cyclic carbon atoms on the aromatic group is 1-30 (e.g., 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). Exemplarily, it can be phenyl, naphthyl, biphenyl, terphenyl, anthracene, phenanthrene, pyrene, triphenylene, etc. "C" 6-20 "aromatic group", "C" 6-12 The aromatic group and others have similar definitions, only differing in the total number of carbon atoms.

[0028] "C containing or not containing type A heteroatoms" 6-20 The linkage group provided by removing any two H atoms from at least one substance in an aromatic compound; the Class A heteroatom is selected from at least one of N, O, and S. "The total number of carbon atoms in an aromatic compound is 6-20 (e.g., the total number of carbon atoms can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) is provided by removing any two H atoms from at least one substance, including but not limited to benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, etc.

[0029] n is an integer representation from 0 to 16, where n can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16; when n is 0, it indicates that the group does not exist.

[0030] m is an integer representation from 0 to 16, and n can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16; when n is 0, it means that the group does not exist.

[0031] As previously stated, a first aspect of the present invention provides an amine-containing organic compound having the structure shown in formula (I):

[0032]

[0033] In equation (I),

[0034] Y does not exist; or, Y is selected from O, S, -C(R) x )2-、N(R y); R x and R y C 1-6 alkyl, C 6-20 Any one of the aromatic groups;

[0035] R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-20 alkyl, C 1-20 alkoxy, halogen, C 6-30 Any of the aromatic groups; m is an integer from 0 to 16;

[0036] R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3;

[0037] L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-20 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-12 alkyl, C 1-12 The alkoxy group is composed of n; n is an integer from 1 to 16.

[0038] In the preferred case, in equation (I-1),

[0039] Y does not exist; or, Y is selected from O, S, -C(R) x )2-、N(R y ); R x and R y C 1-4 alkyl, C 6-12 Any one of the aromatic groups;

[0040] R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10;

[0041] R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3;

[0042] L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

[0043] According to a preferred embodiment (hereinafter referred to as preferred embodiment 1), Y does not exist in formula (I-1);

[0044] R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10;

[0045] R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3;

[0046] L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12 At least one of the linking groups provided by the removal of any two H atoms from at least one substance in the aromatic compound; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

[0047] In the preferred embodiment 1, more preferably, the organic compound is selected from any one of the following:

[0048]

[0049]

[0050]

[0051]

[0052] According to a preferred embodiment (hereinafter referred to as preferred embodiment 2), in formula (I-1), Y is selected from O, S, -C(R) x )2-、N(R y ); R x and R y C1-4 alkyl, C 6-12 Any one of the aromatic groups;

[0053] R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10;

[0054] R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3;

[0055] L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

[0056] In the preferred embodiment 2, more preferably, the organic compound is selected from any one of the following:

[0057]

[0058]

[0059]

[0060] According to a preferred embodiment, the organic compound is selected from any one of the following:

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068] This invention does not impose any particular limitation on the specific methods for preparing the aforementioned organic 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 listed 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.

[0069] As previously stated, a second aspect of the present invention provides the use of the organic compounds described in the first aspect in perovskite solar cells.

[0070] 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.

[0071] 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 organic compounds provided by this invention in the presence of perovskite solar cells, the following section of this invention provides an exemplary fabrication process and specific parameters for a perovskite solar cell in the device embodiment section. Those skilled in the art should not interpret this as a limitation of the invention.

[0072] As previously stated, a third aspect of the present invention provides a perovskite solar cell containing at least one of the organic compounds described in the first aspect.

[0073] Preferably, the organic compound is present in the hole transport layer of the perovskite solar cell.

[0074] Preferably, 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.

[0075] Preferably, the conductive substrate is a conductive glass substrate.

[0076] 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.

[0077] Preferably, 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.

[0078] Preferably, the material forming the electron transport layer is a metal oxide electron transport material and / or an organic small molecule electron transport material.

[0079] Particularly preferably, the organic small molecule electron transport material is selected from at least one of fullerenes and their derivatives.

[0080] More preferably, the metal oxide electron transport material is selected from at least one of TiO2, ZnO or SnO2.

[0081] 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.

[0082] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, the raw materials used are all commercially available products.

[0083] The room temperature or normal temperature mentioned below refers to 25±1℃.

[0084] Preparation Example 1: Synthesis of Compound 1

[0085]

[0086] Synthesis of intermediate 1-1: 0.1 mol of starting material a was dissolved in 240 ml of toluene, and 0.1 mol of starting material b, 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 atmosphere 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 1-1 was obtained by column chromatography (yield: 67.1%).

[0087] Synthesis of intermediate 1-2: The synthesis method is the same as that of intermediate 1-1, to obtain intermediate 1-2 (yield: 67.5%).

[0088] Synthesis of Compound 1: 0.03 mol of intermediate 3-2 was dissolved in 190 mL of dichloromethane, cooled to 0 °C, and 0.07 mol of boron tribromide was added. The mixture was stirred at 0 °C for 24 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 1 was obtained by column chromatography (yield: 90.2%).

[0089] Mass spectrometry: C38H30N3O3P, theoretical value: 607.20, measured value: 607.19. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.84~1.97 (2H, m), 3.53~3.62 (2H, m), 7.05~7.24 (8H, m), 7.27~7.35 (4H, m), 7.35~7.43 (2H, m), 7.46~7.56 (2H, m), 7.64~7.72 (4H, m), 8.13~8.23 (2H, m), 8.49~8.59 (2H, m), 11.95~11.98 (2H, m).

[0090] Preparation Example 2: Synthesis of Compound 5

[0091]

[0092] Synthesis of intermediate 5-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 5-1 (yield: 67.7%).

[0093] Synthesis of intermediate 5-2: The synthesis method is the same as that of intermediate 1-2, yielding intermediate 5-2 (yield: 67.5%).

[0094] Synthesis of compound 5: The synthesis method was the same as that of compound 1, yielding compound 5 (yield: 89.9%).

[0095] Mass spectrometry: C40H34N3O3P, theoretical value: 635.23, measured value: 635.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.19~1.31(2H, m), 1.42~1.53(2H, m), 1.59~1.72(2H, m), 3.88~3.97(2H, m), 7 .05~7.23(8H,m), 7.27~7.35(4H,m), 7.35~7.44(2H,m), 7.48~7.54(2H,m), 7 .64~7.72(4H,m), 8.13~8.22(2H,m), 8.49~8.59(2H,m), 11.95~11.98(2H,m).

[0096] Preparation Example 3: Synthesis of Compound 12

[0097]

[0098] Synthesis of intermediate 12-1: 0.1 mol of starting material e was dissolved in 220 ml of 1,4-dioxane solvent and stirred under nitrogen purging. 0.1 mol of pinacol diborate, 0.25 mol of potassium acetate, and 3 mmol of ferrocene palladium dichloride were added sequentially. The mixture was heated to reflux and reacted. After 8 h, HPLC analysis showed that the reaction of the starting material was basically complete. 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 12-1 (yield: 76.9%).

[0099] Synthesis of intermediate 12-2: 0.07 mol of starting material f was dissolved in 185 mL of toluene solvent, nitrogen gas was introduced and stirred, and 0.07 mol of intermediate 12-1, 0.18 mol of potassium carbonate, and 2.1 mmol of tetrakis(triphenylphosphine)palladium were added sequentially. The mixture was heated to reflux, and after 12 h, HPLC analysis showed that the reaction of the starting material was basically complete. The reaction was stopped, and the mixture was 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 12-2 (yield: 79.2%).

[0100] Synthesis of intermediate 12-3: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 12-3 (yield: 67.6%).

[0101] Synthesis of intermediate 12-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 12-4 (yield: 67.3%).

[0102] Synthesis of compound 12: The synthesis method was the same as that of compound 1, yielding compound 12 (yield: 90.6%).

[0103] Mass spectrometry: C44H33N3O3S, theoretical value: 683.22, measured value: 683.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=2.58~2.67 (2H, m), 3.31~3.40 (2H, m), 6.65~6.68 (1H, s), 7.00~7.24 (12H, m), 7.28~7.45 (6H, m), 7.48~7.56 (2H, m), 7.65~7.73 (4H, m), 8.14~8.24 (2H, m), 8.50~8.60 (2H, m).

[0104] Preparation Example 4: Synthesis of Compound 17

[0105]

[0106] Synthesis of intermediate 17-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 17-1 (yield: 68.2%).

[0107] Synthesis of compound 17: The synthesis method was the same as that of compound 1, yielding compound 17 (yield: 90.2%).

[0108] Mass spectrometry: C44H42N3O3P, theoretical value: 691.30, measured value: 691.29. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.21~1.31(2H, m), 1.44~1.53(2H, m), 1.61~1.71(2H, m), 2.48~2.52(12H, s), 3.90~3.95(2H,m), 7.15~7.20(2H,m), 7.29~7.41(8H,m), 7.45~7.49(2H,d), 7 .66~7.72(4H,m), 8.02~8.04(2H,d), 8.79~8.81(2H,d), 11.90~11.93(2H,m).

[0109] Preparation Example 5: Synthesis of Compound 31

[0110]

[0111] Synthesis of intermediate 31-1: The synthesis method is the same as that of intermediate 12-1, yielding intermediate 31-1 (yield: 76.8%).

[0112] Synthesis of intermediate 31-2: The synthesis method is the same as that of intermediate 12-2, yielding intermediate 31-2 (yield: 78.4%).

[0113] Synthesis of intermediate 31-3: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 31-3 (yield: 67.4%).

[0114] Synthesis of intermediate 31-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 31-4 (yield: 67.5%).

[0115] Synthesis of compound 31: The synthesis method was the same as that of compound 1, yielding compound 31 (yield: 91.3%).

[0116] Mass spectrometry: C48H43N3O7Si, theoretical value: 801.29, measured value: 801.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=0.92~1.00(2H, m), 2.35~2.43(2H, m), 3.79~3.82(12H, s), 4.79~4.81(3H, s), 6.58~6.62(2H, m), 7.00~7.05(2H, m), 7.16~7.22(4H, m), 7.29~7.35(6H, m), 7.38~7.42(2H, d), 7.66~7.73(6H, m), 8.23~8.25(2H, d).

[0117] Preparation Example 6: Synthesis of Compound 37

[0118]

[0119] Synthesis of intermediate 37-1: 0.1 mol of starting material i was dissolved in 330 mL of dioxane solvent, followed by the addition of 0.1 mol of Boc2O and 0.25 mol of sodium hydroxide. The mixture was heated to reflux and after 12 h, HPLC analysis showed that the reaction of the starting material was basically complete. The reaction was then 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 37-1 (yield: 89.3%).

[0120] Synthesis of intermediate 37-2: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 37-2 (yield: 67.9%).

[0121] Synthesis of intermediate 37-3: 0.05 mol of intermediate 37-2 was dissolved in 730 mL of dioxane solvent, and 0.05 mol of hydrochloric acid was added sequentially. The mixture was heated to reflux and after 6 h, HPLC analysis showed that the reaction of the starting material was basically complete. The reaction was stopped, and the mixture was 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 37-3 (yield: 90.1%).

[0122] Synthesis of intermediate 37-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 37-4 (yield: 67.7%).

[0123] Synthesis of compound 37: The synthesis method was the same as that of compound 1, yielding compound 37 (yield: 89.6%).

[0124] Mass spectrometry: C38H26ClN3O3P, theoretical value: 743.05, measured value: 743.00. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.84~1.97 (2H, m), 3.53~3.61 (2H, m), 7.05~7.11 (2H, m), 7.27~7.37 (8H, m), 7.42~7.48 (2H, d), 7.64~7.72 (4H, m), 7.84~7.88 (2H, m), 8.04~8.08 (2H, d), 11.92~11.94 (2H, m).

[0125] Preparation Example 7: Synthesis of Compound 49

[0126]

[0127] Synthesis of intermediate 49-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 49-1 (yield: 68.1%).

[0128] Synthesis of compound 49: The synthesis method was the same as that of compound 1, yielding compound 49 (yield: 89.4%).

[0129] Mass spectrometry: C38H34N7O3P, theoretical value: 667.25, measured value: 667.26. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.84~1.96(2H, m), 3.52~3.60(2H, m), 3.61~3.65(8H, s), 6.62~6.67(2H, m), 6.81~6.86(2H, m), 7.04~7.06(2H, d), 7.14~7.19(2H, d), 7.25~7.31(6H, m), 7.48~7.50(2H, d), 7.62~7.68(4H, m), 11.92~11.95(2H, m).

[0130] Preparation Example 8: Synthesis of Compound 58

[0131]

[0132] Synthesis of intermediate 58-1: The synthesis method is the same as that of intermediate 37-1, yielding intermediate 58-1 (yield: 89.6%).

[0133] Synthesis of intermediate 58-2: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 58-2 (yield: 67.3%).

[0134] Synthesis of intermediate 58-3: The synthesis method is the same as that for intermediate 37-3, yielding intermediate 58-3 (yield: 89.2%).

[0135] Synthesis of intermediate 58-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 58-4 (yield: 67.1%).

[0136] Synthesis of intermediate 58-5: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 58-5 (yield: 67.7%).

[0137] Synthesis of compound 58: The synthesis method was the same as that for compound 1, yielding compound 58 (yield: 91.1%).

[0138] Mass spectrometry: C41H37N7O2, theoretical value: 659.30, measured value: 659.29. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.42~1.59 (4H, m), 2.17~2.25 (2H, m), 3.89~3.96 (2H, s), 4.71~4.75 (8H, m), 5.89~5.94 (2H, m), 6.76~6.88 (6H, m), 6.95~7.02 (4H, m), 7.29~7.35 (4H, m), 7.66~7.72 (4H, m), 8.64~8.66 (1H, d).

[0139] Preparation Example 9: Synthesis of Compound 65

[0140]

[0141] Synthesis of intermediate 65-1: The synthesis method is the same as that of intermediate 12-1, yielding intermediate 65-1 (yield: 76.4%).

[0142] Synthesis of intermediate 65-2: The synthesis method is the same as that for intermediate 12-2, yielding intermediate 65-2 (yield: 78.3%).

[0143] Synthesis of intermediate 65-3: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 65-3 (yield: 67.6%).

[0144] Synthesis of intermediate 65-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 65-4 (yield: 67.1%).

[0145] Synthesis of compound 65: The synthesis method was the same as that of compound 1, yielding compound 65 (yield: 89.8%).

[0146] Mass spectrometry: C44H38N7O3P, theoretical value: 743.28, measured value: 743.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.95~2.07 (2H, m), 2.82~2.90 (2H, m), 3.65~3.69 (8H, s), 6.65~6.70 (2H, m), 6 .85~6.89(2H,m), 7.00~7.05(2H,m), 7.08~7.10(2H,d), 7.16~7.22(4H,m), 7 .29~7.35(6H,m), 7.52~7.54(2H,d), 7.66~7.72(4H,m), 11.89~11.91(2H,m).

[0147] Preparation Example 10: Synthesis of Compound 70

[0148]

[0149] Synthesis of intermediate 70-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 70-1 (yield: 69.1%).

[0150] Synthesis of intermediate 70-2: The synthesis method is the same as that of intermediate 37-3, yielding intermediate 70-2 (yield: 89.5%).

[0151] Synthesis of intermediate 70-3: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 70-3 (yield: 68.7%).

[0152] Synthesis of intermediate 70-4: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 70-4 (yield: 68.3%).

[0153] Synthesis of compound 70: The synthesis method was the same as that of compound 1, yielding compound 70 (yield: 89.6%).

[0154] Mass spectrometry: C40H36N5O3P, theoretical value: 665.26, measured value: 665.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.18~1.32(2H, m), 1.41~1.54(2H, m), 1.59~1.72(2H, m), 3.63~3.67(4H, s), 3.88~3.96(2H, m), 6.83~6.88(2H, m), 7.05~7.21(8H, m), 7.27~7.34(4H, m), 7.47~7.53(2H, m), 7.64~7.70(4H, m), 8.50~8.56(2H, m), 11.90~11.93(2H, d).

[0155] Preparation Example 11: Synthesis of Compound 80

[0156]

[0157] Synthesis of intermediate 80-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 80-1 (yield: 69.4%).

[0158] Synthesis of intermediate 80-2: The synthesis method is the same as that of intermediate 37-3, yielding intermediate 80-2 (yield: 89.8%).

[0159] Synthesis of intermediate 80-3: The synthesis method is the same as that of intermediate 1-1, to obtain intermediate 80-3 (yield: 68.5%).

[0160] Synthesis of compound 80: The synthesis method was the same as that of compound 1, yielding compound 80 (yield: 89.2%).

[0161] Mass spectrometry: C44H41N3O3S, theoretical value: 691.29, measured value: 691.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.67~1.71 (12H, s), 3.22~3.29 (2H, m), 3.70~3.77 (2H, m), 6.66~6.67 (1H, s), 6.89~7.00 (4H, m), 7.12~7.23 (20H, m).

[0162] Preparation Example 12: Synthesis of Compound 93

[0163]

[0164] Synthesis of intermediate 93-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 93-1 (yield: 68.7%).

[0165] Synthesis of intermediate 93-2: The synthesis method is the same as that of intermediate 37-3, yielding intermediate 93-2 (yield: 89.5%).

[0166] Synthesis of intermediate 93-3: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 93-3 (yield: 68.2%).

[0167] Synthesis of compound 93: The synthesis method was the same as that of compound 1, yielding compound 93 (yield: 89.4%).

[0168] Mass spectrometry: C38H30N3O5P, theoretical value: 639.19, measured value: 639.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.85~1.97 (2H, m), 3.54~3.62 (2H, m), 6.89~7.05 (12H, m), 7.09~7.18 (12H, m), 11.90~11.93 (2H, d).

[0169] Device Example 1

[0170] 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.

[0171] Compound 1 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] A 100 nm silver electrode was deposited under a pressure of 2 × 10⁻⁴ Pa to complete the fabrication of a perovskite solar cell.

[0176] The remaining device embodiments of the present invention are prepared using a method similar to that of device embodiment 1, except that the compound in the hole transport layer of device embodiment 1 is replaced with the corresponding compound in Table 1.

[0177] Device Comparison Examples 1-3

[0178] The comparative device was prepared using a method similar to that of Device Example 1, except that the compounds in the hole transport layer of Device Example 1 were replaced with compounds Ref-1, Ref-2, and Ref-3.

[0179]

[0180] Test case

[0181] 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 scanning rate was 10mV / s, and the scanning direction was forward and reverse scanning -0.2V to 1.2V.

[0182] The photovoltaic parameters of each device embodiment and device comparison example are shown in Table 1.

[0183] Table 1

[0184]

[0185]

[0186] In summary, the compounds provided by this invention, as SAM 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 solutions, making the preparation process convenient.

[0187] 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 combining the 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 organic compound containing an amino group, characterized in that, The organic compound has the structure shown in formula (I): In equation (I), Y does not exist; or, Y is selected from O, S, -C(R) x )2-、N(R y ); R x and R y C 1-6 alkyl, C 6-20 Any one of the aromatic groups; R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-20 alkyl, C 1-20 alkoxy, halogen, C 6-30 Any of the aromatic groups; m is an integer from 0 to 16; R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3; L and L1 may or may not exist independently, and L and L1 are optionally selected from C with or without type A heteroatoms. 6-20 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-12 alkyl, C 1-12 The alkoxy group composition; n is an integer from 1 to 16.

2. The amine-containing organic compound according to claim 1, characterized in that, In equation (I), Y does not exist; or, Y is selected from O, S, -C(R) x )2-、N(R y ); R x and R y C 1-4 alkyl, C 6-12 Any one of the aromatic groups; R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10; R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3; L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

3. The amine-containing organic compound according to claim 1 or 2, characterized in that, In equation (I), Y does not exist; R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10; R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3; L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

4. The amine-containing organic compound according to claim 3, characterized in that, The amine-containing organic compound is selected from any one of the following:

5. The amine-containing organic compound according to claim 1 or 2, characterized in that, In equation (I), Y is selected from O, S, and -C(R) x )2-、N(R y ); R x and R y C 1-4 alkyl, C 6-12 Any one of the aromatic groups; R1 and R2 are each independently selected from H and -(CH2). m -NH2, C 1-12 alkyl, C 1-12 alkoxy, halogen, C 6-20 Any of the aromatic groups; m is an integer from 0 to 10; R is selected from any one of -P(O)(OH)2, -S(O)2(OH), -COOH, and -Si(OH)3; L and L1 exist independently or not, and their presence is arbitrarily chosen from C atoms that contain or do not contain type A heteroatoms. 6-12 The aromatic compound contains a linking group provided by the removal of any two H atoms from at least one substance; the type A heteroatom is selected from at least one of N, O, and S; the aromatic compound optionally contains at least one substituent selected from combination A; combination A is composed of C 1-8 alkyl, C 1-8 The alkoxy group is composed of n; n is an integer from 1 to 10.

6. The amine-containing organic compound according to claim 5, characterized in that, The amine-containing organic compound is selected from any one of the following:

7. The organic compound according to claim 1 or 2, characterized in that, The amine-containing organic compound is selected from any one of the following:

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

9. A perovskite solar cell, characterized in that, The perovskite solar cell contains at least one of the amine-containing organic compounds as described in any one of claims 1-7.

10. The perovskite solar cell according to claim 9, 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.

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