Organic compound and preparation method thereof, hole transport material and solar cell

Abstract

The invention relates to an organic compound and a preparation method thereof, a hole transport material and a solar cell. The structure of the organic compound is shown as a formula (I). According to the organic compound, polymethyl methacrylate is used as a main chain, a pyridine ring is used as a linking group, phenothiazine or phenoxazine is connected to the main chain, and a sulfenyl aniline fluorene group is connected to phenothiazine or phenoxazine, so that the stability of the organic compound is relatively good. The organic compound is used as a hole transport material of the perovskite solar cell, has relatively good mobility, is beneficial to hole extraction and transport, has a relatively deep HOMO energy level matched with perovskite, and can effectively improve the photoelectric conversion efficiency and the stability of the perovskite solar cell.

Description

Technical Field

[0001] The present application relates to the technical field of batteries, and particularly to an organic compound, a preparation method thereof, a hole transporting material, and a solar cell. Background Art

[0002] In perovskite solar cells, the hole transporting material, as an important transport layer material between the perovskite light-absorbing layer and the electrode, is not only responsible for the extraction and transport of holes to improve the photoelectric conversion efficiency of perovskite cells, but also can modify the interface and block the flow of electrons to enhance the stability of perovskite cells. Currently, the hole transporting materials in perovskite solar cells are mainly divided into three categories: inorganic hole transporting materials, organic small molecule hole transporting materials, and organic polymer hole transporting materials. Among them, organic polymer hole transporting materials have become the commonly used hole transporting materials in perovskite solar cells due to their good film-forming properties and strong solvent tolerance. However, the stability of traditional organic polymer hole transporting materials still needs to be further improved. Summary of the Invention

[0003] Based on this, the present application provides an organic compound with good stability, a preparation method thereof, a hole transporting material, and a solar cell.

[0004] The technical solutions for solving the above technical problems in the present application are as follows.

[0005] In a first aspect of the present application, an organic compound is provided, and the structure of the organic compound is shown in formula (I):

[0006]

[0007] Wherein, X is selected from an oxygen atom or a sulfur atom;

[0008] R1 is selected from a substituted or unsubstituted C1-C 18 alkyl group;

[0009] R2 to R4 are each independently selected from hydrogen, a substituted or unsubstituted C1-C 18 alkyl group, a substituted or unsubstituted C1-C 18 alkoxy group, a substituted or unsubstituted C1-C 18 alkylthio group, a halogen atom, a trifluoromethyl group, a hydroxyl group, a mercapto group, a cyano group, an amino group, and a substituted or unsubstituted C6-C 18 aryl group;

[0010] Each of the substituents of the substituted ones is independently selected from one of a C1-C4 alkyl group, an amino group, a halogen, a nitro group, a hydroxyl group, a mercapto group, a carboxyl group, and a cyano group;

[0011] Each occurrence of a and b is independently selected from an integer of 1 to 4;

[0012] Each occurrence of c is independently selected from an integer of 1 to 3;

[0013] n is an integer from 10 to 1000.

[0014] In some embodiments, in the organic compound, the organic compound satisfies at least one of the following characteristics:

[0015] (1) R1 is selected from C1-C4 alkyl;

[0016] (2) R2 to R4 are each independently selected from one of hydrogen, C1-C4 alkyl, C1-C4 alkoxy, halogen atom, trifluoromethyl, hydroxyl, mercapto, cyano, and amino.

[0017] In some embodiments, in the organic compound, the structure of the organic compound is as shown in Formula (I-1) to Formula (I-2):

[0018] .

[0019] The second aspect of the present application provides a method for preparing an organic compound, including the following steps:

[0020] Performing a nucleophilic substitution reaction on the compound shown in Formula (II) and the compound shown in Formula (III) to prepare the compound shown in Formula (IV);

[0021] Performing a reduction reaction on the compound shown in Formula (IV) to prepare the compound shown in Formula (V);

[0022] Performing an alcoholysis reaction on the compound shown in Formula (V) and acryloyl chloride to prepare the compound shown in Formula (VI);

[0023] Performing a polymerization reaction on the compound shown in Formula (VI) to prepare the organic compound; the structure of the organic compound is as shown in Formula (I):

[0024]

[0025] Wherein, X is selected from an oxygen atom or a sulfur atom;

[0026] Y is a halogen atom;

[0027] R1 is selected from substituted or unsubstituted C1-C 18 alkyl;

[0028] R2 to R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C 18 alkyl, substituted or unsubstituted C1-C 18 alkoxy, substituted or unsubstituted C1-C 18Alkylthio, halogen atom, trifluoromethyl, hydroxyl, mercapto, cyano, amino and substituted or unsubstituted C6~C 18 One of the aromatic groups;

[0029] Each of the substituted substituents is independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano;

[0030] Each occurrence of a and b is independently selected from integers from 1 to 4;

[0031] Each occurrence of c is independently selected from an integer from 1 to 3;

[0032] n is an integer from 10 to 1000.

[0033] In some embodiments, in the method for preparing an organic compound, the method satisfies at least one of the following characteristics:

[0034] (1) In the nucleophilic displacement reaction, the molar ratio of the compound represented by formula (II) to the compound represented by formula (III) is 1:(2.2-3);

[0035] (2) The nucleophilic displacement reaction is carried out in the presence of a first catalyst and a first ligand, wherein the first catalyst comprises palladium acetate and the first ligand comprises tri-tert-butylphosphine; optionally, the molar ratio of the first catalyst to the compound represented by formula (II) is (0.03-0.1):1;

[0036] (3) The nucleophilic displacement reaction is carried out in the presence of a first base, wherein the first base comprises sodium tert-butoxide; optionally, the molar ratio of the first base to the compound represented by formula (II) is (0.8-2):1;

[0037] (4) The temperature of the nucleophilic displacement reaction is 85°C to 100°C;

[0038] (5) The reduction reaction is carried out in the presence of a reducing agent, wherein the reducing agent comprises sodium borohydride; optionally, the molar ratio of the reducing agent to the compound represented by formula (IV) is (0.03-0.1):1;

[0039] (6) The reduction reaction includes a first reduction reaction and a second reduction reaction performed sequentially, wherein the temperature of the first reduction reaction is -5°C to 0°C, and the temperature of the second reduction reaction is 25°C to 35°C;

[0040] (7) In the alcoholysis reaction, the molar ratio of the compound represented by formula (V) to acryloyl chloride is 1:(1.1-2);

[0041] (8) The alcoholysis reaction is carried out under the condition of containing a second base, and the second base includes triethylamine; optionally, the molar ratio of the second base to the compound represented by formula (V) is (50~300):1;

[0042] (9) The temperature of the polymerization reaction is 65°C to 85°C;

[0043] (10) The polymerization reaction is carried out in the presence of an initiator, and the initiator includes azobisisobutyronitrile.

[0044] In some embodiments, in the preparation method of the organic compound, the preparation of the compound represented by formula (II) includes the following steps:

[0045] The compound represented by formula (VII) is subjected to a halogenation reaction to prepare the compound represented by formula (II);

[0046]

[0047] wherein, X is selected from an oxygen atom or a sulfur atom;

[0048] [[ID=2×]] Optionally, the preparation method satisfies at least one of the following characteristics:

[0049] (1) The halogenation reaction is carried out under the condition of containing a halogenating agent, and the halogenating agent includes N-halosuccinimide, and the molar ratio of the halogenating agent to the compound represented by formula (VII) is (2.2~3):1;

[0050] (2) The temperature of the halogenation reaction is -5°C to 0°C.

[0051] In some embodiments, in the preparation method of the organic compound, the preparation of the compound represented by formula (VII) includes the following steps:

[0052] The compound represented by formula (VIII) and 2-halo-4-pyridinebenzaldehyde are subjected to a substitution reaction to prepare the compound represented by formula (VIII);

[0053]

[0054] [[ID=×9]] wherein, X is selected from an oxygen atom or a sulfur atom.

[0055] In some embodiments, in the preparation method of the organic compound, the preparation method satisfies at least one of the following characteristics:

[0056] (1) In the substitution reaction, the molar ratio of the compound represented by formula (VIII) to the 2-halo-4-pyridinebenzaldehyde is 1:(1.1~1.5);

[0057] It should be noted that there seems to be a typo in "2×" in the translation of line , which should probably be "21". The above translation is based on the content you provided. If you have any other questions, please feel free to let me know.(2) The substitution reaction is carried out under the conditions of a second catalyst and a second ligand. The second catalyst includes cuprous iodide, and the second ligand includes cis-1,2-cyclohexanediamine; optionally, the molar ratio of the second catalyst to the compound shown in formula (VIII) is (0.05~0.1):1, and the molar ratio of the second ligand to the compound shown in formula (VIII) is (0.05~0.1):1;

[0058] (3) The substitution reaction is carried out under the conditions of a third base. The third base includes potassium phosphate; optionally, the molar ratio of the third base to the compound shown in formula (VIII) is (3~10):1;

[0059] (4) The temperature of the substitution reaction is 110°C~120°C.

[0060] The third aspect of the present application provides a hole transport material, which includes the organic compound provided in the first aspect or the organic compound prepared by the preparation method provided in the second aspect.

[0061] The fourth aspect of the present application provides a solar cell, which includes the hole transport material provided in the third aspect.

[0062] The organic compound provided in the present application has a polymethyl methacrylate main chain, a pyridine ring as a linking group, connects phenothiazine or phenoxazine to the main chain, and connects a thiophenylamine fluorene group to the phenothiazine or phenoxazine, so that the organic compound has good stability.

[0063] Using the organic compound of the present application as the hole transport material of the perovskite solar cell, it has a good mobility, which is beneficial to the extraction and transport of holes, and has a HOMO energy level that matches the perovskite and is relatively deep, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] In order to more clearly illustrate the technical solutions in the embodiments of the present application and more completely understand the present application and its beneficial effects, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0065] Figure 1 It is a schematic structural diagram of a solar cell provided in an embodiment;

[0066] Figure 2 It is a 1H NMR spectrum of the compound PMAPy-POZ;

[0067] Figure 31H NMR spectrum of compound PMAPy-PTZ.

[0068] Reference numerals:

[0069] 100: solar cell; 110: transparent conductive electrode; 120: hole transport layer; 130: perovskite light-absorbing layer; 140: electron transport layer; 150: metal electrode. Detailed implementation manners

[0070] The present application will be further described in detail below in combination with implementation manners and examples. It should be understood that these implementation manners and examples are only used to illustrate the present application and not to limit the scope of the present application. The purpose of providing these implementation manners and examples is to make the understanding of the disclosed content of the present application more thorough and comprehensive.

[0071] It should also be understood that the present application can be implemented in many different forms and is not limited to the implementation manners and examples described herein. Those skilled in the art can make various changes or modifications without departing from the connotation of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, the features described as part of one implementation manner can be combined with another implementation manner in a suitable way to produce a new implementation manner. In addition, in the following description, a large number of specific details are given to provide a more thorough understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing implementation manners and examples and are not intended to limit the present application.

[0073] Unless otherwise stated or there is a contradiction, the terms or phrases used herein have the following meanings:

[0074] In the present application, the terms "a plurality of", "a variety of", "multiple times", etc., unless otherwise specified, refer to a quantity greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0075] As used herein, "combinations thereof", "any combinations thereof", "any combination manners thereof", etc. include all suitable combination manners of any two or more of the listed items.

[0076] In this document, the "suitable combination manners", "suitable manners", "any suitable manners", etc. described as "suitable" are subject to being able to implement the technical solution of the present application, solve the technical problems of the present application, and achieve the expected technical effects of the present application.

[0077] In this application, terms such as "further", "even further", "especially", etc. are used for descriptive purposes, indicating differences in content, but should not be construed as limiting the scope of protection of this application.

[0078] In this application, in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or quantity, nor can it be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumerative description and should be understood not to constitute a closed limitation on quantity.

[0079] In this application, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, as well as an open technical solution containing the listed features.

[0080] In this application, regarding numerical intervals (i.e., numerical ranges), unless otherwise specified, the distribution of the selectable numerical values within this numerical interval is considered continuous, and it includes the two numerical endpoints of this numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within this numerical interval, it includes the two endpoint integers of this numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When providing multiple numerical ranges to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad inclusion of numerical interval types such as percentage intervals, ratio intervals, ratio value intervals, etc.

[0081] The temperature parameter in this application, unless otherwise specified, allows for both constant temperature treatment and fluctuations within a certain temperature range. It should be understood that the so-called constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed.

[0082] In this application, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, such as 20°C ± 5°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0083] In this application, for units related to data ranges, if a unit is only attached to the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of both the left endpoint "3" and the right endpoint "5" are h (hours).

[0084] All documents mentioned in this application are incorporated herein by reference as if each document was individually incorporated by reference. Unless it conflicts with the inventive purpose and / or technical solution of this application, the cited documents involved in this application are cited for their entire content and entire purpose. When this application involves cited documents, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also incorporated by reference. When this application involves cited documents, the examples and preferred methods of the relevant technical features cited can also be incorporated into this application as references, but only to the extent that this application can be implemented. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or be modified adaptively according to the description in this application.

[0085] The mass or weight of the relevant components mentioned in the specification of the embodiments of this application can not only refer to the specific content of each component, but also represent the proportional relationship of the mass or weight between the components. Therefore, as long as the content of the relevant components in the specification of the embodiments of this application is scaled up or down proportionally, it is within the scope disclosed in the specification of the embodiments of this application. Specifically, the mass or weight described in the specification of the embodiments of this application can be units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0086] In this application, "substituted or unsubstituted" - "substituted" means that the hydrogen atom in the group is replaced by a substituent, and "unsubstituted" in "substituted or unsubstituted" means that the hydrogen atom in the group is not replaced by other atoms or atomic groups.

[0087] Traditional organic polymer hole transport materials include poly(3 - hexylthiophene) (P3HT), poly[bis(4 - phenyl)(2,4,6 - trimethylphenyl)amine] (PTAA), poly(3,4 - ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS); the inherent acidity and hygroscopicity of PEDOT:PSS will corrode and accelerate the degradation of perovskite materials, and will affect the stability of inverted PSCs; problems such as the strong hydrophobicity of PTAA and the insufficient depth of the HOMO energy level all increase the instability of the device, and the cost of PTAA is relatively high ($1980 / g).

[0088] One embodiment of this application provides an organic compound, and the structure of the organic compound is shown in formula (I):

[0089]

[0090] Among them, X is selected from an oxygen atom or a sulfur atom;

[0091] R1 is selected from substituted or unsubstituted C1-C 18 alkyl;

[0092] R2 to R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C 18 alkyl, substituted or unsubstituted C1-C 18 alkoxy, substituted or unsubstituted C1-C 18 alkylthio, halogen atom, trifluoromethyl, hydroxyl, mercapto, cyano, amino and substituted or unsubstituted C6-C 18 aryl;

[0093] Each substituent of the substituents is independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano;

[0094] Each time a and b appear, they are independently selected from integers from 1 to 4;

[0095] Each time c appears, it is independently selected from integers from 1 to 3;

[0096] n is an integer from 10 to 1000.

[0097] The organic compound provided by this application uses polymethyl methacrylate as the main chain, a pyridine ring as the linking group, connects phenothiazine or phenoxazine to the main chain, and connects a thiophenylamine fluorene group to the phenothiazine or phenoxazine, so that the stability of the organic compound is relatively good.

[0098] Using the organic compound of this application as a hole transporting material for perovskite solar cells, it has a relatively good mobility, which is beneficial to the extraction and transport of holes, and has a HOMO energy level that matches the perovskite and is relatively deep, which can effectively improve the photoelectric conversion efficiency and stability of perovskite solar cells.

[0099] Among them, the O atom in the main chain of polymethyl methacrylate can interact with Pb in the perovskite light-absorbing layer 2+ and can passivate the interfacial defects of the perovskite light-absorbing layer / hole transporting layer (HTM), inhibit the non-radiative recombination at the interface, and contribute to the improvement of the efficiency of PSCs (Perovskite Solar Cells) devices.

[0100] Organic compounds incorporating pyridine linking groups can effectively improve the surface wettability of perovskite precursor solutions on film layers containing such organic compounds, thereby promoting the growth of high-quality perovskite thin films. Meanwhile, they can also effectively enhance hole mobility, promote energy level alignment with perovskite, and improve interfacial defect passivation ability, thus improving interfacial charge extraction and reducing interfacial VOC losses. By generating good inherent thermal / optical stability and stronger interactions at the interface through pyridine linking groups, interfacial stress is released, effectively improving the thermal performance and operational stability of PSCs devices.

[0101] Connecting phenothiazine or phenoxazine to the main chain and attaching sulfanyl aniline fluorene groups to phenothiazine or phenoxazine can play a role in regulating energy levels.

[0102] It can be understood that C1~C 18 refers to the number of carbon atoms being 1~18, which can be a straight chain or a branched chain, and this number of carbon atoms does not include the carbon atoms of substituents when substituting; further, the number of carbon atoms in C1~C 18 includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18; in some examples, it can be within the range formed by any two of these point values as the end values, the same hereinafter; for example, R1~R2 can be independently selected from substituted or unsubstituted C1~C 15 alkyl, C2~C 10 alkyl, C3~C6 alkyl, C1~C4 alkyl, etc.; C1~C 18 alkoxy and C1~C 18 alkylthio and so on; C6~C 18 aryl refers to the number of carbon atoms on the aromatic ring being 6~18; a, b, c refer to the number of substituents, and each occurrence of a and b independently includes 1, 2, 3, or 4, and each occurrence of c independently includes 1, 2, or 3; for example, a(R2) means the number of R2 groups can be 1, 2, 3, or 4, respectively substituting the hydrogen on the benzene ring.

[0103] In some of these examples, in the organic compound, R1 is selected from C1~C4 alkyl.

[0104] In some of these examples, in the organic compound, R1 is selected from one of methyl and ethyl; optionally, R1 is methyl.

[0105] In some of these examples, in the organic compound, R2~R4 are independently selected from one of hydrogen, C1~C4 alkyl, C1~C4 alkoxy, halogen atom, trifluoromethyl, hydroxyl, mercapto, cyano, and amino.

[0106] In some of these examples, in the organic compound, R2 to R4 are each independently selected from one of hydrogen, methyl, and ethyl; optionally, R2 to R4 are all hydrogen.

[0107] In some of these examples, the structure of the organic compound is as shown in formula (I-1) or formula (I-2):

[0108] 。

[0109] The organic compound of the present application has a relatively high thermal decomposition temperature and good thermal stability; it has good wettability for the perovskite precursor solution, promoting perovskite crystallization and film formation; it has good mobility, which is beneficial to hole extraction and transport; it has a relatively deep HOMO energy level that matches the perovskite. When used as a hole transport material in a reverse perovskite solar cell, without doping other additives, it can obtain good photoelectric conversion efficiency and high repeatability, and is suitable for preparing large-area reverse PSCs.

[0110] One embodiment of the present application provides a method for preparing an organic compound, including the following steps:

[0111] Step S100: Perform a nucleophilic substitution reaction on the compound shown in formula (II) and the compound shown in formula (III) to prepare the compound shown in formula (IV);

[0112] Step S200: Perform a reduction reaction on the compound shown in formula (IV) to prepare the compound shown in formula (V);

[0113] Step S300: Perform an alcoholysis reaction on the compound shown in formula (V) and acryloyl chloride to prepare the compound shown in formula (VI);

[0114] Step S400: Perform a polymerization reaction on the compound shown in formula (VI) to prepare an organic compound; the structure of the organic compound is as shown in formula (I):

[0115]

[0116] Wherein, X is selected from an oxygen atom or a sulfur atom;

[0117] Y is a halogen atom;

[0118] R1 is selected from a substituted or unsubstituted C1-C 18 alkyl;

[0119] R2 to R4 are each independently selected from hydrogen, a substituted or unsubstituted C1-C 18 alkyl, a substituted or unsubstituted C1-C 18 alkoxy, a substituted or unsubstituted C1-C 18Alkylthio, halogen atom, trifluoromethyl, hydroxyl, mercapto, cyano, amino and substituted or unsubstituted C6~C 18 One of the aromatic groups;

[0120] Each substituted substituent is independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano;

[0121] Each occurrence of a and b is independently selected from integers from 1 to 4;

[0122] Each occurrence of c is independently selected from an integer from 1 to 3;

[0123] n is an integer from 10 to 1000.

[0124] In some examples, in step S100 , the compound of formula (III) includes methylthioaniline fluorene.

[0125] In some examples, in step S100, the molar ratio of the compound represented by formula (II) to the compound represented by formula (III) is 1:(2.2-3). It is understood that the molar ratio refers to the ratio of the amounts of substances; further, the molar ratio of the compound represented by formula (II) to the compound represented by formula (III) includes but is not limited to 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, and 1:3.

[0126] In some examples, in step S100, the nucleophilic displacement reaction is carried out in the presence of a first catalyst and a first ligand; optionally, the first catalyst comprises palladium acetate; optionally, the first ligand comprises tri-tert-butylphosphine; optionally, the molar ratio of the first catalyst to the compound represented by formula (II) is (0.03-0.1):1. It is understood that the molar ratio of the first catalyst to the compound represented by formula (II) includes, but is not limited to, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, and 0.1:1.

[0127] In some examples, in step S100, the nucleophilic displacement reaction is carried out in the presence of a first base; optionally, the first base comprises sodium tert-butoxide; optionally, the molar ratio of the first base to the compound represented by formula (II) is (0.8-2):1. It is understood that the molar ratio of the first base to the compound represented by formula (II) includes, but is not limited to, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, and 2:1.

[0128] In some of these examples, in step S100, the temperature of the nucleophilic substitution reaction is 85°C to 100°C. It can be understood that the temperature of the nucleophilic substitution reaction includes, but is not limited to, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C.

[0129] In some of these examples, in step S100, the nucleophilic substitution reaction is carried out under conditions containing a first organic solvent; optionally, the first organic solvent includes toluene.

[0130] In some of these examples, in step S100, the nucleophilic substitution reaction is carried out under an inert atmosphere condition. It can be understood that the inert atmosphere condition includes, but is not limited to, at least one of nitrogen, argon, etc.

[0131] In some of these examples, in step S200, the reduction reaction is carried out under conditions containing a reducing agent; optionally, the reducing agent includes sodium borohydride; optionally, the molar ratio of the reducing agent to the compound represented by formula (IV) is (0.03 - 0.1):1. It can be understood that the molar ratio of the reducing agent to the compound represented by formula (IV) includes, but is not limited to, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1.

[0132] In some of these examples, in step S200, the reduction reaction includes a first reduction reaction and a second reduction reaction carried out in sequence. The temperature of the first reduction reaction is -5°C to 0°C, and the temperature of the second reduction reaction is 25°C to 35°C. It can be understood that the temperature of the first reduction reaction includes, but is not limited to, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C; the temperature of the second reduction reaction includes, but is not limited to, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C.

[0133] In some of these examples, in step S200, the reduction reaction is carried out under conditions containing a second solvent; optionally, the second solvent includes tetrahydrofuran.

[0134] In some of these examples, in step S300, in the alcoholysis reaction, the molar ratio of the compound represented by formula (V) to acryloyl chloride is 1:(1.1 - 2). It can be understood that the molar ratio of the compound represented by formula (V) to acryloyl chloride includes, but is not limited to, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1.

[0135] In some of these examples, in step S300, the alcoholysis reaction is carried out under the condition of containing a second base; optionally, the second base includes triethylamine; optionally, the molar ratio of the second base to the compound represented by formula (V) is (50~300):1. It can be understood that the molar ratio of the second base to the compound represented by formula (V) includes but is not limited to 50:1, 70:1, 100:1, 130:1, 150:1, 170:1, 200:1, 230:1, 250:1, 270:1, 300:1.

[0136] In some of these examples, in step S300, the alcoholysis reaction is carried out under the condition of containing a third organic solvent; optionally, the third organic solvent includes at least one of DCM and triethylamine.

[0137] In some of these examples, in step S300, the alcoholysis reaction is carried out under an inert atmosphere condition.

[0138] In some of these examples, in step S400, the temperature of the polymerization reaction is 65°C to 85°C. It can be understood that the temperature of the polymerization reaction includes but is not limited to 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C.

[0139] In some of these examples, in step S400, the polymerization reaction includes an initiation stage and a reaction stage that are carried out in sequence. The temperature of the initiation stage is 65°C to 75°C, and the time is 3 h to 5 h; the temperature of the reaction stage is 76°C to 85°C, and the time is 72 h to 86 h.

[0140] In some of these examples, in step S400, the polymerization reaction is carried out in the presence of an initiator; optionally, the initiator includes azobisisobutyronitrile (AIBN). Optionally, the mass ratio of the initiator to the compound represented by formula (VI) is 1% to 2%.

[0141] In some of these examples, in step S400, the polymerization reaction is carried out in the presence of a fourth organic solvent; optionally, the fourth organic solvent includes at least one of toluene, tetrahydrofuran, and N-methylpyrrolidone.

[0142] In some of these examples, in step S400, in the reaction solution of the polymerization reaction, the concentration of the compound represented by formula (VI) is 0.1 mol / L to 1 mol / L. It can be understood that the concentration of the compound represented by formula (VI) includes but is not limited to 0.1 mol / L, 0.2 mol / L, 0.5 mol / L, 0.8 mol / L, 1 mol / L.

[0143] In some of these examples, in step S400, in the reaction solution of the polymerization reaction, the concentration of the initiator is 1×10 -3 mol / L to 10×10 -3 mol / L. It can be understood that the concentration of the initiator includes but is not limited to 1×10 -3 mol / L, 2×10 -3 mol / L, 5×10 -3 mol / L, 8×10 -3 mol / L, 10×10 -3 mol / L.

[0144] In some of these examples, in step S400, the polymerization reaction is carried out under an inert atmosphere condition.

[0145] It can be understood that in step S400, before the polymerization reaction, the reaction system is treated with an inert atmosphere; optionally, the reaction system is cooled with liquid nitrogen, evacuated, heated, and purged with nitrogen in sequence; this can be cycled multiple times to remove oxygen in the system.

[0146] Furthermore, in step S400, the reaction flask used is soaked and washed in a potassium dichromate cleaning solution, then the salt layer on the inner wall is removed with saturated steam, and finally it is baked in a flame and cooled under nitrogen protection. This is to achieve the purpose of removing oxygen on the bottle wall.

[0147] In some of these examples, after the polymerization reaction in step S400, it further includes a post-treatment step. The post-treatment includes quenching the reaction with methanol, precipitating the polymer crude product with methanol or performing crystallization with n-hexane (or ethanol) / dichloromethane, and then performing extraction with acetone or ethanol as the solvent to obtain an organic compound with a narrow molecular weight distribution.

[0148] In some of these examples, in the method for preparing an organic compound, the preparation of the compound shown in formula (II) includes step S500:

[0149] Performing a halogenation reaction on the compound shown in formula (VII) to prepare the compound shown in formula (II);

[0150]

[0151] Wherein, X is selected from an oxygen atom or a sulfur atom.

[0152] In some of these examples, in step S500, the halogenation reaction is carried out under conditions containing a halogenating reagent; optionally, the halogenating reagent includes N-halosuccinimide; further, the N-halosuccinimide includes N-bromosuccinimide (NBS); optionally, the molar ratio of the halogenating reagent to the compound represented by formula (VII) is (2.2~3):1. It can be understood that the molar ratio of the halogenating reagent to the compound represented by formula (VII) includes but is not limited to 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1.

[0153] In some of these examples, in step S500, the temperature of the halogenation reaction is -5°C to 0°C. It can be understood that the temperature of the halogenation reaction includes but is not limited to -5°C, -4°C, -3°C, -2°C, -1°C, 0°C.

[0154] In some of these examples, in step S500, the time of the halogenation reaction is 6 h to 12 h. It can be understood that the time of the halogenation reaction includes but is not limited to 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h.

[0155] In some of these examples, in the method for preparing an organic compound, the preparation of the compound represented by formula (VII) includes step S600:

[0156] The compound represented by formula (VIII) and 2-halo-4-pyridinebenzaldehyde are subjected to a substitution reaction to prepare the compound represented by formula (VIII);

[0157]

[0158] Wherein, X is selected from an oxygen atom or a sulfur atom.

[0159] In some of these examples, in step S600, the 2-halo-4-pyridinebenzaldehyde includes 2-bromo-4-pyridinebenzaldehyde.

[0160] In some of these examples, in step S600, in the substitution reaction, the molar ratio of the compound represented by formula (VIII) to 2-halo-4-pyridinebenzaldehyde is 1:(1.1~1.5). It can be understood that the molar ratio of the compound represented by formula (VIII) to 2-halo-4-pyridinebenzaldehyde includes but is not limited to 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5.

[0161] In some of these examples, in step S600, the substitution reaction is carried out under conditions containing a second catalyst and a second ligand; optionally, the second catalyst includes cuprous iodide; optionally, the second ligand includes cis-1,2-cyclohexanediamine; optionally, the molar ratio of the second catalyst to the compound represented by formula (VIII) is (0.05~0.1):1; optionally, the molar ratio of the second ligand to the compound represented by formula (VIII) is (0.05~0.1):1. It can be understood that the molar ratio of the second catalyst to the compound represented by formula (VIII) includes but is not limited to 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1; the molar ratio of the second ligand to the compound represented by formula (VIII) includes but is not limited to 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1.

[0162] In some of these examples, in step S600, the substitution reaction is carried out under conditions containing a third base; optionally, the third base includes potassium phosphate; optionally, the molar ratio of the third base to the compound represented by formula (VIII) is (3~10):1. It can be understood that the molar ratio of the third base to the compound represented by formula (VIII) includes but is not limited to 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0163] In some of these examples, in step S600, the temperature of the substitution reaction is 110°C~120°C. It can be understood that the temperature of the substitution reaction includes but is not limited to 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C.

[0164] In some of these examples, in step S600, the substitution reaction is carried out under conditions containing a second organic solvent; optionally, the second organic solvent includes 1,4-dioxane.

[0165] In some of these examples, in step S600, the substitution reaction is carried out under an inert atmosphere condition.

[0166] In some of these examples, in the preparation method of the organic compound, the synthesis route is as follows:

[0167]

[0168] Wherein, X is a single O atom or S atom.

[0169] The preparation method of the organic compound provided by this application has low raw material cost and simple preparation process.

[0170] One embodiment of the present application provides an application of the above-mentioned organic compound or an organic compound prepared by the above-mentioned preparation method of the organic compound in the preparation of a hole transport material. Another embodiment of the present application provides a hole transport material, which includes the above-mentioned organic compound or an organic compound prepared by the above-mentioned preparation method of the organic compound.

[0171] One embodiment of the present application provides an application of the above-mentioned hole transport material in the preparation of a solar cell. Further, one embodiment of the present application provides an application of the above-mentioned hole transport material in the preparation of a perovskite solar cell.

[0172] One embodiment of the present application provides a solar cell, which includes the above-mentioned hole transport material.

[0173] In some examples, the solar cell includes a perovskite solar cell.

[0174] In some examples, in the solar cell, it includes a first electrode, a hole transport layer, a perovskite light-absorbing layer, and a second electrode. The hole transport layer is located between the first electrode and the perovskite light-absorbing layer, and the perovskite light-absorbing layer is located between the hole transport layer and the second electrode. The hole transport layer includes the above-mentioned hole transport material.

[0175] It can be understood that in the hole transport layer, the above-mentioned organic compound or an organic compound prepared by the above-mentioned preparation method can be used alone as the hole transport material, or the above-mentioned organic compound or an organic compound prepared by the above-mentioned preparation method can be used in combination with other hole transport materials, such as in combination with carbazole-based hole transport materials (such as 2PACZ, MEO-2PACZ, 4PACz, and Me-4PACz, etc.).

[0176] In some examples, in the solar cell, the perovskite light-absorbing layer has a crystal structure of ABX3. The crystal structure of ABX3 is the crystal structure of an organic-inorganic hybrid perovskite material, which is embodied as a cubic or octahedral structure. Among them, A includes at least one of methylammonium (MA), formamidine (FA), benzylammonium (BA), and cesium (Cs), B includes at least one of lead (Pb), tin (Sn), and copper (Cu), and X includes at least one of bromine (Br), chlorine (Cl), and iodine (I).

[0177] In some examples, in the solar cell, it further includes an electron transport layer, and the electron transport layer is disposed between the perovskite light-absorbing layer and the second electrode. Optionally, the electron transport layer includes at least one of, but is not limited to, metal oxides, fullerenes and their derivatives, etc.; further, the metal oxides include at least one of, but is not limited to, tin oxide, zinc oxide, etc.; the fullerenes and their derivatives include at least one of C60, PC61BM, PC71BM, etc.

[0178] In some of these examples, in a solar cell, at least one of the first electrode and the second electrode is a transparent conductive electrode (transparent conductive oxide TCO), and the other is one of a transparent conductive electrode and a metal electrode; optionally, the transparent conductive electrode includes, but is not limited to, at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), antimony-doped tin oxide (ATO), etc.; the metal electrode includes, but is not limited to, at least one of chromium (Cr), gold (Au), silver (Ag), copper (Cu), aluminum (Al), etc.

[0179] In some of these examples, the perovskite solar cell is a p-i-n perovskite solar cell. That is, the first electrode is a transparent conductive electrode.

[0180] See Figure 1 , in some of these examples, the solar cell 100 includes a transparent conductive electrode 110, a hole transport layer 120, a perovskite light-absorbing layer 130, an electron transport layer 140, and a metal electrode 150 that are sequentially stacked. It can be understood that the solar cell 100 is a p-i-n perovskite solar cell.

[0181] An embodiment of the present application provides a method for manufacturing a solar cell, including the following steps:

[0182] Prepare a hole transport layer on the first electrode; the hole transport layer includes the above-mentioned organic compound.

[0183] Prepare a perovskite light-absorbing layer on a side of the hole transport layer away from the first electrode;

[0184] Prepare a second electrode on a side of the perovskite light-absorbing layer away from the hole transport layer.

[0185] In some of these examples, in the method for manufacturing a solar cell, the method for preparing the hole transport layer includes a solution method; further, the solution method includes a solution spin coating method.

[0186] In some of these examples, in the method for manufacturing a solar cell, preparing the hole transport layer on the first electrode includes the following steps:

[0187] Dissolve the above-mentioned organic compound in an organic solvent to obtain a mixed solution;

[0188] Spin coat the mixed solution onto the first electrode and anneal.

[0189] Optionally, the organic solvent includes at least one of dimethyl sulfoxide, N,N'-dimethylformamide, toluene, chlorobenzene, and dichloromethane.

[0190] The organic compound provided by the present application has good solubility in dimethyl sulfoxide, N,N'-dimethylformamide, toluene, chlorobenzene, and dichloromethane.

[0191] Optionally, the concentration of the organic compound in the mixed solution is 3 mg / mL to 15 mg / mL.

[0192] Optionally, the rotation speed of spin coating is 4000 rpm to 5000 rpm.

[0193] Optionally, the annealing temperature is 90 °C to 110 °C.

[0194] In some of these examples, in the method for preparing a solar cell, before preparing the second electrode, it further includes a step of preparing an electron transport layer on a side of the perovskite light-absorbing layer away from the hole transport layer.

[0195] It can be understood that the present application does not limit the manner of preparing the perovskite light-absorbing layer and the electron transport layer, including but not limited to the solution method; nor does it limit the method for preparing the second electrode, including but not limited to evaporation coating.

[0196] In some of these examples, the method for preparing a solar cell includes the following steps:

[0197] (1) Cleaning: Ultrasonically clean the transparent conductive electrode TCO successively with water, acetone, and ethanol. Optionally, the cleaning time is 15 min to 20 min; then use an N2 gas gun to blow dry the solvent remaining on the surface of the transparent conductive electrode, and then perform oxygen plasma treatment. Optionally, the treatment is 10 min to 15 min; subsequently, transfer the transparent conductive electrode TCO to a nitrogen glove box;

[0198] (2) Preparation of the hole transport layer: Dissolve the compound shown in formula (I) in an organic solvent. Optionally, the organic solvent includes chlorobenzene; drop the prepared mixed solution onto the transparent conductive electrode TCO, and perform spin coating. Optionally, the spin coating rate is 4000 rpm to 5000 rpm, and optionally, the spin coating time is 20 s to 30 s; then anneal at 90 °C to 110 °C. Optionally, the annealing time is 10 min to 20 min;

[0199] (3) Preparation of perovskite light-absorbing layer: Cool the obtained TCO / hole transport layer to room temperature, preheat it at 130°C to 140°C. Optionally, the preheating time is 3 min to 5 min; place the perovskite precursor solution on the surface of the hole transport layer away from ITO, and spin-coat it. Optionally, the spin-coating rate is 4000 rpm to 5000 rpm, and optionally, the spin-coating time is 20 s to 30 s; then anneal it at 90°C to 100°C. Optionally, the annealing time is 10 min to 15 min to prepare the perovskite light-absorbing layer. Optionally, the thickness of the perovskite light-absorbing layer is 500 nm to 1000 nm; wherein the perovskite precursor solution includes 3-halobenzylammonium iodide, methylammonium chloride, and lead iodide; 3-halobenzylammonium iodide is selected from 3-bromobenzylammonium iodide and / or 3-chlorobenzylammonium iodide; the solvent of the perovskite precursor solution includes but is not limited to at least one of DMF and DMSO;

[0200] (4) Preparation of electron transport layer: Cool the obtained TCO / hole transport layer / perovskite light-absorbing layer to room temperature, place the electron transport solution on the surface of the perovskite light-absorbing layer away from the hole transport layer. Optionally, the electron transport material in the electron transport solution includes PC61BM, spin-coat it. Optionally, the spin-coating time is 30 s to 50 s, and then anneal it at 90°C to 100°C. Optionally, the annealing time is 10 min to 15 min to prepare the electron transport layer. Optionally, the thickness of the electron transport layer is 100 nm to 500 nm;

[0201] (5) Preparation of electrode: Place the above substrate in a vacuum evaporation chamber, and evaporate metal on the electron transport layer; optionally, the metal includes Cr and Au; further, the thickness of Cr is 6 nm to 10 nm, and the thickness of Au is 80 nm to 100 nm to obtain a reverse-type quasi-two-dimensional perovskite solar cell.

[0202] One embodiment of the present application provides a tandem cell, including the above solar cell or a solar cell prepared by the above method for preparing a solar cell.

[0203] It can be understood that the tandem cell includes but is not limited to a two-terminal tandem cell, a three-terminal tandem cell, and a four-terminal tandem cell.

[0204] One embodiment of the present application provides a photovoltaic module, including the above-provided solar cell, a solar cell prepared by the above-provided method for preparing a solar cell, or the above-provided tandem cell.

[0205] In some of these examples, the photovoltaic module includes:

[0206] A battery string, which is formed by electrically connecting a plurality of the above-mentioned solar cells or solar cells prepared by the above-mentioned method for preparing solar cells, or is formed by electrically connecting a plurality of the above-mentioned laminated cells;

[0207] An encapsulation film, which is used to cover the surface of the battery string; and

[0208] A cover plate, which is used to cover the surface of the encapsulation film facing away from the battery string.

[0209] It can be understood that the solar cells or laminated cells are electrically connected in the form of a whole piece or multiple sub-pieces to form a plurality of battery strings, and the plurality of battery strings are electrically connected in series and / or in parallel. Further, the solar cells or laminated cells can be whole-piece cells or sliced cells, and the sliced cells refer to cells formed by cutting a complete whole-piece cell through a cutting process.

[0210] In some examples, the plurality of battery strings can be electrically connected through conductive bands.

[0211] In some examples, the encapsulation film includes a first encapsulation layer and a second encapsulation layer. The first encapsulation layer covers one of the front and back surfaces of the battery, and the second encapsulation layer covers the other of the front and back surfaces of the battery; further, the first encapsulation layer and the second encapsulation layer can each independently include at least one of organic encapsulation films such as polyvinyl butyral (PVB) film, ethylene-vinyl acetate copolymer (EVA) film, polyoctene copolymer (POE) film, and polyethylene terephthalate (PET) film.

[0212] In some examples, the cover plate can be a cover plate with a light-transmitting function such as a glass cover plate or a plastic cover plate.

[0213] The following further describes the present application in detail in conjunction with specific embodiments, but the embodiments of the present application are not limited thereto.

[0214] Example 1

[0215] (1) Weigh 5 mmol of Compound 1, 5.2 mmol of 2-bromo-4-pyridine benzaldehyde, 0.5 mmol of cis-1,2-cyclohexanediamine, 0.5 mmol of copper iodide, and 25 mmol of potassium phosphate and add them to a reaction flask. Then add 60 ml of 1,4-dioxane and react at 120 °C for 36 hours. Extract with DCM and water, dry with anhydrous magnesium sulfate, and use column chromatography with PE:DCM = 10:1 to obtain Compound 2 with a yield of 40%.

[0216]

[0217] (2) Weigh compound 2 (3 mmol) and add it to a 500 mL three-necked flask. Then add 30 mL of dry THF. After degassing the mixture, rinse it with N2 gas and stir at 0 °C for 10 min. Then dissolve NBS (6 mmol) in THF (20 mL) and add it dropwise to the mixture. Continue the reaction at 0 °C for 3 hours. Quench the reaction with 50 mL of deionized water, extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, distill under reduced pressure, and finally purify it by column chromatography (PE:DCM = 6:1) to obtain solid compound 3 with a yield of 90%.

[0218]

[0219] (3) Weigh compound 4 (4 mmol), compound 5 (4.2 mmol), Pd2(dba)3 (0.2 mmol), DPPF (0.2 mmol), sodium tert-butoxide (4 mmol) and toluene and add them to a flask. React at 120 °C for 24 hours. Extract with DCM, dry with anhydrous magnesium sulfate, and obtain compound 6 by column chromatography with PE / DCM of 6 / 1 with a yield of 67.5%.

[0220]

[0221] (4) Weigh compound 3 (2 mmol), compound 6 (5 mmol), sodium tert-butoxide (2.5 mmol), palladium acetate (0.09 mmol), 0.3 ml of tri-tert-butylphosphine toluene solution, and 60 ml of toluene and add them to a flask. React at 85 °C for 6 hours and then cool to room temperature. Obtain compound 7 by column chromatography with PE / DCM of 6 / 1 with a yield of 70%.

[0222]

[0223] (5) Weigh compound 7 (1 mmol) and add it to 40 mL of dry THF. Stir at 0 °C for 10 min. Add sodium borohydride (10 mmol) to the reaction system in three portions and continuously stir at 0 °C for 3 hours. Then transfer it to room temperature and react for 12 hours. Cool to room temperature, quench the reaction with 50 mL of water, extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, distill under reduced pressure, and finally precipitate and filter with n-hexane / dichloromethane to obtain solid powder of compound 8 with a yield of 90%.

[0224]

[0225] (6) Weigh 1 mmol of Compound 8 and add it to 15 mL of dry DCM and 15 mL of dry triethylamine. Flush with N2 to remove oxygen, stir at 0 °C for 10 min, slowly dropwise add acryloyl chloride (0.2 mL), and react for 6 hours. Add 50 mL of water to quench the reaction, extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, distill under reduced pressure, and finally precipitate with n-hexane / dichloromethane and filter by suction to obtain the solid powder of Compound 9 with a yield of 90%.

[0226]

[0227] (7) Weigh 300 mg of Compound 9 and azobisisobutyronitrile (previously recrystallized from ethanol) with a mass ratio of 1% of the monomer and add them to toluene solution. Freeze-dry with liquid nitrogen and evacuate for 1 minute, then fill with nitrogen, repeat three times and seal. After initiating the reaction at 65 °C for 3 hours, react at 85 °C for 3 days. After the reaction is completed and cooled to room temperature, crystallize with n-hexane / dichloromethane, filter by suction and dry, then use acetone as the solvent and extract with a Soxhlet extractor for three days to obtain 150 mg of PMAPy-POZ, which is the compound shown in Formula (I-1); the 1H NMR spectrum is as Figure 1 shown.

[0228]

[0229] Example 2

[0230] (1) Weigh 5 mmol of Compound 10, 5.2 mmol of 2-bromo-4-pyridine benzaldehyde, 0.5 mmol of cis-1,2-cyclohexanediamine, 0.5 mmol of copper(I) iodide, and 25 mmol of potassium phosphate and add them to a reaction flask. Then add 60 ml of 1,4-dioxane and react at 120 °C for 36 hours. Extract with DCM and water, dry with anhydrous magnesium sulfate, and use column chromatography with PE:DCM = 10:1 to obtain Compound 11 with a yield of 41%.

[0231]

[0232] (2) Weigh 3 mmol of Compound 11 and add it to a 500 mL three-necked flask. Then add 30 mL of dry THF, degas the mixture, flush with N2 gas, and stir at 0 °C for 10 min. Then dissolve NBS (6 mmol) in THF (20 mL) and add it dropwise to the mixture, and continue to react at 0 °C for 3 hours. Quench the reaction with 50 mL of deionized water, extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, distill under reduced pressure, and finally purify by column chromatography (PE:DCM = 6:1) to obtain the solid of Compound 12 with a yield of 91%.

[0233]

[0234] (3) Weigh 12 (2 mmol), 6 (5 mmol, see the preparation in step (3) of Example 1), sodium tert-butoxide (2.5 mmol), palladium acetate (0.09 mmol), and 0.3 ml of tri-tert-butylphosphine toluene solution. Add 60 ml of toluene to the flask. After reacting at 85 °C for 6 hours, cool to room temperature. Compound 13 was obtained by column chromatography with PE / DCM at a ratio of 6 / 1, and the yield was 72%.

[0235]

[0236] (4) Weigh 13 (1 mmol) and add it to 40 mL of dry THF. Stir at 0 °C for 10 min. Divide sodium borohydride (10 mmol) into three portions and add them to the reaction system. Continuously stir at 0 °C for 3 hours, then transfer to room temperature and react for 12 hours. Cool to room temperature, add 50 mL of water to quench the reaction. Extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, and distill under reduced pressure. Finally, precipitate with n-hexane / dichloromethane and filter to obtain the solid powder of compound 14, with a yield of 91%.

[0237]

[0238] (5) Weigh 14 (1 mmol) and add it to 15 mL of dry DCM and 15 mL of dry triethylamine. Flush with N2 to remove oxygen. Stir at 0 °C for 10 min, and slowly drop in acryloyl chloride (0.2 mL), then react for 6 hours. Add 50 mL of water to quench the reaction. Extract the mixture with DCM, dry the organic phase with anhydrous Mg2SO4, filter, and distill under reduced pressure. Finally, precipitate with n-hexane / dichloromethane and filter to obtain the solid powder of compound 9, with a yield of 89%.

[0239]

[0240] (6) Weigh 300 mg of compound 9 and azobisisobutyronitrile (previously recrystallized from ethanol) at a ratio of 1% of the monomer mass and add them to toluene solution. Freeze-dry with liquid nitrogen and evacuate for 1 minute, then refill with nitrogen. Repeat three times and seal. Initiate the reaction at 65 °C for 3 hours, and then react at 85 °C for 3 days. After the reaction is completed, cool to room temperature. Crystallize with n-hexane / dichloromethane, filter and dry. Use acetone as the solvent and extract with a Soxhlet extractor for three days to obtain PMAPy-PTZ (160 mg), which is the compound shown in formula (I-2); the 1H NMR spectrum is as Figure 2 shown.

[0241]

[0242] Comparative Example 1

[0243] Traditional hole transport material: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA).

[0244] Comparative Example 2

[0245] (1) Using Compound 1 and 3-bromobenzaldehyde as reaction substrates to prepare Compound 17;

[0246] (2) Using Compound 17 and NBS as reaction substrates to prepare Compound 18;

[0247] (3) Using Compound 18 and Compound 16 as reaction substrates to prepare Compound 19;

[0248] (4) Using Compound 19 and sodium borohydride as reaction substrates to prepare Compound 20;

[0249] (5) Using Compound 20 and acryloyl chloride as reaction substrates to prepare Compound 21;

[0250] (6) Polymerizing Compound 21 to prepare the compound shown in Formula (IX).

[0251] .

[0252] Using the compounds prepared in each example and comparative example as hole transport materials to prepare perovskite solar cells:

[0253] (1) Cleaning: Sequentially ultrasonically cleaning the ITO glass substrate with deionized water, acetone, and ethanol for 15 - 20 minutes, then using an N2 gas gun to blow dry the solvent residues on the ITO surface, followed by 10 - 15 minutes of oxygen plasma treatment, and then transferring the ITO glass substrate to a nitrogen glove box;

[0254] (2) Preparation of the hole transport layer: Weigh 3 - 15 mg of the polynorbornene-based hole transport material and completely dissolve it in 1 mL of chlorobenzene solution. Take an appropriate amount of the solution and evenly drop it onto the ITO glass substrate, spin-coat it at 4000 rpm - 5000 rpm for 20 - 30 seconds, and then anneal it at 90°C - 110°C for 10 minutes;

[0255] (3) Preparation of the perovskite light-absorbing layer: Cool the obtained ITO / hole transport layer substrate to room temperature, preheat it at 130°C - 140°C for 3 - 5 minutes, take 50 μl of the perovskite solution (a mixture of 3-chlorobenzylammonium iodide, methylammonium chloride, and lead iodide in DMF and DMSO) and spread it evenly over the ITO / hole transport layer substrate, spin-coat it at 3000 - 5000 rpm for 20 - 30 seconds, and then anneal it at 90°C - 100°C for 10 minutes to prepare the perovskite light-absorbing layer;

[0256] (4) Preparation of the electron transport layer: Cool the obtained ITO / hole transport layer / perovskite substrate to room temperature. Prepare a solution of PC61BM at a concentration of 15 mg / mL, and then take 40 μL of the PC61BM solution to cover the ITO / hole transport layer / perovskite substrate, and spin-coat it at 1000 rpm for 30 - 50 seconds;

[0257] (5) Preparation of the electrode: Place the above-mentioned substrate in a vacuum evaporation chamber, and evaporate Cr (6 nm) and Au (80 nm) on the PC61BM layer respectively, then the required inverted quasi-two-dimensional perovskite solar cell can be fabricated.

[0258] Film-forming performance: PMAPy-POZ and PMAPy-PTZ as the HTM substrates are beneficial to the diffusion and growth of quasi-two-dimensional perovskite, thus obtaining a dense, uniform and smooth perovskite film. Further, AFM was used to study the crystal growth of quasi-two-dimensional perovskite films on different polymer HTMs: The quasi-two-dimensional perovskite films based on PMAPy-POZ and PMAPy-PTZ respectively exhibited lower RMS roughness, which were 15.7 nm and 16.3 nm respectively.

[0259] The space charge limited current method was used to measure the hole mobility. A single-hole device of ITO / PEDOT:PSS / HTMs to be tested / MoO3 / Ag was fabricated, and the film thickness of each layer was determined by a step profiler. Under dark conditions, the J-V characteristic curve of the device was obtained through a Keithley 2450 Source-Measure instrument, and the curve was analyzed by non-linear fitting to obtain the carrier mobility of the sample, as shown in Table 1.

[0260] Table 1

[0261]

[0262] Adjust the power of the solar simulator to 100 mw / cm 2 to simulate the AM 1.5G radiation standard, and read the current and voltage values of the device through a computer connected to a Keithley2450 source meter. Before measuring the current density-voltage curve, the light intensity was calibrated using a Newport standard silicon cell 91150. The device adopted a forward and reverse scan mode, and the scan rate was 0.05 V / s. The detailed open-circuit voltage Voc, short-circuit current (Jsc), fill factor (FF) and power conversion efficiency (PCE) are shown in Table 2.

[0263] Table 2

[0264]

[0265] As can be seen from Table 2, compared with Comparative Example 1, the organic compound prepared in this application can obtain better device performance.

[0266] The unencapsulated devices prepared with different HTMs were placed in an environment of darkness, room temperature (25°C), and low humidity (10%) for 500 h for stability testing. The retention rate of the photoelectric conversion efficiency of Example 1 was 89%, and that of Example 2 was 87%, which was superior to Comparative Example 1 with a traditional HTM.

[0267] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0268] The above-described embodiments only represent several implementation manners of the present application, which are convenient for understanding the technical solutions of the present application specifically and in detail. However, it should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can still be made, and these all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning, or limited experiments based on the technical solutions provided in the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application should be subject to the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. An organic compound, characterized in that, The structure of the organic compound is shown in formula (I): wherein X is selected from an oxygen atom or a sulfur atom; R1 is selected from substituted or unsubstituted C1-C 18 alkyl; R2 to R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C 18 alkyl, substituted or unsubstituted C1-C 18 alkoxy, substituted or unsubstituted C1-C 18 alkylthio, halogen atom, trifluoromethyl, hydroxy, mercapto, cyano, amino and substituted or unsubstituted C6-C 18 aryl; Each of the substituted substituents is independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano; Each occurrence of a and b is independently selected from integers from 1 to 4; Each occurrence of c is independently selected from an integer from 1 to 3; n is an integer from 10 to 1000.

2. The organic compound according to claim 1, wherein The organic compound satisfies at least one of the following characteristics: (1) R1 is selected from C1~C4 alkyl; (2) R2 to R4 are each independently selected from one of hydrogen, C1 to C4 alkyl, C1 to C4 alkoxy, halogen, trifluoromethyl, hydroxy, mercapto, cyano and amino groups.

3. The organic compound according to any one of claims 1 to 2, characterized in that, The structure of the organic compound is shown in Formula (I-1) to Formula (I-2): 。 4. A method for preparing an organic compound, characterized in that, The following steps are involved: The compound represented by formula (II) and the compound represented by formula (III) are subjected to a nucleophilic displacement reaction to prepare the compound represented by formula (IV); The compound represented by formula (IV) is subjected to a reduction reaction to prepare the compound represented by formula (V); The compound represented by formula (V) is subjected to alcoholysis reaction with acryloyl chloride to prepare the compound represented by formula (VI); The compound represented by formula (VI) is subjected to a polymerization reaction to prepare the organic compound; the structure of the organic compound is shown in formula (I): wherein X is selected from an oxygen atom or a sulfur atom; Y is a halogen atom; R1 is selected from substituted or unsubstituted C1-C 18 alkyl; R2 to R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C 18 alkyl, substituted or unsubstituted C1-C 18 alkoxy, substituted or unsubstituted C1-C 18 alkylthio, halogen atom, trifluoromethyl, hydroxy, mercapto, cyano, amino and substituted or unsubstituted C6-C 18 aryl; Each of the substituted substituents is independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano; Each occurrence of a and b is independently selected from integers from 1 to 4; Each occurrence of c is independently selected from an integer from 1 to 3; n is an integer from 10 to 1000.

5. The method for preparing the organic compound according to claim 4, wherein, The preparation method satisfies at least one of the following characteristics: (1) In the nucleophilic displacement reaction, the molar ratio of the compound represented by formula (II) to the compound represented by formula (III) is 1:(2.2-3); (2) The nucleophilic displacement reaction is carried out in the presence of a first catalyst and a first ligand, wherein the first catalyst comprises palladium acetate and the first ligand comprises tri-tert-butylphosphine; optionally, the molar ratio of the first catalyst to the compound represented by formula (II) is (0.03-0.1):1; (3) The nucleophilic displacement reaction is carried out in the presence of a first base, wherein the first base comprises sodium tert-butoxide; optionally, the molar ratio of the first base to the compound represented by formula (II) is (0.8-2):1; (4) The temperature of the nucleophilic displacement reaction is 85°C to 100°C; (5) The reduction reaction is carried out in the presence of a reducing agent, wherein the reducing agent comprises sodium borohydride; optionally, the molar ratio of the reducing agent to the compound represented by formula (IV) is (0.03-0.1):1; (6) The reduction reaction includes a first reduction reaction and a second reduction reaction performed sequentially, wherein the temperature of the first reduction reaction is -5°C to 0°C, and the temperature of the second reduction reaction is 25°C to 35°C; (7) In the alcoholysis reaction, the molar ratio of the compound represented by formula (V) to acryloyl chloride is 1:(1.1-2); (8)The alcoholysis reaction is carried out under the condition of containing a second base, and the second base includes triethylamine; optionally, the molar ratio of the second base to the compound shown in formula (V) is (50~300):1; (9)The temperature of the polymerization reaction is 65°C to 85°C; (10)The polymerization reaction is carried out in the presence of an initiator, and the initiator includes azobisisobutyronitrile.

6. The method for preparing an organic compound according to claim 4 or 5, characterized in that, The preparation of the compound shown in formula (II) includes the following steps: The compound shown in formula (VII) is subjected to a halogenation reaction to prepare the compound shown in formula (II); Wherein, X is selected from an oxygen atom or a sulfur atom; Optionally, the preparation method satisfies at least one of the following characteristics: (1)The halogenation reaction is carried out under the condition of containing a halogenating agent, and the halogenating agent includes N-halosuccinimide, and the molar ratio of the halogenating agent to the compound shown in formula (VII) is (2.2~3):1; (2)The temperature of the halogenation reaction is -5°C to 0°C.

7. The method for preparing an organic compound according to claim 6, wherein The preparation of the compound shown in formula (VII) includes the following steps: The compound shown in formula (VIII) and 2-halo-4-pyridinebenzaldehyde are subjected to a substitution reaction to prepare the compound shown in formula (VIII); Wherein, X is selected from an oxygen atom or a sulfur atom.

8. The method for preparing an organic compound according to claim 7, wherein, The preparation method satisfies at least one of the following characteristics: (1)In the substitution reaction, the molar ratio of the compound shown in formula (VIII) to the 2-halo-4-pyridinebenzaldehyde is 1:(1.1~1.5); (2)The substitution reaction is carried out under the condition of containing a second catalyst and a second ligand. The second catalyst includes cuprous iodide, and the second ligand includes cis-1,2-cyclohexanediamine; optionally, the molar ratio of the second catalyst to the compound shown in formula (VIII) is (0.05~0.1):1, and the molar ratio of the second ligand to the compound shown in formula (VIII) is (0.05~0.1):1; (3)The substitution reaction is carried out under the condition of containing a third base, and the third base includes potassium phosphate; optionally, the molar ratio of the third base to the compound shown in formula (VIII) is (3~10):1; (4)The temperature of the substitution reaction is 110°C to 120°C.

9. A hole transporting material, characterized in that, It includes the organic compound according to any one of claims 1 to 3 or the organic compound prepared by the preparation method according to any one of claims 4 to 8.

10. A solar cell, characterized in that, It includes the hole transport material according to claim 9.

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