Nitrogen-containing organic compound, perovskite solar cell and preparation method therefor, and electric device

Abstract

The application relates to a nitrogen-containing organic compound, a perovskite solar cell and a preparation method thereof and an electric device. The structure of the nitrogen-containing organic compound is shown in the figure; the structure of Ar is shown in the figure; the structure of L1 is shown in the figure; the N atom in formula (III) is connected with L2; L2 is selected from one of C2-C8 alkylene, phenylene, naphthylene and biphenylene; L3-L4 are independently selected from one of a bond, a single bond, O, S and -C(R7)2-; R1 is selected from one of phosphonic acid, carboxylic acid and cyanophosphonic acid; R2 is selected from one of phenyl, substituted phenyl, pyridyl, anilino and benzoyl; R7 is selected from one of hydrogen and C1-C4 alkyl; m, n and p are independently selected from integers of 0-3, and q is selected from integers of 0-4. The anchoring ability, carrier transport ability and defect passivation ability of the nitrogen-containing organic compound are high, and the stability under the action of light and heat is high.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to nitrogen-containing organic compounds, perovskite solar cells and their preparation methods, and electrical devices. Background Technology

[0002] Perovskite solar cells (PSCs), as a new generation of photovoltaic devices, have experienced rapid development in recent years due to their advantages such as high light absorption coefficient, excellent carrier mobility, and solution processability. The performance of charge transport materials is crucial for the commercialization of PSCs, with hole transport materials (HTMs) being particularly important in terms of efficiency, stability, and low cost, directly affecting the photoelectric conversion efficiency and long-term operational reliability of the cells. Currently, anchor-based self-assembly strategies have been proven effective for constructing hole transport layers in high-performance pin-structured PSCs. This strategy utilizes molecular HTMs containing anchoring groups (such as phosphonic acid groups), which can spontaneously adsorb onto the surface of oxide substrates to form a monolayer. Compared to the thick hole transport layers prepared by traditional spin-coating or spray pyrolysis, this strategy offers significant advantages in terms of lower material consumption and lower parasitic absorption. However, traditional self-assembled molecular layers still have defects, leading to poor device stability and limiting the industrialization of perovskite solar cells.

[0003] Therefore, it is necessary to improve traditional technologies. Summary of the Invention

[0004] Based on this, this application provides a nitrogen-containing organic compound with good stability, a perovskite solar cell, a method for preparing the same, and an electrical device thereof.

[0005] The technical solution to the above-mentioned technical problems in this application is as follows.

[0006] The first aspect of this application provides a nitrogen-containing organic compound, the structure of which is shown in formula (I):

[0007]

[0008] Wherein, Ar is selected from one of the structures shown in formula (II):

[0009]

[0010] L1 is selected from one of the structures shown in equation (III):

[0011]

[0012] In formula (III), the N atom is connected to L2;

[0013] L2 is selected from one of C2~C8 alkylene, phenylene, naphthylene, and biphenylene;

[0014] L3 to L4 are each independently selected from one of the following: single bond, O, S, and -C(R7)2-, or they may not exist.

[0015] R1 is selected from one of phosphonic acid group, carboxylic acid group and cyanophosphonic acid group;

[0016] R2 is selected from phenyl, substituted phenyl and pyridyl, wherein the substituent on the substituted phenyl is selected from at least one of C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, amino, aldehyde and C2-C8 acyl;

[0017] R3 to R6 are each independently selected from at least one of C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 alkylthio, halogen atom, hydroxyl, mercapto, cyano and amino groups;

[0018] R7 is selected from hydrogen and C1~C4 alkyl groups;

[0019] m, n, and p are each independently selected from integers from 0 to 3, and q is selected from integers from 0 to 4.

[0020] In some of these embodiments, Ar in the nitrogen-containing organic compound is selected from one of formulas (II-1) to (II-5):

[0021] .

[0022] In some embodiments, in nitrogen-containing organic compounds, in formulas (II-1) to (II-5), R2 is independently selected from one of phenyl, substituted phenyl and pyridyl, and the substituents on the substituted phenyl are independently selected from one of C1-C4 alkyl, C1-C4 alkoxy and C2-C8 acyl.

[0023] In some of the embodiments, in the nitrogen-containing organic compounds, R2 in formulas (II-1) to (II-5) is independently selected from one of phenyl, mesitylene, 3,5-dimethoxyphenyl, p-benzoylphenyl and pyridyl.

[0024] In some embodiments, each L1 in the nitrogen-containing organic compound is independently selected from one of formulas (III-1) to (III-5):

[0025] .

[0026] In some of these embodiments, each L2 in the nitrogen-containing organic compound is independently selected from one of C2-C6 alkylene and phenylene.

[0027] In some of these embodiments, each L2 in the nitrogen-containing organic compound is independently selected from butylene and phenylene.

[0028] In some embodiments, the nitrogen-containing organic compound comprises at least one of the structures shown in formulas (I-1) to (I-7):

[0029] .

[0030] The second aspect of this application provides a method for preparing the above-mentioned nitrogen-containing organic compound, comprising the following steps:

[0031] Compound (IV) and compound (V) were mixed and subjected to a Suzuki coupling reaction to prepare compound (VI);

[0032] Compounds of formula (VI) and (VII) are subjected to alkylation or Ullman reaction to prepare compound (VIII);

[0033] The nitrogen-containing organic compound is prepared by performing an Arbuzov reaction or a Hirao cross-coupling reaction on the compound shown in formula (VIII) and a phosphite compound, followed by a hydrolysis reaction.

[0034]

[0035] X, Y1, and Y2 are each independently selected from Br and I.

[0036] A third aspect of this application provides a hole transport material comprising the aforementioned nitrogen-containing organic compound.

[0037] A fourth aspect of this application provides a perovskite solar cell, comprising a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer stacked sequentially, wherein the hole transport layer comprises the aforementioned nitrogen-containing organic compound.

[0038] The fifth aspect of this application provides a method for fabricating a perovskite solar cell, comprising the following steps:

[0039] A hole transport layer is formed on the surface of a substrate; the raw materials for preparing the hole transport layer include the aforementioned nitrogen-containing organic compounds.

[0040] A perovskite light-absorbing layer is formed on the surface of the hole transport layer away from the substrate;

[0041] An electron transport layer is formed on the surface of the perovskite light-absorbing layer away from the hole transport layer.

[0042] The sixth aspect of this application provides a tandem solar cell, including the perovskite solar cell described above or the perovskite solar cell prepared by the above preparation method.

[0043] The seventh aspect of this application provides a photovoltaic module, including the perovskite solar cell described above, the perovskite solar cell prepared by the above preparation method, or the tandem cell described above.

[0044] The eighth aspect of this application provides an electrical device, including the perovskite solar cell described above, the perovskite solar cell prepared by the above preparation method, or the tandem cell described above.

[0045] The nitrogen-containing organic compound of this application uses a π-conjugated unit Ar as the parent core, coupled with two nitrogen-containing aryl groups L1, and connects the anchoring group R1 to the nitrogen-containing aryl group L1 through the linker L2, so that the anchoring group R1 is on the same side, which effectively improves the anchoring ability of the nitrogen-containing organic compound; at the same time, the N atom in Ar is replaced by R2 of a specific aryl group, which can effectively improve the carrier transport ability and defect passivation ability of the nitrogen-containing organic compound, and has high stability under photothermal action.

[0046] Applying the nitrogen-containing organic compounds of this application as hole transport materials to perovskite solar cells can effectively enhance the anchoring ability of the hole transport layer to the substrate and the passivation ability of the perovskite light-absorbing layer, while effectively suppressing the interfacial reaction under photothermal action. Thus, while maintaining high photoelectric conversion efficiency, it can effectively improve the stability of perovskite solar cells. Attached Figure Description

[0047] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0048] Figure 1 The 1H NMR spectrum of DSAM1 prepared in this application;

[0049] Figure 2 The 1H NMR spectrum of DSAM3 prepared in this application. Detailed Implementation

[0050] The present application will be further described in detail below with reference to the embodiments and examples. It should be understood that these embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous specific details are set forth in the following description to provide a more complete understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.

[0052] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0053] In this application, the terms "multiple", "various", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0054] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0055] In this document, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0056] In this document, terms such as "preferred," "better," "more suitable," and "ideal" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0057] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0058] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0059] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0060] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0061] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0062] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0063] In this application, the terms "room temperature" or "normal temperature" generally refer to 4℃~35℃, for example, 20℃±5℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10℃~30℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20℃~0℃.

[0064] In this application, if the unit of a data range is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0065] The mass or weight of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass or weight mentioned in the embodiments of this application can be units known in the chemical industry, such as μg, mg, g, and kg.

[0066] Analysis suggests that the poor stability of devices caused by traditional self-assembled molecular layers can be attributed to several factors: traditional dimer self-assembled single molecules (SAMs) are linked by C-C covalent bonds, resulting in significant steric hindrance and severe distortion, which hinders the formation of stable molecular arrangements through π-π interactions; or, due to the molecular configuration of traditional dimer SAMs, the two anchoring groups face opposite directions, preventing complete bonding with the substrate. Consequently, the self-assembled molecular layer is insufficiently anchored to the substrate, making it prone to desorption and leading to poor device stability.

[0067] One embodiment of this application provides a nitrogen-containing organic compound, the structure of which is shown in formula (I):

[0068]

[0069] Wherein, Ar is selected from one of the structures shown in formula (II):

[0070]

[0071] L1 is selected from one of the structures shown in equation (III):

[0072]

[0073] In formula (III), the N atom is connected to L2;

[0074] L2 is selected from one of C2~C8 alkylene, phenylene, naphthylene, and biphenylene;

[0075] L3 to L4 are each independently selected from one of the following: single bond, O, S, and -C(R7)2-, or they may not exist.

[0076] R1 is selected from one of phosphonic acid group, carboxylic acid group and cyanophosphonic acid group;

[0077] R2 is selected from one of phenyl, substituted phenyl and pyridyl, and the substituent on the substituted phenyl is selected from at least one of C1~C8 alkyl, C1~C8 alkoxy, C1~C8 alkylthio, amino, aldehyde and C2~C8 acyl;

[0078] R3 to R6 are each independently selected from at least one of C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 alkylthio, halogen atom, hydroxyl, mercapto, cyano and amino groups;

[0079] R7 is selected from hydrogen and C1~C4 alkyl groups;

[0080] m, n, and p are each independently selected from integers from 0 to 3, and q is selected from integers from 0 to 4.

[0081] Using the π-conjugated unit Ar as the parent nucleus, two nitrogen-containing aryl groups L1 are coupled together, and the anchoring group R1 is connected to the nitrogen-containing aryl group L1 through the linker L2, so that the anchoring group R1 is on the same side, which effectively improves the anchoring ability of nitrogen-containing organic compounds; at the same time, the N atom in Ar is replaced by R2 of specific aryl groups, which can effectively improve the carrier transport ability and defect passivation ability of nitrogen-containing organic compounds, and has high stability under photothermal action.

[0082] The study found that if the N atom in Ar is not substituted, the NH active site is prone to interfacial reaction under photothermal action, which in turn affects the stability of the device. It can be understood that if the N atom in Ar is substituted by R2 of a specific aryl group, it can interact with the perovskite interface, thereby improving the carrier transport capability and defect passivation capability of nitrogen-containing organic compounds. If the N atom in Ar is substituted by a non-aryl group, such as an alkane, this type of substituent cannot interact with the perovskite interface. At the same time, as the carbon chain length of the alkane increases, its hydrophobicity increases, which will also affect the crystal quality of the subsequently deposited perovskite layer.

[0083] It can be understood that the structure of nitrogen-containing organic compounds is as follows:

[0084]

[0085] It can be understood that "independently" means that the same group can be chosen, or different groups can be chosen. In formulas (II) and (III), when L3~L4 are selected from "not present", the two benzene rings are only connected by N atoms, and no additional ring is formed between the two benzene rings. At this time, the main structure is a diphenylamine structure. When L3~L4 are selected from single bonds, in addition to being connected by N atoms, the two benzene rings also form a covalent connection between the adjacent carbon atoms of the two benzene rings through the single bond, forming a three-membered ring structure together with the N atom. At this time, the main structure is a carbazole structure. When L3~L4 are selected from O, in addition to being connected by N atoms, the two benzene rings also form a covalent connection between the adjacent carbon atoms of the two benzene rings through the O atom, forming an oxygen-containing three-membered ring structure together with the N atom. At this time, the main structure is a carbazole structure. The main structure is a phenoxazine structure; when L3~L4 are selected from S, in addition to being connected by N atoms, the two benzene rings are also covalently connected between the adjacent carbon atoms of the two benzene rings through S atoms, forming a sulfur-containing three-membered ring structure together with the N atoms. At this time, the main structure is a phenthiazine structure; when L3~L4 are selected from -C(R7)2-, in addition to being connected by N atoms, the two benzene rings are also covalently connected between the C atoms in -C(R7)2- and the adjacent carbon atoms of the two benzene rings respectively, forming a three-membered ring structure together with the N atoms. At this time, the main structure is a dialkyl(R7)acridine structure. When R7 is methyl, the main structure is a dimethylacridine structure.

[0086] It can be understood that Ar includes the following structural formulas:

[0087] .

[0088] L1 to L2 are each independently selected from the following structural formulas:

[0089] .

[0090] It can be understood that in formula (III), the N atom is connected to L2, and the other connection site is connected to Ar; C2~C8 alkylene refers to a group formed by losing one hydrogen atom from an alkyl group with 2~8 carbon atoms, including but not limited to one of ethylene, isopropylene, butylene, etc.; phenylene refers to a divalent group formed by losing one hydrogen atom from each of two different carbon atoms on a benzene ring, with the general formula -C6H4-; according to the relative positions of the two connection sites, it can be divided into three isomers: ortho-phenylene (1,2-phenylene), meta-phenylene (1,3-phenylene), and para-phenylene (1,4-phenylene), among which para-phenylene is the most commonly used linear connection group; naphthylene refers to a divalent group formed by losing one hydrogen atom from each of two different carbon atoms on a naphthalene ring, with the general formula -C 10H6-; Depending on the bonding site, various isomers can be formed, commonly including 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene, etc.; Biphenylene refers to a divalent group formed by the loss of one hydrogen atom from each of two different carbon atoms (which can be located on two separate benzene rings or on the same benzene ring) on ​​a biphenyl (a structure in which two benzene rings are directly linked by a single bond), with the general formula -C. 12 H8-; the most commonly used is 4,4'-biphenyl (the two linking sites are located at the para positions of the two benzene rings respectively).

[0091] It can be understood that C2~C8 acyl groups refer to the groups shown in the formula "-C(=O)-R", where R is a C1~C7 hydrocarbon group and the total number of carbon atoms in the acyl group is 2~8. C2~C8 acyl groups include alkanoyl groups and aromatic acyl groups, such as acetyl, propionyl, benzoyl, etc.

[0092] Benzoyl group: -C(=O)Ph; Phosphonic acid group: -P(=O)(OH)2; Carboxylic acid group: -COOH; Cyanophosphonic acid group: -CH(CN)-P(=O)(OH)2.

[0093] It can be understood that m, n, p, and q represent the number of substituents on the benzene ring, with 0 indicating that it has not been substituted by other substituents; m, n, and p are independently selected from 0, 1, 2, or 3, respectively; and q is selected from 0, 1, 2, 3, or 4.

[0094] In some of these examples, in nitrogen-containing organic compounds, Ar is selected from one of formulas (II-1) to (II-5):

[0095] .

[0096] Optionally, Ar is selected from one of formulas (II-1), (II-4) and (II-5).

[0097] In some of these examples, in nitrogen-containing organic compounds, in formulas (II-1) to (II-5), R2 is independently selected from one of phenyl, substituted phenyl and pyridyl, and the substituents on the substituted phenyl are independently selected from one of C1 to C4 alkyl, C1 to C4 alkoxy and C2 to C8 acyl.

[0098] In some of these examples, in nitrogen-containing organic compounds, R2 in formulas (II-1) to (II-5) is independently selected from one of phenyl, mesitylene, 3,5-dimethoxyphenyl, p-benzoylphenyl and pyridyl.

[0099] In some of these examples, each L1 in the nitrogen-containing organic compound is independently selected from one of formulas (III-1) to (III-5):

[0100] .

[0101] In some of these examples, each L2 in the nitrogen-containing organic compound is independently selected from one of the C2-C6 alkylene and phenylene groups.

[0102] In some of these examples, each L2 in the nitrogen-containing organic compound is independently selected from butylene and phenylene.

[0103] In some of these examples, the nitrogen-containing organic compounds include at least one of the structures shown in formulas (I-1) to (I-7):

[0104] .

[0105] One embodiment of this application provides a method for preparing the above-mentioned nitrogen-containing organic compound, comprising the following steps:

[0106] Step S110: Mix the compound shown in formula (IV) and the compound shown in formula (V) and carry out a Suzuki coupling reaction to prepare the compound shown in formula (VI);

[0107] Step S120: The compound shown in formula (VI) and the compound shown in formula (VII) are subjected to alkylation or Ullman reaction to prepare the compound shown in formula (VIII);

[0108] Step S130: After the compound shown in formula (VIII) and the phosphite compound undergo Arbuzov reaction or Hirao cross-coupling reaction, hydrolysis reaction is carried out to prepare nitrogen-containing organic compound.

[0109]

[0110] X, Y1, and Y2 are each independently selected from Br and I.

[0111] It can be understood that L2~L4, R2~R6, m, n, p and q in the compounds shown in formulas (IV) to (VIII) correspond to L3~L4, R2~R6, m, n, p and q in the compound shown in formula (I).

[0112] It is understandable that in some of these examples, in step S110, the Suzuki coupling reaction occurs under the action of a palladium catalyst, and the compound shown in formula (IV) undergoes a C-C cross-coupling reaction with the compound shown in formula (V) in the presence of a base.

[0113] In some of these examples, in step S110, the Suzuki coupling reaction is carried out in the presence of a palladium catalyst; optionally, the palladium catalyst includes, but is not limited to, tetratriphenylphosphine palladium.

[0114] In some of these examples, in step S110, the Suzuki coupling reaction is carried out in the presence of a base; optionally, the base includes, but is not limited to, potassium carbonate.

[0115] In some of these examples, in step S110, the Suzuki coupling reaction is carried out in the presence of a solvent; optionally, the solvent includes, but is not limited to, 1,4-dioxane and water.

[0116] In some examples, in step S110, the temperature of the Suzuki coupling reaction is 100℃~120℃, and the time is 18 h~36 h. It can be understood that the temperature of the Buchwald coupling reaction includes, but is not limited to, 100℃, 102℃, 105℃, 108℃, 110℃, 112℃, 115℃, 118℃, and 120℃, and the time includes, but is not limited to, 18 h, 20 h, 22 h, 25 h, 28 h, 30 h, 32 h, 35 h, and 36 h. In some examples, any two of these point values ​​can be used as endpoints within a range, and the same applies below.

[0117] It is understood that in step S120, when L2 in the compound shown in formula (VII) is selected from C2~C8 alkylene, an alkylation reaction occurs, and when L2 is selected from phenylene, naphthylene, or biphenylene, a Ullmann reaction occurs.

[0118] In some of these examples, in step S120, the alkylation reaction is carried out in the presence of a base; optionally, the base includes, but is not limited to, potassium hydroxide.

[0119] In some of these examples, the alkylation reaction in step S120 is carried out at a temperature of 65°C to 75°C.

[0120] In some of these examples, in step S120, the Ullman reaction is carried out in the presence of a copper catalyst; optionally, the copper catalyst includes, but is not limited to, cuprous iodide.

[0121] In some examples, in step S130, L2 in the compound shown in formula (VIII) is selected from C2-C8 alkylene groups, and the phosphite compound includes a triphosphite; optionally, the triphosphite includes triethyl phosphite; at this time, the compound shown in formula (VIII) and the phosphite compound undergo an Arbuzov reaction; optionally, the Arbuzov reaction is carried out at a temperature of 140°C to 160°C for a time of 18 h to 36 h. It is understood that the temperature of the Arbuzov reaction includes, but is not limited to, 140°C, 142°C, 145°C, 148°C, 150°C, 152°C, 155°C, 158°C, and 160°C, and the time includes, but is not limited to, 18 h, 20 h, 22 h, 25 h, 28 h, 30 h, 32 h, 35 h, and 36 h.

[0122] In some examples, in step S130, L2 in the compound of formula (VIII) is selected from phenylene, naphthylene, or biphenylene, and the phosphite compound includes a diester of phosphite; optionally, the triester of phosphite includes diethyl phosphite. At this time, the compound of formula (VIII) and the phosphite compound undergo a Hirao cross-coupling reaction; optionally, the Hirao cross-coupling reaction is carried out in the presence of a palladium catalyst; optionally, the palladium catalyst includes 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride.

[0123] In some examples, step S130 involves hydrolysis of a compound prepared by the Arbuzov reaction or the Hirao cross-coupling reaction, a Lewis acid, and an organic solvent. Optionally, the Lewis acid includes, but is not limited to, at least one of trimethylchlorosilane, trimethylbromosilane, and trimethyliodosilane. Optionally, the organic solvent includes, but is not limited to, at least one of 1,4-dioxane and dichloromethane. Optionally, the hydrolysis reaction is carried out at a temperature of 20°C to 30°C for 8 h to 15 h.

[0124] In some examples, step S130, after the hydrolysis reaction is completed, includes a post-processing step: removing the organic solvent from the reaction solution after the hydrolysis reaction, adding methanol to dissolve it, adding water dropwise until solid precipitates in the system, continuing to stir and hydrolyze, and then washing by filtration.

[0125] One embodiment of this application provides a hole transport material comprising the aforementioned nitrogen-containing organic compound.

[0126] Applying the aforementioned nitrogen-containing organic compounds as hole transport materials to perovskite solar cells can effectively enhance the anchoring ability of the hole transport layer to the substrate and the passivation ability of the perovskite light-absorbing layer. At the same time, it can effectively suppress the interfacial reaction under photothermal action, thereby effectively improving the stability of perovskite solar cells while maintaining high photoelectric conversion efficiency.

[0127] It is understandable that the aforementioned nitrogen-containing organic compounds belong to the "π"-type dual-anchored hole transport materials.

[0128] One embodiment of this application provides a perovskite solar cell, comprising a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer stacked sequentially, wherein the hole transport layer comprises the aforementioned nitrogen-containing organic compound.

[0129] The perovskite solar cell provided in this application has a hole transport layer comprising the aforementioned nitrogen-containing organic compound, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0130] In some examples, in perovskite solar cells, the hole transport layer comprises an inorganic hole layer and an organic hole transport layer, wherein the organic hole transport layer is disposed between the inorganic hole layer and the perovskite light-absorbing layer, and the organic hole transport layer comprises the aforementioned nitrogen-containing organic compound. Optionally, the inorganic hole layer comprises nickel oxide.

[0131] In some examples, the perovskite solar cell includes a perovskite light-absorbing layer comprising an ABX3 type perovskite material, wherein A comprises at least one of cesium ions, rubidium ions, potassium ions, methylamine ions, formamidinium ions, methylenediamine ions, benzylamidinium cations, and guanidine cations; B comprises at least one of lead ions and divalent tin ions; and X comprises at least one of fluoride ions, chloride ions, bromide ions, iodide ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, and acetate ions.

[0132] In some of these examples, the electron transport layer in perovskite solar cells includes [6,6]-phenyl-C 61 methyl butyrate (PCBM), C 60 At least one of tin oxide and tin oxide.

[0133] In some examples, the perovskite solar cell further includes a first electrode and a second electrode. The first electrode is disposed on the side of the hole transport layer away from the perovskite light-absorbing layer, and the second electrode is disposed on the side of the electron transport layer away from the perovskite light-absorbing layer. Optionally, the first electrode is a transparent conductive electrode. Optionally, the transparent conductive electrode includes, but is not limited to, at least one of indium tin oxide (ITO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), and aluminum-doped zinc oxide (AZO). Optionally, the second electrode includes, but is not limited to, at least one of silver, copper, conductive oxide, and carbon electrodes.

[0134] In some examples, the perovskite solar cell also includes a hole-blocking layer disposed between the electron transport layer and the second electrode. Optionally, the hole-blocking layer includes, but is not limited to, at least one of copper bath (BCP, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and zirconium acetylacetonate.

[0135] It is understood that perovskite solar cells can be at least one of the following: individual cells, cell modules, and cell packs.

[0136] One embodiment of this application provides a method for fabricating a perovskite solar cell, comprising the following steps:

[0137] A hole transport layer is formed on the surface of the substrate; the raw materials for preparing the hole transport layer include the aforementioned nitrogen-containing organic compounds.

[0138] A perovskite light-absorbing layer is formed on the surface of the hole transport layer away from the substrate;

[0139] An electron transport layer is formed on the surface of the perovskite light-absorbing layer, away from the hole transport layer.

[0140] By preparing a perovskite light-absorbing layer on a hole transport layer containing the aforementioned nitrogen-containing organic compounds, perovskite crystal growth can be induced, improving the quality of the perovskite crystals, enhancing interfacial interactions, and thus improving the photoelectric conversion efficiency and stability of perovskite solar cells.

[0141] It is understandable that the substrate can be the first electrode or a silicon substrate, etc.

[0142] In some examples, the fabrication method of perovskite solar cells includes, after the step of forming the electron transport layer, a step of forming a second electrode on the surface of the electron transport layer away from the perovskite light-absorbing layer.

[0143] In some examples, the method for fabricating a perovskite solar cell includes, after the step of forming the electron transport layer and before the step of forming the second electrode, a step of setting a hole blocking layer on the surface of the electron transport layer away from the perovskite light-absorbing layer.

[0144] It is understood that this application does not limit the formation method of each layer, such as, but not limited to, one of magnetron sputtering, spin coating, slot coating and vapor deposition.

[0145] In some of these examples, the hole transport layer is prepared using a solution method in the fabrication of perovskite solar cells.

[0146] In some of these examples, the solution method includes the following steps:

[0147] The above-mentioned nitrogen-containing organic compound and solvent were mixed to prepare a hole transport solution;

[0148] Hole transport solution is spin-coated onto the conductive side surface of the first electrode and then annealed to form a hole transport layer.

[0149] In some of these examples, the solvent in the solution method includes ethanol.

[0150] In some of these examples, the concentration of the hole transport solution in the solution method is 0.5 mg / mL to 2 mg / mL.

[0151] It is understood that the concentration of the hole transport solution includes, but is not limited to, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, and 2 mg / mL.

[0152] In some of these examples, in the solution method, the annealing temperature is 80℃~120℃ and the time is 8 min~20 min.

[0153] It is understood that the annealing temperature includes, but is not limited to, 80℃, 90℃, 100℃, 110℃, and 120℃, and the time is 8 min, 10 min, 12 min, 15 min, and 20 min.

[0154] One embodiment of this application provides a tandem solar cell, including the perovskite solar cell described above or the perovskite solar cell prepared by the above preparation method.

[0155] One embodiment of this application provides the application of the above-described perovskite solar cell or the above-described perovskite tandem cell in the fabrication of a photovoltaic module. Another embodiment of this application provides a photovoltaic module comprising the above-described perovskite solar cell, the perovskite solar cell prepared by the above-described preparation method, or the above-described tandem cell.

[0156] It is understandable that photovoltaic (PV) modules can be used in PV power plants, such as ground-mounted, rooftop, and floating power plants, as well as in equipment or devices that utilize solar energy to generate electricity, such as user solar power supplies, solar streetlights, solar cars, and solar buildings. It is also understood that the application scenarios of PV systems include, but are not limited to, all areas that require solar energy for power generation. Taking a PV power grid as an example, a PV system can include PV arrays, combiner boxes, and inverters. A PV array can be a combination of multiple PV modules; for example, multiple PV modules can form multiple PV arrays. The PV arrays are connected to combiner boxes, which collect the current generated by the PV arrays. The collected current flows through an inverter, converts it into AC power required by the mains grid, and then connects to the mains grid to achieve solar power supply.

[0157] The photovoltaic modules provided in this application may be used, but are not limited to, in electrical installations such as vehicles and ships.

[0158] This application provides an electrical device, including the perovskite solar cell described above, the perovskite solar cell prepared by the above method, or the tandem cell described above. It is understood that the electrical device can be, but is not limited to, a mobile phone, tablet, laptop, electric toy, power tool, electric vehicle, electric car, ship, etc. Among them, electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc.

[0159] The present application will be described in further detail below with reference to specific embodiments, but the embodiments of the present application are not limited thereto.

[0160] Preparation of DSAM1

[0161]

[0162] Step 1: In a 100 mL two-necked flask, add 9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-9-hydro-carbazole (0.99 g, 2.0 mmol), 3-bromocarbazole (1.23 g, 5.0 mmol), 2M potassium carbonate solution (6 mL), tetrabutylammonium bromide (129 mg, 0.4 mmol), tetratetraphenylphosphine palladium (69 mg, 0.06 mmol), and 1,4-dioxane (25 mL). Under a nitrogen atmosphere, heat to 100 °C and reflux with stirring for 24 hours. After the reaction is complete, quench the reaction with water, extract three times with dichloromethane, dry the organic phase with anhydrous sodium sulfate, concentrate to obtain the crude product, further purify by column chromatography, and finally obtain intermediate M11 0.84 g as a white solid powder, with a yield of 73%.

[0163] Step 2: In a 100 mL single-necked flask, intermediate M11 (0.80 g, 1.39 mmol) and tetrabutylammonium bromide (45 mg, 0.14 mmol) were dissolved in 20 mL of 1,4-bromobutane. A 50% potassium hydroxide solution (2.8 mL) was added dropwise, and the mixture was heated to 65 °C and stirred for 24 hours. After the reaction was complete, the inorganic salts and alkali were removed by washing with water. The organic phase was dried, concentrated, and extracted by column chromatography, finally yielding 1.10 g of colorless, transparent, slimy, fatty intermediate M12, with a yield of 94%.

[0164] Step 3: In a 100 mL single-necked flask, M12 (1.10 g, 1.30 mmol) was dissolved in 20 mL of triethyl phosphite. The mixture was heated to 150 °C and stirred for 24 hours. After the reaction was complete, excess triethyl phosphite was removed by vacuum rotary evaporation, and the mixture was further purified by column chromatography. The final product was 1.20 g of a light yellow liquid fatty meat intermediate, M13, with a yield of 96%.

[0165] Step 4: In a 100 mL single-necked flask, M13 (1.20 g, 1.25 mmol) was dissolved in 30 mL of dichloromethane, and then trimethylbromosilane (1.91 g, 12.5 mmol) was added dropwise. The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation, 15 mL of methanol was added, and deionized water was added dropwise until a white solid precipitated. The reaction was continued with stirring for 8 hours, and then filtered to obtain approximately 800 mg of the final product DSAM1 as a light green solid, with a yield of 75.6%. NMR information: 1H NMR (400 MHz, DMSO-d6) δ 8.84(d, J = 1.9 Hz, 2H), 8.62 (d, J = 1.8 Hz, 2H), 8.29 (d, J = 7.7 Hz, 2H), 7.91(ddd, J = 13.6, 8.5, 1.9 Hz, 4H), 7.77 -7.70 (m, 6H), 7.64 (d, J = 8.2 Hz,2H), 7.57 (dt, J = 8.7, 4.3 Hz, 1H), 7.51 (d, J = 8.6 Hz, 2H), 7.49 -7.43 (m,2H), 7.22 (t, J = 7.4 Hz, 2H), 4.44 (t, J = 7.1 Hz, 4H), 1.90 (p, J = 7.0 Hz, 4H), 1.63 -1.48 (m, 8H).

[0166] Preparation of DSAM2

[0167]

[0168] Step 1: In a 100 mL two-necked flask, add M11 (0.86 g, 1.50 mmol), p-bromoiodobenzene (0.99 g, 3.50 mmol), cuprous iodide (57 mg, 0.30 mmol), potassium phosphate (0.96 g, 4.50 mmol), N,N-dimethylethylenediamine (36 mg, 0.40 mmol), and toluene (30 mL). Under a nitrogen atmosphere, heat to 110 °C and stir for 24 hours. After the reaction is complete, dilute with dichloromethane, filter through diatomaceous earth to remove the catalyst and inorganic salts, and concentrate the filtrate under vacuum to obtain a brownish-brown crude product. Recrystallize using a mixed solvent of N,N-dimethylformamide and ethanol to obtain 0.75 g of intermediate M21 as a light yellow solid, with a yield of 56.7%.

[0169] Step 2: In a 100 mL two-necked flask, add M21 (0.75 g, 0.85 mmol), potassium acetate (33 mg, 0.34 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (125 mg, 0.17 mmol), triethylamine (258 mg, 2.55 mmol), and anhydrous tetrahydrofuran (30 mL). Under a nitrogen atmosphere, heat to 80 °C and reflux for 15 minutes with stirring. Then add diethyl phosphite (0.70 g, 5.10 mmol) and continue stirring and reflux for 24 hours. After the reaction is complete, extract with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated to obtain the crude product. Further purification by column chromatography yields intermediate M22 (0.69 g), a yellow-green solid, with a yield of 81.3%.

[0170] Step 3: In a 100 mL single-necked flask, M22 (0.69 g, 0.69 mmol) was dissolved in 30 mL of dichloromethane, and then trimethylbromosilane (1.58 g, 10.35 mmol) was added dropwise. The reaction was carried out at room temperature for 12 hours. The organic solvent was then removed by rotary evaporation. 30 mL of methanol and 5 mL of deionized water were added, and the reaction was continued with stirring for 8 hours. The mixture was then filtered to obtain approximately 480 mg of the final product DSAM2 as a light green solid, with a yield of 78.6%. NMR information: 1 H NMR (500 MHz, DMSO-d6) δ 8.16 -8.12 (m,3H), 8.06 (dd, J = 4.8, 2.0 Hz, 3H), 7.74 -7.71 (m, 5H), 7.68 -7.63 (m, 9H),7.58 (dd, J = 7.0, 2.4 Hz, 1H), 7.54 (td, J = 6.5, 2.1 Hz, 3H), 7.52 -7.46(m, 3H), 7.43 -7.40 (m, 2H), 7.33 -7.29 (m, 4H).

[0171] Preparation of DSAM3

[0172]

[0173] The preparation process was essentially the same as that for DSAM1, except that 9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-9-hydro-carbazole in step one of the DSAM1 preparation was replaced with an equimolar amount of N,N-bis(4-boronic acid pinene ester phenyl)-2,4,6-trimethylaniline, while all other conditions remained unchanged. The final product, DSAM3, was obtained as a white solid powder. NMR information: 1H NMR (400 MHz, DMSO-d6) δ 8.41 (d, J = 1.8 Hz, 2H), 8.22 (d,J = 7.7 Hz, 2H), 7.74 -7.60 (m, 10H), 7.49 -7.42 (m, 2H), 7.20 (t, J = 7.5Hz, 2H), 7.08 -7.01 (m, 6H), 4.41 (s, 4H), 2.32 (s, 3H), 2.04 (s, 6H), 1.86 (d, J = 7.3 Hz, 4H), 1.59 -1.48 (m, 8H).

[0174] Preparation of DSAM4

[0175]

[0176] Step 1: In a 100 mL round-bottom flask, add 3,6-dibromocarbazole (1.62 g, 5.0 mmol), 4-iodopyridine (1.23 g, 6.0 mmol), cuprous iodide (95 mg, 0.5 mmol), N,N'-dimethylethylenediamine (88 mg, 1.0 mmol), potassium phosphate (3.18 g, 15.0 mmol), and 30 mL of toluene. Heat to 100 °C under a nitrogen atmosphere and reflux for 24 hours with stirring. After the reaction is complete, filter with diatomaceous earth to remove inorganic salts. Concentrate the filtrate to obtain the crude product, which is then purified by column chromatography to finally obtain intermediate M41 1.53 g as a white solid powder, with a yield of 76%.

[0177] Step 2: In a 100 mL round-bottom flask, intermediate M41 (0.80 g, 2.0 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)-carbazole (0.88 g, 3.0 mmol), potassium carbonate (1.66 g, 12.0 mmol), tetrabutylammonium bromide (0.13 g, 0.4 mmol), tetratetraphenylphosphine palladium (70 mg, 0.06 mmol), and 1,4-dioxane (30 mL) were added sequentially. The mixture was heated to 100 °C under a nitrogen atmosphere and stirred under reflux for 24 hours. After the reaction was completed, the reaction was quenched with water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain the crude product. After purification by column chromatography, intermediate M42 was obtained as a light yellow solid powder, 0.93 g, with a yield of 81%.

[0178] Steps three, four, and five are essentially the same as steps two, three, and four in the preparation of DSAM 1, except that intermediate M11 is replaced with an equimolar amount of intermediate M42, while all other conditions remain unchanged. The final product, DSAM4, is a light green solid powder. NMR information: 1 H NMR (500 MHz, DMSO-d6) δ 8.61 -8.59 (m,2H), 8.17 -8.13 (m, 3H), 8.06 (d, J = 2.4 Hz, 1H), 8.03 (d, J = 2.2 Hz, 2H),7.71 (dd, J = 30.8, 6.8 Hz, 2H), 7.62 (d, J = 6.8 Hz, 2H), 7.56 (ddd, J =16.5, 6.9, 2.1 Hz, 2H), 7.51 (dd, J = 6.9, 2.1 Hz, 2H), 7.45 -7.39 (m, 4H),7.32 -7.30 (m, 2H), 7.28 (ddd, J = 7.9, 6.5, 2.1 Hz, 2H), 4.28 (t, J = 5.1Hz, 4H), 1.95 -1.82 (m, 4H), 1.67 -1.57 (m, 8H).

[0179] Preparation of DSAM5

[0180]

[0181] The preparation process is essentially the same as that for DSAM 4, except that 4-iodopyridine in step one of the DSAM 4 preparation is replaced with an equimolar amount of 3,5-dimethoxyiodobenzene, while all other conditions remain unchanged. The final product, DSAM 5, is a yellow-green solid powder. NMR information: 1H NMR (500 MHz, DMSO-d6) δ 8.17 -8.13 (m, 3H), 8.04 (dd, J =17.2, 2.1 Hz, 3H), 7.71 (d, J = 6.7 Hz, 1H), 7.66 -7.59 (m, 4H), 7.57 (dd, J= 6.9, 1.9 Hz, 1H), 7.51 (dd, J = 6.9, 2.2 Hz, 2H), 7.45 -7.39 (m, 4H), 7.28 (ddd, J = 7.9, 6.5, 2.1 Hz, 2H), 6.80 (d, J = 2.2 Hz, 2H), 6.31 (t, J = 2.1Hz, 1H), 4.28 (t, J = 5.1 Hz, 4H), 3.80 (s, 6H), 1.95 (dt, J = 11.9, 9.5 Hz, 4H), 1.86 -1.57 (m, 8H).

[0182] Preparation of DSAM6

[0183]

[0184] The preparation process is essentially the same as that for DSAM 4, except that 4-iodopyridine in step one of the DSAM 4 preparation is replaced with an equimolar amount of 4-iodobenzophenone, while all other conditions remain unchanged. The final product, DSAM 6, is a yellow-green solid powder. NMR information: 1 H NMR (500 MHz, DMSO-d6) δ 8.17 -8.12 (m, 3H), 8.04 (dd, J = 16.0,2.3 Hz, 3H), 7.93 -7.89 (m, 2H), 7.82 -7.75 (m, 4H), 7.71 (dd, J = 30.8, 6.8Hz, 2H), 7.62 (d, J = 6.8 Hz, 2H), 7.60 -7.47 (m, 7H), 7.45 -7.39 (m, 4H), 7.28 (ddd, J = 7.9, 6.5, 2.1 Hz, 2H), 4.28 (s, 4H), 1.95 (dt, J = 12.0, 9.5Hz, 4H), 1.87 -1.56 (m, 8H).

[0185] Preparation of DSAM7

[0186]

[0187] The preparation process is essentially the same as steps two through five of DSAM 4, except that intermediate M41 in step two is replaced with an equimolar amount of 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacrylidine, while all other conditions remain unchanged. The final product, DSAM7, is a light green solid powder. NMR information: 1 H NMR (500 MHz, DMSO-d6) δ8.17 -8.14 (m, 2H), 8.03 -8.01 (m, 2H), 7.64 (d, J = 6.9 Hz, 2H), 7.58 -7.54(m, 3H), 7.47 (dt, J = 4.6, 2.3 Hz, 3H), 7.45 -7.40 (m, 4H), 7.36 -7.32 (m,2H), 7.28 (ddd, J = 7.8, 6.5, 2.1 Hz, 2H), 7.19 -7.14 (m, 3H), 7.02 (dd, J =42.5, 6.8 Hz, 2H), 4.28 (d, J = 10.3 Hz, 4H), 1.95 (dt, J = 12.0, 9.5 Hz, 4H), 1.65 -1.55 (m, 8H), 1.45 (s, 6H).

[0188] The synthetic steps for 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (intermediate b) are as follows:

[0189]

[0190] Step a: In a 100 mL round-bottom flask, add 2.09 g (10.0 mmol) of 9,9-dimethyl-9,10-dihydroacrylidine, 3.91 g (22.0 mmol) of N-bromosuccinimide, and 50 mL of N,N-dimethylformamide. Gradually reduce the temperature to room temperature under an ice-water bath and stir for 12 hours. After the reaction is complete, quench the reaction with water, extract with dichloromethane, and concentrate the organic phase after drying with anhydrous sodium sulfate to obtain the crude product. Purify by column chromatography to obtain intermediate a, 3.0 g of a light yellow solid powder, in 82% yield.

[0191] Step b: In a 100 mL round-bottom flask, add intermediate a (1.83 g, 5.0 mmol), iodobenzene (1.22 g, 6.0 mmol), cuprous iodide (95 mg, 0.5 mmol), N,N'-dimethylethylenediamine (88 mg, 1 mmol), potassium phosphate (3.18 g, 15.0 mmol), and toluene. Heat to 100 °C and reflux under a nitrogen atmosphere for 24 hours. After the reaction is complete, filter through diatomaceous earth to remove inorganic salts. The organic phase is concentrated to obtain the crude product. Purify by column chromatography to finally obtain intermediate b, a white solid powder, 1.73 g, with a yield of 78%.

[0192] Preparation of DSAM8

[0193]

[0194] The preparation process is essentially the same as steps two through five of DSAM 4, except that intermediate M41 in step two is replaced with an equimolar amount of 3,6-dibromo-9-ethylcarbazole, while all other conditions remain unchanged. The final product, DSAM 8, is a light yellow solid powder. NMR information: 1 H NMR (500 MHz, DMSO-d6) δ 8.17 -8.14 (m, 2H),8.08 (d, J = 2.3 Hz, 1H), 8.03 (d, J = 2.2 Hz, 2H), 7.95 (d, J = 1.8 Hz, 1H),7.71 (d, J = 6.8 Hz, 1H), 7.62 (d, J = 6.9 Hz, 2H), 7.59 (d, J = 6.9 Hz, 1H), 7.56 -7.49 (m, 4H), 7.45 -7.39 (m, 4H), 7.28 (ddd, J = 7.9, 6.5, 2.1 Hz, 2H),4.40 (q, J = 5.1 Hz, 2H), 4.28 (d, J = 10.3 Hz, 4H), 1.95 (dt, J = 12.0, 9.5Hz, 4H), 1.67 -1.58 (m, 8H), 1.37 (t, J = 5.2 Hz, 3H).

[0195] Example 1

[0196] A method for fabricating a perovskite solar cell includes the following steps:

[0197] (1) The TCO conductive glass was ultrasonically cleaned with deionized water, acetone and isopropanol for 15 min in sequence, and then dried in a drying oven at 75°C for later use. The dried TCO glass substrate was placed in an ultraviolet ozone machine for 25 min to remove organic impurities on its surface and optimize its surface wettability.

[0198] (2) Disperse 0.5 mg of SAM material (DSAM1) in 1 mL of ethanol solution; sonicate for 20 min to obtain a hole transport material dispersion;

[0199] (3) Take 30 μL of hole transport material dispersion, drop it onto TCO glass, spin coat it at 5000 rpm for 30s, place the TCO glass on a hot plate and heat it at 100℃ for 10 min to obtain the hole transport layer.

[0200] (3) Dissolve 722.08 mg lead iodide and 238.50 mg methyl iodide solid in 1 mL of N,N-dimethylformamide (DMF) and stir at room temperature until completely dissolved to obtain a perovskite precursor solution; in a nitrogen glove box, take 30 μL of the perovskite precursor solution and drop it onto the ITO conductive glass to form the hole transport layer. First spin coat at 1000 rpm for 10 s, then spin coat at 5000 rpm for 30 s. During this process, add 125 μL of chlorobenzene quickly at 25 s. Then place the TCO glass on a hot stage and heat it at 100℃ for annealing for 40 min to form a perovskite light-absorbing layer of 500 nm.

[0201] (5) Dissolve 20 mg PCBM in 1 mL of chlorobenzene and stir at room temperature to obtain PCBM solution; take 30 μL of PCBM solution and spin coat it on ITO conductive glass with perovskite light-absorbing layer at 3000 rpm for 60s to form an electron transport layer of 30 nm.

[0202] (6) Dissolve 0.5 mg of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in 1 mL of isopropanol and stir at room temperature to obtain a hole blocking layer solution; take 40 μL of hole blocking layer solution and drop it onto the electron transport layer, spin coat at 5000 rpm for 35 s to form a 6 nm hole blocking layer;

[0203] (7) Transfer the TCO conductive glass, which forms the hole blocking layer, electron transport layer, perovskite light-absorbing layer, and hole transport layer, to a vacuum coating instrument and wait for its vacuum level to reach 3*10 -4 Silver electrodes are deposited by vapor deposition at Pa, forming a 100 nm thick silver electrode on the hole blocking layer, thus obtaining the electrode layer.

[0204] Example 2

[0205] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM2.

[0206] Example 3

[0207] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM3.

[0208] Example 4

[0209] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM4.

[0210] Example 5

[0211] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM5.

[0212] Example 6

[0213] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM6.

[0214] Example 7

[0215] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM7.

[0216] Comparative Example 1

[0217] The process is basically the same as in Example 1, except that in step (2), the SAM material is Me-4PACz, and its molecular structure is:

[0218] .

[0219] Comparative Example 2

[0220] The process is basically the same as in Example 1, except that in step (2), the SAM material is 4PABCz, and its molecular structure is:

[0221] .

[0222] Comparative Example 3

[0223] The process is basically the same as in Example 1, except that in step (2), the SAM material is DCZ-4P, and its molecular structure is:

[0224] .

[0225] Comparative Example 4

[0226] It is basically the same as Example 1, except that in step (2), the SAM material is DSAM8.

[0227] The open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and power conversion efficiency (PCE) of the perovskite solar cells prepared in each embodiment and comparative example were measured. a The performance was tested using the IV curve, under the following conditions: AM 1.5G standard solar spectrum and irradiance of 1000 W / m². 2 .

[0228] Stability testing: After the battery was exposed to standard AM1.5G solar irradiation at 85℃ for 24 hours, performance testing was conducted under the above conditions to obtain the photoelectric conversion efficiency (PCE). b Photoelectric conversion efficiency attenuation rate = (PCE) a -PCE b ) / PCE a ×100%.

[0229] The experimental test results are detailed in Table 1.

[0230] Table 1

[0231]

[0232] As shown in Table 1, the π-type dual-anchored hole transport material provided in the examples exhibits higher open-circuit voltage and fill factor, indicating that the specific dual-anchored SAM material has a strong anchoring ability with the substrate and reduces direct contact between the substrate and the perovskite, avoiding recombination losses. Simultaneously, the passivation of the hole transport layer formed by the specific dual-anchored SAM material at the perovskite substrate interface induces perovskite layer growth and crystallization, forming a low-defect, high-quality perovskite film. The prepared perovskite photovoltaic device exhibits lower efficiency degradation after photothermal aging. In contrast, Comparative Examples 1 and 2 used Me-4PACz and 4PABCz as hole transport materials, respectively. Both are single-anchored SAMs with weaker bonding to the substrate. The unanchored SAM molecules were dissolved and diffused into the perovskite layer during subsequent perovskite preparation, disrupting the uniformity and continuity of the hole transport layer and thus affecting the photovoltaic performance of the device. In Comparative Example 3, DCZ-4P, with its dual anchoring, serves as the hole transport layer. However, its molecular configuration results in the phosphonic acid anchoring groups being distributed on both sides of the carbazole conjugated group, limiting its ability to enhance the binding strength with the substrate. Furthermore, the phosphonic acid groups facing the perovskite layer have a negative effect during subsequent device aging, accelerating device degradation. In Comparative Example 4, the two phosphonic acid anchoring groups of DSAM8 are located on the same side of the conjugated body, enhancing the anchoring ability with the substrate. The device performance and stability are improved compared to Comparative Examples 1-3. However, the N atom in Ar is replaced by a non-aryl-ethyl group, preventing interaction with the perovskite interface, resulting in inferior device performance and stability compared to the examples.

[0233] The technical features of the above embodiments can be combined in any way. For the sake of brevity, 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, they should be considered to be within the scope of this specification.

[0234] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A nitrogen-containing organic compound, characterized in that, The structure of the nitrogen-containing organic compound is shown in formula (I): Wherein, Ar is selected from one of the structures shown in formula (II): L1 is selected from one of the structures shown in equation (III): In formula (III), the N atom is connected to L2; L2 is selected from one of C2~C8 alkylene, phenylene, naphthylene, and biphenylene; L3 to L4 are each independently selected from one of the following: single bond, O, S, and -C(R7)2-, or they may not exist. R1 is selected from one of phosphonic acid group, carboxylic acid group and cyanophosphonic acid group; R2 is selected from phenyl, substituted phenyl and pyridyl, wherein the substituent on the substituted phenyl is selected from at least one of C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, amino, aldehyde and C2-C8 acyl; R3 to R6 are each independently selected from at least one of C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 alkylthio, halogen atom, hydroxyl, mercapto, cyano and amino groups; R7 is selected from hydrogen and C1~C4 alkyl groups; m, n, and p are each independently selected from integers from 0 to 3, and q is selected from integers from 0 to 4.

2. The nitrogen-containing organic compound according to claim 1, characterized in that, Ar is selected from one of formulas (II-1) to (II-5): 。 3. The nitrogen-containing organic compound according to claim 2, characterized in that, In formulas (II-1) to (II-5), R2 is independently selected from one of phenyl, substituted phenyl and pyridyl, and the substituents on the substituted phenyl are independently selected from one of C1-C4 alkyl, C1-C4 alkoxy and C2-C8 acyl.

4. The nitrogen-containing organic compound according to claim 3, characterized in that, In formulas (II-1) to (II-5), R2 is independently selected from one of phenyl, mesitylene, 3,5-dimethoxyphenyl, p-benzoylphenyl and pyridyl.

5. The nitrogen-containing organic compound according to any one of claims 1 to 4, characterized in that, Each L1 is independently selected from one of equations (III-1) to (III-5): 。 6. The nitrogen-containing organic compound according to any one of claims 1 to 4, characterized in that, Each L2 is independently selected from one of C2-C6 alkylene and phenylene.

7. The nitrogen-containing organic compound according to claim 6, characterized in that, Each L2 is independently selected from either butylene or phenylene.

8. The nitrogen-containing organic compound according to claim 1, characterized in that, The nitrogen-containing organic compound includes at least one of the structures shown in formulas (I-1) to (I-7): 。 9. The method for preparing the nitrogen-containing organic compound according to any one of claims 1 to 8, characterized in that, Includes the following steps: Compound (IV) and compound (V) were mixed and subjected to a Suzuki coupling reaction to prepare compound (VI); Compounds of formula (VI) and (VII) are subjected to alkylation or Ullman reaction to prepare compound (VIII); The nitrogen-containing organic compound is prepared by performing an Arbuzov reaction or a Hirao cross-coupling reaction on the compound shown in formula (VIII) and a phosphite compound, followed by a hydrolysis reaction. X, Y1, and Y2 are each independently selected from Br and I.

10. A hole transport material, characterized in that, Includes nitrogen-containing organic compounds as described in any one of claims 1 to 8.

11. A perovskite solar cell, characterized in that, It includes a hole transport layer, a perovskite light-absorbing layer and an electron transport layer stacked sequentially, wherein the hole transport layer includes a nitrogen-containing organic compound as described in any one of claims 1 to 8.

12. A method for fabricating a perovskite solar cell, characterized in that, Includes the following steps: A hole transport layer is formed on the surface of a substrate; the raw materials for preparing the hole transport layer include nitrogen-containing organic compounds as described in any one of claims 1 to 8; A perovskite light-absorbing layer is formed on the surface of the hole transport layer away from the substrate; An electron transport layer is formed on the surface of the perovskite light-absorbing layer away from the hole transport layer.

13. A stacked battery, characterized in that, This includes the perovskite solar cell as described in claim 11 or the perovskite solar cell prepared by the preparation method as described in claim 12.

14. A photovoltaic module, characterized in that, This includes the perovskite solar cell as described in claim 11, the perovskite solar cell prepared by the preparation method as described in claim 12, or the tandem cell as described in claim 13.

15. An electrical appliance, characterized in that, This includes the perovskite solar cell as described in claim 11, the perovskite solar cell prepared by the preparation method as described in claim 12, or the tandem cell as described in claim 13.

Images