Perovskite solar cell, organic compound, method for producing the same, stacked cell, photovoltaic module, power generation device, electric device

Abstract

This invention relates to the field of batteries, specifically disclosing perovskite solar cells, organic compounds and their preparation methods, tandem solar cells, photovoltaic modules, power generation devices, and power consumption devices. The perovskite solar cell of this invention comprises: a first electrode layer; a hole transport layer disposed on one side of the first electrode layer; a perovskite layer disposed on the side of the hole transport layer opposite to the first electrode layer; and a second electrode layer disposed on the side of the perovskite layer opposite to the hole transport layer; the hole transport layer comprises a compound represented by Formula I. This invention uses fused rings to connect the electron donor and electron acceptor in A2, expanding the conjugated range of A2, thereby enhancing the π-π interaction force of the compound represented by Formula I, and simultaneously promoting the further formation of ordered hole transport pathways in the compound represented by Formula I, thereby improving the efficiency and stability of the perovskite solar cell.

Description

Technical Field

[0001] This invention relates to the field of batteries, specifically to perovskite solar cells, organic compounds and their preparation methods, tandem cells, photovoltaic modules, power generation devices, and power consumption devices. Background Technology

[0002] With the rapid development of the new energy field, solar cells have been widely used in military, aerospace, industrial, commercial, agricultural, and communication fields. Perovskite solar cells (PSCs) have gradually become a hot topic in next-generation solar cell research due to their high photoelectric conversion efficiency, simple fabrication process, and low production and material costs. Currently, the long-term stability of perovskite cells is limited by the stability of hole transport materials. Therefore, improving hole transport materials to enhance the long-term stability of perovskite cells is crucial for their application. Summary of the Invention

[0003] In one aspect, the present invention provides perovskite solar cells, organic compounds and their preparation methods, tandem solar cells, photovoltaic modules, power generation devices, and power consumption devices. The perovskite solar cells of the present invention include a compound represented by Formula I in the hole transport layer. This compound has a stable molecular conformation and a relatively ordered hole transport path, which enables the perovskite solar cells to have high efficiency and stability.

[0004] The first aspect of this invention provides a perovskite solar cell, comprising:

[0005] First electrode layer;

[0006] A hole transport layer is disposed on one side of the first electrode layer;

[0007] A perovskite layer is disposed on the side of the hole transport layer opposite to the first electrode layer;

[0008] The second electrode layer is disposed on the side of the perovskite layer opposite to the hole transport layer.

[0009] The hole transport layer comprises the compound shown in Formula I;

[0010] Formula I: A1-(CH2) m -A2-(CH2) m -A3;

[0011] In Equation I, m is any integer between 0 and 10;

[0012] A1 and A3 independently include oxyacid groups or their salts;

[0013] A2 includes A21 Or A 22 ;

[0014]

[0015] n 21 n 22 Independently, it can be any integer between 1 and 3;

[0016] R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino.

[0017] The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

[0018] The perovskite solar cell of the present invention comprises a hole transport layer including a compound of Formula I. The present invention uses a fused ring splicing method to connect the electron donor (a group having a thiophene or derivative structure) in A2 with an electron acceptor (a group having a benzothiadiazole dipyrrole structure), expanding the conjugation range of A2 and increasing its conjugation degree, thereby enhancing the π-π interaction force of the compound of Formula I. This results in a stable molecular conformation for the compound of Formula I, and simultaneously promotes the further formation of ordered hole transport pathways in the compound of Formula I, thereby improving the efficiency and stability of the perovskite solar cell.

[0019] In some embodiments of the present invention, A1 includes any one of -COOH or a salt thereof, -PO(OH)2 or a salt thereof, -PHO(OH) or a salt thereof, -SO2(OH) or a salt thereof, -B(OH)2 or a salt thereof, and -SO3H or a salt thereof. Therefore, selecting the above-mentioned oxyacid groups or their salts for A1 helps to enhance their anchoring effect at the lower interface, thereby improving the efficiency and stability of perovskite solar cells.

[0020] In some embodiments of the present invention, the substituents in the substituted alkyl, substituted carboxyl, substituted aldehyde, substituted aryl, substituted thiophene, substituted ester, and substituted amino groups independently include at least one selected from O, S, ester, halogen, hydroxyl, carboxyl, sulfonic acid, and phosphate groups. Therefore, by selecting the above-mentioned substituents for A2, an ordered hole transport pathway can be formed, thereby improving the efficiency and stability of perovskite solar cells.

[0021] In some embodiments of the present invention, R211 R 212 R 221 R 222 The substituents of A2 independently include any one of H, F, Cl, Br, I, -COOH, -CHO, R', and -N(R')2; R' independently includes any one of substituted or unsubstituted phenyl, substituted or unsubstituted thiophene, or substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms. Therefore, by selecting the above-mentioned substituents for A2, an ordered hole transport pathway can be formed, thereby improving the efficiency and stability of perovskite solar cells.

[0022] In some embodiments of the present invention, the substituents in the substituted phenyl group, the substituted thiophene group, and the substituted alkyl group with 1-10 carbon atoms may independently include at least one of halogen, O, S, and ester groups. Therefore, selecting the above-mentioned substituents for A2 can further improve its hole transport efficiency, thereby improving the efficiency and stability of the perovskite solar cell.

[0023] In some embodiments of the present invention, in n 21 When A is 1, 21 Including any of the following:

[0024]

[0025] Therefore, A 21 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0026] In some embodiments of the present invention, in n 22 When A is 1, 22 Including any of the following:

[0027]

[0028] Therefore, A 22 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0029] In some other embodiments of the present invention, m is any integer between 1 and 5. Thus, a carbon chain of 1 to 5 carbon atoms is selected, which has suitable steric hindrance. The carbon chain of 1 to 5 carbon atoms is connected with the A1 and A2 groups to jointly improve hole transport, thereby improving the efficiency and stability of the perovskite solar cell.

[0030] In some embodiments of the present invention, the compound represented by Formula I includes any one of the following:

[0031]

[0032]

[0033] Therefore, the compound shown in Formula I is selected from the above-mentioned compounds, which has both a good anchoring effect on the lower interface and a high hole transport efficiency, thereby improving the efficiency and stability of perovskite solar cells.

[0034] In some embodiments of the present invention, the hole transport layer includes:

[0035] A first hole transport layer is disposed on one side of the first electrode layer;

[0036] The second hole transport layer is disposed on the side of the first hole transport layer opposite to the first electrode layer;

[0037] The second hole transport layer comprises the compound shown in Formula I. The compound shown in Formula I provided by this invention can be disposed between an existing hole transport layer material and a perovskite layer, passivating surface defects in the perovskite layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0038] In some embodiments of the present invention, the thickness of the second hole transport layer is 0.1-5 nm. The compound represented by Formula I provided by the present invention can be used alone as the hole transport layer of a perovskite solar cell. Further control over the thickness of the hole transport layer formed by the compound represented by Formula I can improve carrier extraction, reduce energy loss, and thus improve the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0039] In some embodiments of the present invention, the thickness of the first hole transport layer is 5-100 nm.

[0040] In some embodiments of the present invention, the first hole transport layer comprises one or more of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiazole, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiazole-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiazole):poly(styrene sulfonate), polythiazole, nickel oxide, molybdenum oxide, cuprous iodide, cuprous oxide, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid. Therefore, selecting the above materials for the first hole transport layer can further enhance the anchoring effect of the compound shown in Formula I, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0041] A second aspect of the present invention provides an organic compound, the structure of which is shown in Formula I;

[0042] Formula I: A1-(CH2) m -A2-(CH2) m -A3;

[0043] In Equation I, m is any integer between 0 and 10;

[0044] A1 and A3 independently include oxyacid groups or their salts;

[0045] A2 includes A 21 Or A 22 ;

[0046]

[0047] n 21 n 22 Independently, it can be any integer between 1 and 3;

[0048] R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino.

[0049] The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

[0050] The compound represented by Formula I of this invention can serve as a hole transport layer in perovskite solar cells. This invention uses a fused ring splicing method to connect the electron donor (a group having a thiophene or derivative structure) in A2 with the electron acceptor (a group having a benzothiadiazole structure), expanding the conjugation range of A2 and increasing its conjugation degree, thereby improving the π-π interaction force of the compound represented by Formula I. This results in a stable molecular conformation for the compound represented by Formula I, while also promoting the further formation of ordered hole transport pathways in the compound represented by Formula I, thereby improving the efficiency and stability of perovskite solar cells.

[0051] In some embodiments of the present invention, A1 includes any one of -COOH or a salt thereof, -PO(OH)2 or a salt thereof, -PHO(OH) or a salt thereof, -SO2(OH) or a salt thereof, -B(OH)2 or a salt thereof, and -SO3H or a salt thereof. Thus, when the compound represented by Formula I serves as the hole transport layer of a perovskite solar cell, the selection of the aforementioned oxyacid groups or their salts in A1 helps to enhance its anchoring effect at the lower interface, thereby improving the efficiency and stability of the perovskite solar cell.

[0052] In some embodiments of the present invention, R 211 R 212 R 221 R 222 The compound of Formula I independently includes any one of H, F, Cl, Br, I, -COOH, -CHO, R', and -N(R')2; R' independently includes any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms. Therefore, the compound of Formula I, when used as the hole transport layer in a perovskite solar cell, with the substituents of A2 selected from the aforementioned groups, can form an ordered hole transport pathway, thereby improving the efficiency and stability of the perovskite solar cell.

[0053] In some embodiments of the present invention, the substituents in the substituted phenyl group, the substituted thiophene group, and the substituted alkyl group with 1-10 carbon atoms may independently include at least one of halogen, O, S, and ester groups. Thus, the compound represented by Formula I, as a hole transport layer in a perovskite solar cell, with the substituents of A2 selected from the aforementioned groups, can form an ordered hole transport pathway, thereby improving the efficiency and stability of the perovskite solar cell.

[0054] In some embodiments of the present invention, the compound represented by Formula I includes any one of the following:

[0055]

[0056] Therefore, the compound shown in Formula I is selected from the above-mentioned compounds and used as the hole transport layer of the perovskite solar cell. It has a good anchoring effect on the lower interface and a high hole transport efficiency, thereby improving the efficiency and stability of the perovskite solar cell.

[0057] A third aspect of the present invention provides a method for preparing an organic compound, comprising the following steps:

[0058] The compound shown in Formula II and the compound shown in Formula III are reacted to obtain the compound shown in Formula VI;

[0059] Formula II includes Formula II-1 and / or Formula II-2;

[0060]

[0061] Formula III: X-(CH2) m -A4;

[0062] In Formula III, X includes any one of F, Cl, Br, and I;

[0063] A4 includes oxyesters;

[0064] In n 21 and n 22 When the value is 1, the compound shown in formula VI is subjected to a substitution reaction to obtain the compound shown in formula I;

[0065] In n 21 and n 22 In the case of 2 or 3, the compound shown in Formula VI is subjected to the first substitution reaction, coupling reaction and second substitution reaction in sequence to obtain the compound shown in Formula I;

[0066] Formula VI includes Formula VI-1 and / or Formula VI-2;

[0067]

[0068] A fourth aspect of the present invention provides a tandem solar cell, comprising: one or more of the following: the perovskite solar cell, the organic compound, and an organic compound prepared by the method of preparing the organic compound.

[0069] A fifth aspect of the present invention provides a photovoltaic module comprising: one or more of the following: the perovskite solar cell, the organic compound, and an organic compound prepared by the method thereof.

[0070] A sixth aspect of the present invention provides a power generation device, comprising: one or more of the following: the perovskite solar cell, the organic compound, and an organic compound prepared by the method of preparing the organic compound.

[0071] A seventh aspect of the present invention provides an electrical device comprising: one or more of the following: the perovskite solar cell, the organic compound, and an organic compound prepared by the method thereof.

[0072] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0073] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0074] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of the present invention;

[0075] Figure 2 This is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of the present invention;

[0076] Figure 3 This is a schematic diagram of the perovskite solar cell in Test Example 1;

[0077] Figure 4 This is a schematic diagram of an electrical device using a perovskite solar cell as a power source according to an embodiment of the present invention.

[0078] Explanation of reference numerals in the attached figures:

[0079] 100 is a perovskite solar cell; 110 is the first electrode layer; 120 is the hole transport layer; 121 is the first hole transport layer; 122 is the second hole transport layer; 130 is the perovskite layer; 140 is the second electrode layer; 150 is the electron transport layer; 160 is the hole blocking layer. Detailed Implementation

[0080] Hereinafter, embodiments of the perovskite solar cell and power-consuming device of the present invention will be specifically disclosed in detail with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present invention and are not intended to limit the subject matter of the claims.

[0081] The "range" disclosed in this invention is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is understood that ranges of 60-110 and 80-120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and if maximum range values ​​3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this invention, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0082] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0083] Unless otherwise specified, all technical features and optional technical features of this invention can be combined to form new technical solutions.

[0084] Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0085] Currently, the perovskite under-interface has numerous defects, significantly impacting the photoelectric conversion efficiency and stability of perovskite solar cells. Therefore, self-assembled molecules designed to modify the perovskite under-interface have been developed. Self-assembled molecules are organic compounds containing head groups, terminal groups, and carbon chains connecting these head and terminal groups.

[0086] To improve hole extraction from the hole transport layer and reduce exciton recombination rate, electron donor-electron acceptor self-assembled molecules have been developed. However, the electron donor and electron acceptor structural units of these molecules are connected by single bonds, resulting in molecular conformational instability, especially under high temperature and light conditions, which hinders further development.

[0087] To overcome the shortcomings of existing self-assembled molecules, this invention employs a fused ring splicing method to splice electron donors and electron acceptors in the terminal groups of the self-assembled molecule, thereby enhancing the intermolecular forces within the self-assembled molecule, giving it a stable molecular conformation, and improving the efficiency and stability of perovskite solar cells.

[0088] The first aspect of this invention provides a perovskite solar cell, comprising:

[0089] First electrode layer;

[0090] A hole transport layer is disposed on one side of the first electrode layer;

[0091] The perovskite layer is located on the side of the hole transport layer opposite to the first electrode layer.

[0092] The second electrode layer is located on the side of the perovskite layer away from the hole transport layer.

[0093] The hole transport layer includes the compound shown in Formula I;

[0094] Formula I: A1-(CH2) m -A2-(CH2) m -A3;

[0095] In Formula I, m is any integer between 0 and 10; A1 and A3 independently include oxyacid groups or their salts; A2 includes A 21 Or A 22 ;

[0096]

[0097] n 21 n 22 Independently, it can be any integer between 1 and 3;

[0098] R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino.

[0099] The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

[0100] The perovskite solar cell of the present invention comprises a hole transport layer including a compound of Formula I. The present invention uses a fused ring splicing method to connect the electron donor (a group having a thiophene or derivative structure) in A2 with an electron acceptor (a group having a benzothiadiazole dipyrrole structure), expanding the conjugation range of A2 and increasing its conjugation degree, thereby enhancing the π-π interaction force of the compound of Formula I. This results in a stable molecular conformation for the compound of Formula I, and simultaneously promotes the further formation of ordered hole transport pathways in the compound of Formula I, thereby improving the efficiency and stability of the perovskite solar cell.

[0101] In some embodiments of the present invention, the perovskite solar cell 100 of the present invention, with reference to... Figure 1 It includes a first electrode layer 110, a hole transport layer 120, a perovskite layer 130, and a second electrode layer 140.

[0102] In some embodiments of the present invention, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or can be a range of any of the above values.

[0103] In some embodiments of the present invention, when m is 0, the -CH2- group is not present, and the A2 group is directly connected to the A1 and A3 groups by chemical bonds.

[0104] In some embodiments of the present invention, A1 includes any one of -COOH or a salt thereof, -PO(OH)2 or a salt thereof, -PHO(OH) or a salt thereof, -SO2(OH) or a salt thereof, -B(OH)2 or a salt thereof, and -SO3H or a salt thereof. Therefore, selecting the above-mentioned oxyacid groups or their salts for A1 helps to enhance their anchoring effect at the lower interface, thereby improving the efficiency and stability of perovskite solar cells.

[0105] As an example, salts of -COOH may include at least one of the following: alkali metal salts, ammonium salts, pyridinium salts, and piperazine salts of -COOH; ammonium salts of -COOH may include -COO-NR”4 + "R" includes hydrogen or a hydrocarbon group with 1-5 carbon atoms; alkali metal salts of -COOH may include -COO - Li + -COO - Na + -COO - K + At least one of them.

[0106] As an example, salts of -PO(OH)2 may include at least one of alkali metal salts, ammonium salts, pyridinium salts, and piperazine salts of -PO(OH)2; ammonium salts of -PO(OH)2 may include -PO3. 2- (NR”'4 + 2. -PO2(OH) - (NR”'4) + At least one of them, R”' includes hydrogen or a hydrocarbon group with 1-5 carbon atoms; the alkali metal salt of -PO(OH)2 may include PO3 2- (Li + )2、-PO 2 (OH) - Li + -PO3 2- (Na + 2. -PO2(OH) - Na + -PO3 2- (K + 2. -PO2(OH) - K + At least one of them.

[0107] As an example, salts of -SO3H may include at least one of the following: alkali metal salts, ammonium salts, pyridinium salts, and piperazine salts of -SO3H; ammonium salts of -SO3H may include -SO3 - NR””4 + "R" includes hydrogen or a hydrocarbon group with 1-5 carbon atoms; the alkali metal salt of -SO3H can be -SO3 - Li + -SO3 - Na + -SO3 - K + At least one of them.

[0108] In some embodiments of the present invention, the substituents in the substituted alkyl, substituted carboxyl, substituted aldehyde, substituted aryl, substituted thiophene, substituted ester, and substituted amino groups independently include at least one selected from O, S, ester, halogen, hydroxyl, carboxyl, sulfonic acid, and phosphate groups. Therefore, by selecting the above-mentioned substituents for A2, an ordered hole transport pathway can be formed, thereby improving the efficiency and stability of perovskite solar cells.

[0109] In some embodiments of the present invention, R 211 R 212 R 221 R 222The substituents of A2 independently include any one of H, F, Cl, Br, I, -COOH, -CHO, R', and -N(R')2; R' independently includes any one of substituted or unsubstituted phenyl, substituted or unsubstituted thiophene, or substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms. Therefore, by selecting the above-mentioned substituents for A2, an ordered hole transport pathway can be formed, improving the efficiency and stability of perovskite solar cells.

[0110] In some embodiments of the present invention, the substituents in the substituted phenyl, substituted thiophene, or substituted alkyl groups with 1-10 carbon atoms may independently include at least one of halogen, O, S, or ester groups. Therefore, selecting the above-mentioned substituents for A2 can further improve its hole transport efficiency, thereby improving the efficiency and stability of the perovskite solar cell.

[0111] In some embodiments of the present invention, the substituted or unsubstituted phenyl groups include any one of phenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, phenoxy, phenylthio, and -COO-Ph.

[0112] As an example, chlorophenyl can include

[0113] In any of the above formulas, the short solid line represents the extraction site of the functional group.

[0114] In some embodiments of the present invention, the substituted or unsubstituted thiophene group includes any one of thiophene, fluorothiophene, chlorothiophene, bromothiophene, iodothiophene, oxythiophene, thiophene, and thiophene.

[0115] As an example, bromothiophene group can include In any of the above formulas, the short solid line represents the extraction site of the functional group.

[0116] In some embodiments of the present invention, the alkyl group with 1-10 carbon atoms can be a straight-chain alkyl group, and when the number of carbon atoms is 3 or more, the alkyl chain can be a branched alkyl group.

[0117] In some embodiments of the present invention, the unsubstituted alkyl group with 1-10 carbon atoms may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other groups, wherein the propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other groups may be straight-chain alkyl groups or branched-chain alkyl groups.

[0118] In some embodiments of the present invention, the substituted alkyl group having 1-10 carbon atoms may include any one of fluoroC1-C10 alkyl, chloroC1-C10 alkyl, bromoC1-C10 alkyl, iodoC1-C10 alkyl, oxoC1-C10 alkyl, thioC1-C10 alkyl, and methyl ester-C1-C10 alkyl. C1-C10 alkyl refers to an alkyl group having 1-10 carbon atoms. As an example, chloroC1-C10 alkyl may include any one of chloromethyl, chloroethyl, chloropropyl, chlorobutyl, chloropentyl, chlorohexyl, chloroheptyl, chlorooctyl, chlorononyl, and chlorodecyl. As an example, oxoC1-C10 alkyl may include any one of methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy. As an example, methyl esters with C1-C10 alkyl groups may include -COOCH3, -COOC2H5, -COOC3H7, -COOC4H9, and -COOC5H. 11 -COOC6H 13 -COOC7H 15 -COOC8H 17 -COOC9H 19 -COOC 10 H 21 Any one of them.

[0119] In some embodiments of the present invention, in n 21 When A is 1, 21 Including any of the following:

[0120]

[0121] Therefore, A 21 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0122] In some embodiments of the present invention, in n 22 When A is 1, 22 Including any of the following:

[0123]

[0124] Therefore, A 22 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0125] In some embodiments of the present invention, in n 21 When A is 2, 21 for:

[0126]

[0127] In some embodiments of the present invention, in n 22 When A is 2, 22 for:

[0128]

[0129] In some embodiments of the present invention, in n 21 When A is 3, 21 for:

[0130]

[0131] In some embodiments of the present invention, in n 22 When A is 3, 22 for:

[0132]

[0133] In some other embodiments of the present invention, m is any integer between 1 and 5. Thus, a carbon chain of 1 to 5 carbon atoms is selected, which has suitable steric hindrance. The carbon chain of 1 to 5 carbon atoms is connected with the A1 and A2 groups to jointly improve hole transport, thereby improving the efficiency and stability of the perovskite solar cell.

[0134] In some embodiments of the present invention, the compound represented by Formula I includes any one of the following:

[0135]

[0136] Therefore, the compound shown in Formula I is selected from the above-mentioned compounds, which has both a good anchoring effect on the lower interface and a high hole transport efficiency, thereby improving the efficiency and stability of perovskite solar cells.

[0137] In some embodiments of the present invention, the hole transport layer includes:

[0138] The first hole transport layer is disposed on one side of the first electrode layer;

[0139] The second hole transport layer is located on the side of the first hole transport layer that is away from the first electrode layer;

[0140] The second hole transport layer comprises the compound shown in Formula I. The compound shown in Formula I provided by this invention can be disposed between an existing hole transport layer material and a perovskite layer, passivating surface defects in the perovskite layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0141] In some embodiments of the present invention, the perovskite solar cell 100 of the present invention, with reference to... Figure 2 It includes a first electrode layer 110, a first hole transport layer 121, a second hole transport layer 122, a perovskite layer 130, and a second electrode layer 140.

[0142] In some embodiments of the present invention, the thickness of the second hole transport layer 122 is 0.1-5 nm. As an example, the thickness of the second hole transport layer 122 can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 nm. The compound represented by Formula I provided by the present invention can be used alone as the hole transport layer of a perovskite solar cell. Further control of the thickness of the hole transport layer formed by the compound represented by Formula I can improve hole extraction, reduce energy loss, and thus improve the photoelectric conversion efficiency and stability of the perovskite solar cell. The thickness was measured using an ellipsometry.

[0143] In some embodiments of the present invention, the thickness of the first hole transport layer 121 is 5-100 nm. As an example, the thickness of the first hole transport layer 121 can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 nm, or a range of any of the above values. The thickness is measured using an ellipsometer.

[0144] In some embodiments of the present invention, the material of the first hole transport layer may include poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), poly-3-hexylthiazole (P3HT), triphenylamine with a triphenylene core (H101), 3,4-ethylenedioxythiazole-methoxytriphenylamine (EDOT-OMeTPA), N- One or more of the following materials are selected: (4-aniline)carbazole-spirobisfluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiazole):poly(styrene sulfonate) (PEDOT:PSS), polythiazole, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz). Therefore, selecting the above materials for the first hole transport layer can further enhance the anchoring effect of the first hole transport layer and the compound shown in Formula I, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0145] In some embodiments of the present invention, the thickness of the perovskite layer is 200-1000 nm. As an example, the thickness of the perovskite layer can be 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 nm, or a range of any of the above values. Reference Figure 2 The thickness of the perovskite layer is 130 mm. The thickness was measured using a profilometer.

[0146] In some embodiments of the present invention, the perovskite material has the general formula ABX3 or A2CDX6, wherein A comprises one or more inorganic or organic monovalent cations, B comprises one or more inorganic divalent cations, C comprises one or more inorganic monovalent cations, D comprises one or more inorganic trivalent cations, and X comprises one or more monovalent anions. This can further improve the photoelectric conversion efficiency and stability of perovskite solar cells. The perovskite material was tested using XPS.

[0147] For example, organic monovalent cations include (NR1R2R3R4). + (R1R2N=CR3R4) + (R1R2N-C(R5)=NR3R4) + and (R1R2N-C(NR5R6)=NR3R4) + One or more of the following, wherein R1, R2, R3, R4, R5, and R6 each independently include H, substituted or unsubstituted C1 to C2. 20 Alkyl, or substituted or unsubstituted aryl groups. Optionally, the organic monovalent cation includes (H₂N=CH-NH₂). + (abbreviated as FA), CH3NH3 + (abbreviated as MA), one or more of the following: ethylamine cation, propylamine cation, butylamine cation, pentamine cation, hexamine cation, and imidazole cation.

[0148] For example, the inorganic monovalent cation includes: Li + Na + K + 、Rb + Cs + Cu + Ag + Au + or Hg + One or more of them.

[0149] For example, the inorganic divalent cation includes: Pb 2+ Sn 2+ Be 2+、 Mg2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2 + Co 2+ Ni 2+ Cd 2+ Cu 2+ Mn 2+ Pd 2+ Yb 2+ Or Eu 2+ One or more of them, and may further include Pb 2+ Sn 2+ One or two of them.

[0150] For example, inorganic trivalent cations include: Bi 3+ Sb 3+ Cr 3+ Fe 3+ Co 3+ Ga 3+ As 3+ Ru 3+ ,Rh 3+ In 3+ Ir 3+ Ni 3+ Au 3+ Or Al 3+ One or more of them.

[0151] For example, monovalent anions include: F - Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - CN - SeCN - One or more of them, and may further include Cl - ,Br - I - One or more of them.

[0152] In some embodiments of the present invention, the thickness of the first electrode layer is 0.5-3 mm. A suitable first electrode layer thickness can increase the mechanical strength of the battery and mitigate damage or breakage of the perovskite material due to thermal expansion, external impact, or pressure. As an example, the thickness of the first electrode layer can be 0.5, 1, 1.5, 2, 2.5, or 3 mm, or a range of any of the above values. (See reference...) Figure 2 The thickness of the first electrode layer is the same as that of the first electrode layer 110. The thickness was measured using a step meter.

[0153] In some embodiments of the present invention, the material of the first electrode layer includes a substrate and a conductive layer.

[0154] In some embodiments of the present invention, the conductive layer comprises a transparent conductive oxide. Exemplarily, the transparent conductive oxide includes one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), tungsten-doped indium oxide (IWO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), or indium zinc oxide (IZO). In some embodiments, the thickness of the conductive layer is 10 nm to 1000 nm. As an example, the thickness of the conductive layer can be 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 650 nm, 700 nm, 800 nm, 850 nm, 900 nm, 1000 nm, or any range of the above values.

[0155] In some embodiments of the present invention, the substrate may include glass or a flexible material.

[0156] In some embodiments of the present invention, the flexible material may include, but is not limited to, organic polymer materials, and further may be a mixture of one or more of the following materials in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), polycarbonate (PC), polystyrene (PS), and polyvinyl chloride (PVC). The material of the first electrode layer is tested using XPS.

[0157] In some embodiments of the present invention, the thickness of the second electrode layer is 10-1000 nm. As an example, the thickness of the second electrode layer can be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 nm, or a range of any of the above values. (See reference) Figure 2The thickness of the second electrode layer is 140 mm. The thickness was measured using an ellipsometer.

[0158] In some embodiments of the present invention, the material of the second electrode layer may include one or more of transparent conductive oxides, metals and their alloys, or carbon materials. Exemplarily, transparent conductive oxides are as defined above; metals and their alloys include one or more of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and their alloys; and carbon materials include one or more of graphite, graphene, and carbon nanotubes. Optionally, it may include one or more of Ag, Cu, C, Au, Al, indium tin oxide (ITO), zinc aluminum oxide (AZO), boron-doped zinc oxide (BZO), and indium zinc oxide (IZO); further, it may include one or more of Cu, Ag, and Au. The material of the second electrode layer is tested using XPS.

[0159] In some embodiments of the present invention, the perovskite solar cell further includes an electron transport layer disposed between the perovskite layer and the second electrode layer. The electron transport layer helps to improve the extraction and transport of electrons generated after the perovskite layer absorbs photons. The electron transport layer transports electrons to the corresponding second electrode layer to draw out the current.

[0160] In some embodiments of the present invention, a perovskite solar cell includes a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked sequentially. Generally, light is incident from the first electrode layer to excite the perovskite layer to generate a photocurrent, and the resulting perovskite solar cell is an inverted perovskite solar cell (pin).

[0161] In some embodiments of the present invention, a perovskite solar cell includes a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked sequentially. Generally, light is incident from the first electrode layer to excite the perovskite layer to generate a photocurrent, and the resulting perovskite solar cell is a formal perovskite solar cell (nip).

[0162] In some embodiments of the present invention, the thickness of the electron transport layer is 5-100 nm. As an example, the thickness of the electron transport layer can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 nm, or a range of any of the above values. The thickness is measured using an ellipsometry.

[0163] In some embodiments of the present invention, the material of the electron transport layer independently comprises one or more of imide compounds, quinone compounds, fullerenes and their derivatives, metal oxides, semiconductor material oxides, titanates, fluorides and their derivatives, and materials obtained by doping or passivation thereof. Exemplarily, imide compounds include one or more of phthalimides, succinimidides, N-bromosuccinimidides, glutarimides, or maleimides. Exemplarily, quinone compounds include one or more of benzoquinone, naphthoquinone, phenanthrenequinone, or anthraquinone. Exemplarily, fullerenes and their derivatives include fullerene C 60 Fullerene C 70 PCBM([6,6]-phenyl-C 61 methyl butyrate), [6,6]-phenyl C 71 Methyl butyrate (PC) 71 One or more of the following metal elements (BM). Exemplarily, the metal element in the metal oxide includes one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr. Optionally, the metal oxide includes one or more of tin dioxide (SnO2) and zinc oxide (ZnO). Exemplarily, the semiconductor material oxide includes silicon oxide. Exemplarily, the titanate includes one or more of strontium titanate and calcium titanate. Exemplarily, the fluoride includes one or more of lithium fluoride and calcium fluoride.

[0164] In some embodiments of the present invention, the perovskite solar cell further includes a hole-blocking layer disposed on the side of the electron transport layer away from the perovskite layer. The hole-blocking layer improves both electron extraction and hole blocking performance. The hole-blocking layer comprises a hole-blocking material. The present invention does not particularly limit the hole-blocking material; exemplaryly, the hole-blocking material may include SnO2, ZnO, or CeO. x One or more of the following: BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline).

[0165] This invention does not impose a particular limitation on the thickness of the hole blocking layer; a thickness commonly used in the art for hole blocking layers can be adopted. For example, the thickness of the hole blocking layer can be from 0.5 nm to 20 nm. As an example, the thickness of the hole blocking layer can be 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm, or a range of any of the above values.

[0166] In some embodiments of the present invention, the solar cell further includes a passivation layer disposed on at least one surface of the perovskite layer, thereby helping to reduce defects at the interface and further improve the performance of the solar cell. The passivation layer may include passivating agents conventionally used in the art for passivating perovskite light-absorbing layers, such as small organic molecules, organic salts, inorganic salts, polymers, etc. Small organic molecule passivating agents include, but are not limited to, phenylethylamine, ethylenediamine, pyridine, butanethiol, 2,5-thiophene dicarboxylic acid, etc. Organic salt passivating materials include, but are not limited to, piperazine iodine, phenylethylamine hydroiodate, dodecyl hydroiodate, guanidine bromide, thiophene ethylamine hydroiodate, ethylenediamine hydroiodate, and oleylamine iodine. Inorganic salt passivating materials include, but are not limited to, zinc chloride, potassium chloride, and gallium chloride. Polymer passivating materials include, but are not limited to, polymethyl methacrylate, polyethylene oxide, polyacrylonitrile, and polyvinyl alcohol.

[0167] In some embodiments of the present invention, the method for preparing a perovskite solar cell includes the following steps:

[0168] S100: A hole transport layer is formed on one side of the first electrode layer; the hole transport layer includes the compound shown in Formula I;

[0169] In some embodiments of the present invention, the compound represented by Formula I is incorporated into the surface of the first electrode layer to form a hole transport layer on one side of the first electrode layer.

[0170] In this invention, the composite may include mechanical composite, such as spin coating, vapor deposition, scalpel coating, heteroepitaxial growth, ultrasonic spraying, hot pressing, roll-to-roll printing, slot coating, inkjet printing, or lamination.

[0171] In some embodiments of the present invention, the composite specifically includes: dissolving the compound (self-assembled molecule) represented by Formula I in an organic solvent, and coating it onto the surface of a transparent electrode or metal oxide by spin coating, spraying, blade coating, slot coating, or roll-to-roll printing; or immersing the surface of the transparent electrode or metal oxide in a precursor solution, wherein the self-assembled molecule self-assembles to form a monolayer on the surface of the first electrode layer. The solvent for dissolving the self-assembled molecule can be methanol, isopropanol, ethanol, chlorobenzene, etc., and the concentration of the self-assembled molecule is 0.1-10 mg / mL. As an example, the concentration of the self-assembled molecule can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.8, 9, 9.5, or 10 mg / mL, or can be any range of the above values. After self-assembled molecules are prepared on the surface of transparent electrodes or metal oxides, the solvent is removed by annealing or vacuum to form a layered material.

[0172] In some embodiments of the present invention, the perovskite solar cell 100 of the present invention, with reference to... Figure 2 It includes a first electrode layer 110, a first hole transport layer 121, a second hole transport layer 122, a perovskite layer 130, and a second electrode layer 140.

[0173] In some embodiments of the present invention, forming a hole transport layer on one side of the first electrode layer specifically includes:

[0174] A first hole transport material is disposed on one side of the first electrode layer 110 to form a first hole transport layer 121, and a compound of Formula I is disposed on the side of the first hole transport layer 121 away from the first electrode layer to form a second hole transport layer 122.

[0175] In some embodiments of the present invention, the material for the first hole transport can be disposed on one side of the first electrode layer by spin coating.

[0176] S200: A perovskite layer is formed on the side of the hole transport layer away from the first electrode layer;

[0177] In some embodiments of the present invention, a perovskite layer can be formed by a perovskite precursor solution; the perovskite layer can be prepared by spin coating, vapor deposition, blade coating, spraying or slot coating.

[0178] S300: A second electrode layer is formed on the side of the perovskite layer away from the hole transport layer.

[0179] In some embodiments of the present invention, the second electrode layer can be formed by vacuum evaporation.

[0180] In some embodiments of the present invention, the perovskite solar cell further includes an electron transport layer disposed between the perovskite layer and the second electrode layer.

[0181] In some embodiments of the present invention, the method for fabricating a perovskite solar cell specifically includes: forming an electron transport layer on the side of the perovskite layer away from the hole transport layer; and forming a second electrode layer on the side of the electron transport layer away from the perovskite layer.

[0182] In some embodiments of the present invention, the electron transport layer can be formed by thermal evaporation.

[0183] In some embodiments of the present invention, the perovskite solar cell further includes a hole blocking layer disposed between the second electrode layer and the electron transport layer.

[0184] In some embodiments of the present invention, the method for fabricating a perovskite solar cell specifically includes: forming a hole blocking layer on the side of the electron transport layer away from the perovskite layer; and forming a second electrode layer on the side of the hole blocking layer away from the electron transport layer.

[0185] In some embodiments of the present invention, a hole-blocking layer can be formed by thermal evaporation.

[0186] A second aspect of the present invention provides an organic compound, the structure of which is shown in Formula I;

[0187] Formula I: A1-(CH2) m -A2-(CH2) m -A3;

[0188] In Equation I, m is any integer between 0 and 10;

[0189] A1 and A3 independently include oxyacid groups or their salts;

[0190] A2 includes A 21 Or A 22 ;

[0191]

[0192] n 21 n 22 Independently, it can be any integer between 1 and 3;

[0193] R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino.

[0194] The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

[0195] The compound represented by Formula I of this invention can serve as a hole transport layer in perovskite solar cells. This invention uses a fused ring splicing method to connect the electron donor (a group having a thiophene or derivative structure) in A2 with the electron acceptor (a group having a benzothiadiazole structure), expanding the conjugation range of A2 and increasing its conjugation degree, thereby improving the π-π interaction force of the compound represented by Formula I. This results in a stable molecular conformation for the compound represented by Formula I, while also promoting the further formation of ordered hole transport pathways in the compound represented by Formula I, thereby improving the efficiency and stability of perovskite solar cells.

[0196] In some embodiments of the present invention, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or can be a range of any of the above values.

[0197] In some embodiments of the present invention, when m is 0, the -CH2- group is not present, and the A2 group is directly connected to the A1 and A3 groups.

[0198] In some embodiments of the present invention, A1 includes any one of -COOH or a salt thereof, -PO(OH)2 or a salt thereof, -PHO(OH) or a salt thereof, -SO2(OH) or a salt thereof, -B(OH)2 or a salt thereof, and -SO3H or a salt thereof. Thus, when the compound represented by Formula I serves as the hole transport layer of a perovskite solar cell, the selection of the aforementioned oxyacid groups or their salts in A1 helps to enhance its anchoring effect at the lower interface, thereby improving the efficiency and stability of the perovskite solar cell.

[0199] In some embodiments of the present invention, the substituents in the substituted alkyl, substituted carboxyl, substituted aldehyde, substituted aryl, substituted thiophene, substituted ester, and substituted amino groups independently include at least one of O, S, ester, halogen, hydroxyl, carboxyl, sulfonic acid, and phosphate groups. Thus, the compound represented by Formula I, as a hole transport layer in a perovskite solar cell, can improve the efficiency and stability of the perovskite solar cell.

[0200] In some embodiments of the present invention, R 211 R 212 R 221 R 222 The compound of Formula I independently includes any one of H, F, Cl, Br, I, -COOH, -CHO, R', and -N(R')2; R' independently includes any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms. Therefore, the compound of Formula I, when used as the hole transport layer in a perovskite solar cell, with the substituents of A2 selected from the aforementioned groups, can form an ordered hole transport pathway, thereby improving the efficiency and stability of the perovskite solar cell.

[0201] In some embodiments of the present invention, the substituents in the substituted phenyl, substituted thiophene, and substituted alkyl groups with 1-10 carbon atoms may independently include at least one of halogen, O, S, and ester groups. Thus, the compound represented by Formula I, as the hole transport layer of a perovskite solar cell, with the substituents of A2 selected from the aforementioned groups, can form an ordered hole transport pathway, thereby improving the efficiency and stability of the perovskite solar cell.

[0202] In some embodiments of the present invention, the substituted or unsubstituted phenyl groups include any one of phenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, phenoxy, phenylthio, and -COO-Ph.

[0203] In some embodiments of the present invention, in n 21When A is 1, 21 Including any of the following:

[0204]

[0205] Therefore, the compound shown in Formula I serves as the hole transport layer in a perovskite solar cell, A 21 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0206] In some embodiments of the present invention, in n 22 When A is 1, 22 Including any of the following:

[0207]

[0208] Therefore, the compound shown in Formula I serves as the hole transport layer in a perovskite solar cell, A 22 By selecting the aforementioned groups, the conjugation range can be expanded, hole transport efficiency can be improved, and thus the efficiency and stability of perovskite solar cells can be enhanced.

[0209] In some embodiments of the present invention, in n 21 When A is 2, 21 for:

[0210]

[0211] In some embodiments of the present invention, in n 22 When A is 2, 22 for:

[0212]

[0213] In some embodiments of the present invention, in n 21 When A is 3, 21 for:

[0214]

[0215] In some embodiments of the present invention, in n 22 When A is 3, 22 for:

[0216]

[0217] In some other embodiments of the present invention, m is any integer between 1 and 5. Thus, the compound shown in Formula I serves as the hole transport layer of a perovskite solar cell. A carbon chain of 1 to 5 carbon atoms is selected, which has suitable steric hindrance. The carbon chain of 1 to 5 carbon atoms is connected with the A1 and A2 groups to jointly improve hole transport, thereby improving the efficiency and stability of the perovskite solar cell.

[0218] In some embodiments of the present invention, the compound represented by Formula I includes any one of the following:

[0219]

[0220] Therefore, the compound shown in Formula I is selected from the above-mentioned compounds and used as the hole transport layer of the perovskite solar cell. It has a good anchoring effect on the lower interface and a high hole transport efficiency, thereby improving the efficiency and stability of the perovskite solar cell.

[0221] A third aspect of the present invention provides a method for preparing an organic compound, comprising the following steps:

[0222] (1) React the compound shown in Formula II with the compound shown in Formula III to obtain the compound shown in Formula VI;

[0223] Formula II includes Formula II-1 and / or Formula II-2;

[0224]

[0225] Formula III: X-(CH2) m -A4;

[0226] In Formula III, X includes any one of F, Cl, Br, and I;

[0227] A4 includes oxyesters.

[0228] In some embodiments of the present invention, A4 includes any one of the following: an ester group of -COOH, an ester group of -PO(OH)2, an ester group of -PHO(OH), an ester group of -SO2(OH), an ester group of sulfonic acid, and an ester group of -B(OH)2.

[0229] As an example, the methyl ester group of -COOH is -COOCH3, and the methyl ester group of -PO(OH)2 is... The methyl ester group of -PHO(OH) is The methyl ester group of -SO2(OH) is The methyl ester group of the sulfonic acid group is The methyl ester group of -B(OH)2 is

[0230] In some embodiments of the present invention, n21 n 22 Independently, it can be any integer between 1 and 3.

[0231] In some embodiments of the present invention, m is any integer between 0 and 10.

[0232] In some other embodiments of the invention, m is any integer between 1 and 5.

[0233] In some embodiments of the present invention, the molar ratio of the compound represented by Formula II to the compound represented by Formula III is 1:(1 to 5). As an example, the molar ratio of the compound represented by Formula II to the compound represented by Formula III is 1:1, 1:2, 1:3, 1:4 or 1:5, or may be a range of any of the above values.

[0234] In some embodiments of the present invention, the reaction temperature of the compound represented by Formula II and the compound represented by Formula III is 120–150°C, and the time is 12–24 h; the solvent for the reaction can be a polar solvent, and in the exemplary example, the polar solvent may include at least one of ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in an alkaline environment, for example, containing an alkaline compound, which may be an inorganic base and / or an organic base.

[0235] (2) In n 21 and n 22 When n is 1, the compound shown in formula VI undergoes a substitution reaction to give the compound shown in formula I; when n 21 and n 22 In the case of 2 or 3, the compound shown in Formula VI is subjected to the first substitution reaction, coupling reaction and second substitution reaction in sequence to obtain the compound shown in Formula I;

[0236] Formula VI includes Formula VI-1 and / or Formula VI-2;

[0237]

[0238] In some embodiments of the present invention, in n 21 and n 22In the case of 1, the starting materials for the substitution reaction include the compound shown in Formula VI and a halosilane. As an example, the halosilane may include any one of trimethylbromosilane, trimethylchlorosilane, and trimethyliodosilane; the molar ratio of the compound shown in Formula VI to the halosilane is 1:(15–25); the temperature of the second substitution reaction is 20–30°C, and the time is 12–24 h; the solvent for the reaction may be a polar solvent, and in the exemplary example, the polar solvent may include at least one of 1,4-dioxane, methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in a protective atmosphere, such as containing nitrogen and / or an inert gas.

[0239] In some embodiments of the present invention, in n 21 and n 22 In the case of 1, before the substitution reaction of the compound shown in Formula VI, the compound shown in Formula VI is subjected to a halogenation reaction; the starting materials for the halogenation reaction include the compound shown in Formula VI and a halogenating agent; the molar ratio of the compound shown in Formula VI to the halogenating agent is 1:(2-5); the halogenating agent may include any one of N-bromosuccinimide, N-chlorosuccinimide, and N-iodosuccinimide; the temperature of the first substitution reaction is 20-30°C, and the time is 12-24 h; the solvent for the reaction may be a polar solvent, and in the example, the polar solvent may include at least one of methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in a protective gas environment, such as containing nitrogen and / or an inert gas.

[0240] In some other embodiments of the invention, in n 21 and n 22 In the case of 1, before the substitution reaction of the compound shown in Formula VI, the compound shown in Formula VI is subjected to an aldehyde-based reaction; the starting materials for the aldehyde-based reaction include the compound shown in Formula VI and the aldehyde-based reagent; the aldehyde-based reagent may include organic amines and chlorine-containing compounds. As an example, the organic amine may include at least one of methylamine, aniline, dimethylamine, diethylamine, and N,N-dimethylformamide; as an example, it may include at least one of phosphorus oxychloride, formyl chloride, chlorine trifluoride, thionyl chloride, phosphate ester, hydrogen chloride, and cyanogen chloride; the temperature of the second substitution reaction is 80–100°C, and the time is 10–20 h; the solvent for the reaction may be a polar solvent, and in an exemplary example, the polar solvent may include at least one of 1,2-dichloroethane, methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in a protective gas environment, such as containing nitrogen and / or an inert gas; the reaction is carried out in an alkaline environment, such as containing a basic compound, which may be an inorganic base and / or an organic base.

[0241] In some embodiments of the present invention, in n 21 and n 22 In the case of 2 or 3, the first substitution reaction can be a halogenation reaction; the starting materials for the halogenation reaction include the compound shown in Formula VI and the halogenating agent; the molar ratio of the compound shown in Formula VI to the halogenating agent is 1:(2-5); the halogenating agent can include any one of N-bromosuccinimide, N-chlorosuccinimide, and N-iodosuccinimide; the temperature of the first substitution reaction is 20-30°C, and the time is 12-24 h; the solvent for the reaction can be a polar solvent, and in the example, the polar solvent can include at least one of methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in a protective gas environment, such as containing nitrogen and / or an inert gas.

[0242] In some embodiments of the present invention, in n 21 and n 22 In the case of 2 or 3, the coupling reaction may include sequentially performing the Miyaura reaction (boration reaction) and the Suzuki reaction (reaction); the Miyaura reaction system includes the product of the first substitution reaction, the bisboron reagent, and the palladium catalyst; the molar ratio of the product of the first substitution reaction to the bisboron reagent is 1:(2-5); the temperature of the Miyaura reaction is 70-100°C, and the time is 12-24 h; the solvent for the reaction can be a polar solvent, and in the example, the polar solvent may include at least one of methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane; the reaction is carried out in an alkaline environment, for example... The reaction system contains a basic compound, which can be an inorganic base and / or an organic base; the Suzuki reaction system includes the product of the first substitution reaction, the product of the Miyauchi reaction, and a palladium catalyst; the molar ratio of the product of the first substitution reaction to the product of the Miyauchi reaction is 1:(2-5); the temperature of the Suzuki reaction is 100-120°C, and the time is 18-24 h; the solvent for the reaction can be a polar solvent, and in the example, the polar solvent may include at least one of methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane; the reaction is carried out in an alkaline environment, for example, containing a basic compound, which can be an inorganic base and / or an organic base.

[0243] In some embodiments of the present invention, in n 21 and n 22In the case of 2 or 3, the starting materials for the second substitution reaction include the product of the coupling reaction and a halosilane. As an example, the halosilane may include any one of trimethylbromosilane, trimethylchlorosilane, and trimethyliodosilane; the molar ratio of the product of the coupling reaction to the halosilane is 1:(15–25); the temperature of the second substitution reaction is 20–30°C, and the time is 12–24 h; the solvent for the reaction may be a polar solvent, and in exemplary cases, the polar solvent may include at least one of 1,4-dioxane, methanol, ethanol, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, and dimethyl sulfoxide; the reaction is carried out in a protective atmosphere, such as one containing nitrogen and / or an inert gas.

[0244] A fourth aspect of this invention provides a tandem battery, comprising one or more of the following: a perovskite solar cell, an organic compound, and an organic compound prepared by a method thereof. Therefore, this tandem battery exhibits good long-term stability and a long service life.

[0245] In one embodiment, the tandem solar cell further includes a light-absorbing layer with a different bandgap than the perovskite layer. Thus, the light-absorbing layer and the perovskite layer can improve light utilization efficiency and enhance the performance of the solar cell by absorbing light of different wavelengths. In some embodiments, the light-absorbing layer can be one or more of a perovskite light-absorbing layer, a crystalline silicon light-absorbing layer, a cadmium telluride light-absorbing layer, a copper indium gallium selenide light-absorbing layer, or a polycrystalline silicon light-absorbing layer. If the light-absorbing layer is a perovskite layer, the resulting solar cell is a fully perovskite tandem solar cell; if the light-absorbing layer is a crystalline silicon light-absorbing layer, the resulting solar cell is a silicon-calcium tandem solar cell. No limitation is imposed here.

[0246] In some implementations, the position of the light-absorbing layer can be adjusted according to actual conditions. For example, it can be set to be insulated from the perovskite solar cell to form a mechanically stacked solar cell. As a further example, the structure of the mechanically stacked solar cell may include a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, a second electrode layer, a transparent insulating layer, a third electrode layer, a third carrier transport layer, a light-absorbing layer, a fourth carrier transport layer, and a fourth electrode layer stacked sequentially. The third carrier transport layer is one of the electron transport layer and the hole transport layer, and the fourth carrier transport layer is the other of the electron transport layer and the hole transport layer. The material selection for the electron transport layer or the hole transport layer is as described above and will not be repeated here. The second and third electrode layers are made of transparent conductive oxide, which facilitates light transmission. Thus, the transparent insulating layer isolates the two cell units in the circuit. Each cell unit has two electrodes, for a total of four electrodes. The circuits of the two cell units are independent of each other, forming a four-terminal stacked solar cell.

[0247] In some implementations, the position of the light-absorbing layer can be adjusted according to actual conditions, such as placing it between perovskite solar cells to form a tandem solar cell. As a further example, the structure of a tandem solar cell may include a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, a recombination layer, a third carrier transport layer, a light-absorbing layer, a fourth carrier transport layer, and a second electrode layer stacked sequentially, wherein the third carrier transport layer is a hole transport layer and the fourth carrier transport layer is an electron transport layer. The material selection for the electron transport layer or hole transport layer is as described above and will not be repeated here. The recombination layer is used to connect the cell units on both sides. Specifically, electrons from the perovskite layer and electrons from the light-absorbing layer recombine and annihilate in the recombination layer, thereby achieving the circuit connection between the two cell units. The resulting tandem solar cell is simple to fabricate; the top cell can be directly deposited on the bottom cell to form a single, complete cell with two electrodes, forming a two-end tandem solar cell.

[0248] In some embodiments, the composite layer is made of one or more of metallic materials, transparent conductive oxides, and carbon materials. Further, the transparent conductive oxide layer comprises, but is not limited to, one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), zinc aluminum oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), indium tungsten oxide (IWO), indium gallium zinc oxide (IGZO), and antimony tin oxide (ATO). Further, the metallic materials include, but are not limited to, one or more of gold, copper, silver, platinum, aluminum, and iron. Further, the carbon materials include one or more of graphite, graphene, and carbon nanotubes.

[0249] A fifth aspect of this invention provides a photovoltaic module comprising: a perovskite solar cell, an organic compound, and one or more of the following: an organic compound prepared by a method thereof. Therefore, this photovoltaic module exhibits good long-term stability and a long service life.

[0250] A sixth aspect of the present invention provides a power generation device, comprising one or more of the following: a perovskite solar cell, an organic compound, and an organic compound prepared by a method thereof. Therefore, the power generation device exhibits good long-term stability and a long service life.

[0251] A photovoltaic (PV) power generation system refers to a system that directly converts solar radiation energy into electrical energy using the photovoltaic effect. It is divided into stand-alone PV systems and grid-connected PV systems. A stand-alone PV system consists of a solar photovoltaic array composed of photovoltaic modules, a battery bank, a charge controller, a power electronic converter (inverter), and loads. A grid-connected PV system consists of a photovoltaic array, a high-frequency DC / DC boost circuit, a power electronic converter (inverter), and a system monitoring system. PV power generation systems can include large-scale ground-mounted PV systems, distributed PV systems, and building-integrated photovoltaic (BIPV) systems.

[0252] A seventh aspect of the present invention provides an electrical device comprising: one or more of the following: a perovskite solar cell, an organic compound, and an organic compound prepared by a method thereof. Therefore, the electrical device exhibits good long-term stability and a long service life.

[0253] Electrical devices can include lighting elements, display elements, mobile devices, etc., specifically including streetlights, signal lights, insect-killing lamps, electric fans, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc. Therefore, this electrical device has good long-term stability and a long service life.

[0254] According to some embodiments of the present invention, Figure 4 This is an example of an electrical device. The electrical device could be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.

[0255] In this invention, the term "electron donor" refers to a group capable of donating electrons to other parts of a molecule; the term "electron acceptor" refers to a group capable of attracting electrons from a molecule.

[0256] In this invention, the term "fused ring splicing" refers to the process of connecting two or more ring structures (which may be carbon rings or heterocycles) by sharing edges to form a polycyclic organic compound.

[0257] In this invention, the term "substitution" refers to the replacement of one or more hydrogen atoms on a specified atom by a group selected from those indicated, provided that the substitution does not exceed the normal valence of the specified atom under its existing condition, and that the substitution produces a stable compound. Substituents and / or variables can be combined, as long as such combinations produce a stable compound.

[0258] In this invention, the term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0259] In this invention, the term "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. In this invention, alkyl groups include (but are not limited to) methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, etc.

[0260] In this invention, the term "alkoxy" refers to a group formed by an alkyl group linked to the remainder of a molecule via an oxygen atom. In this invention, alkoxy groups include (but are not limited to) methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, etc. Alkoxy groups in this invention may optionally be substituted with one or more substituents described in this invention.

[0261] In this invention, the term "aryl" refers to a monocyclic or fused polycyclic aromatic hydrocarbon group having a conjugated π-electron system. In this invention, aryl includes (but is not limited to) phenyl, naphthyl, anthraceneyl, phenanthryl, acenaphthene, azulene, fluorenyl, indene, pyrene, etc. The aryl group in this invention may optionally be substituted with one or more substituents described in this invention (such as halogen, hydroxyl, cyano, nitro, alkyl, etc.).

[0262] In this invention, the term "each independently" or "independently" means that at least two groups (or ring systems) in the structure with the same or similar value ranges can have the same or different meanings under specific circumstances. For example, if substituent 1 and substituent 2 are each independently hydrogen, halogen, hydroxyl, cyano, alkyl, or aryl, then when substituent 1 is hydrogen, substituent 2 can be hydrogen, halogen, hydroxyl, cyano, alkyl, or aryl; similarly, when substituent 2 is hydrogen, substituent 1 can be hydrogen, halogen, hydroxyl, cyano, alkyl, or aryl.

[0263] In this invention, the term "halogenation reaction" refers to the process by which an organic compound reacts with a halogen (fluorine, chlorine, bromine, iodine, etc.) to form a halogenated product. In a halogenation reaction, one or more halogen atoms are introduced into the carbon chain or ring structure of an organic molecule, replacing the original hydrogen atoms. The term "halogenating agent" is a reagent that carries out a halogenation reaction, providing halogen atoms or halide ions in the reaction.

[0264] In this invention, the term "aldehyde hydration reaction" refers to the process in organic chemistry of introducing an aldehyde group (-CHO) into the structure of a target compound. The term "aldehyde hydration reagent" is a reagent used to carry out the aldehyde hydration reaction. The aldehyde hydration reagent can react to generate an active aldehyde hydration intermediate, which can be electrophilically attacked by the target compound to form an aldehyde group.

[0265] The present invention will be described below through specific embodiments. It should be noted that these embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0266] Example 1

[0267] The preparation method of the organic compound SAM1 in this embodiment specifically includes the following steps:

[0268] (1): Compound 1 (1 mmol), compound 2 (2.2 mmol), and catalyst tetraphenylphosphine palladium (Pd(PPh3)4, 0.05 mmol) were dissolved in toluene (20 mL). The mixture was heated to 110 °C under nitrogen protection and reacted for 18 h. After separation by silica gel chromatography, compound 3 was obtained with a yield of approximately 94%. 1 H NMR (400MHz, DMSO-d6) δ7.69 (dd, J = 7.4, 1.5 Hz, 2H), 7.57 (dd, J = 7.4, 1.5 Hz, 2H), 7.17 (t, J = 7.4 Hz, 2H).

[0269]

[0270] (2): Compound 3 (1 mmol) and triphenylphosphine (PPh3, 10 mmol) were dissolved in o-dichlorobenzene (o-DCB, 20.00 mL) under nitrogen protection. The mixture was then heated to 180 °C and reacted for 12 h. After cooling to room temperature, the solvent was concentrated by evaporation under reduced pressure. Without further purification, anhydrous potassium iodide (1 mmol), potassium carbonate (10 mmol), diethyl (4-bromobutyl)phosphonate (4 mmol), and anhydrous N,N-dimethylformamide (DMF, 20.00 mL) were added to the residue, and the mixture was stirred at 130 °C for 24 h. After cooling to room temperature, the mixture was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated by evaporation under reduced pressure, and separated by silica gel chromatography to give compound 5 in approximately 52% yield. The 1H NMR spectrum was obtained. 1H NMR (400MHz, DMSO-d6) δ7.59(d,J=7.7Hz,2H),7.27(d,J=7.4Hz,2H),4.31(t,J=7.0Hz,4H),4.14(dp,J=12 .6,8.1Hz,4H),3.97(dp,J=12.3,8.0Hz,4H),1.96-1.82(m,8H),1.64(q,J=6.9Hz,4H),1.40-1.29(m,12H).

[0271]

[0272] (3): Compound 5 (1 mmol) was dissolved in N,N-dimethylformamide (DMF, 15 ml). Under nitrogen protection, N-bromosuccinimide (NBS, 2 mmol) was slowly added to the mixture of compound 5 and DMF. The mixture was stirred at room temperature for 12 h. The reaction process was detected by thin-layer chromatography (TLC). After separation by silica gel chromatography column, compound 6 was obtained with a yield of about 72%. The 1H NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.21 (s, 2H), 4.33 (t, J = 7.1Hz, 4H), 4.22-4.08 (m, 4H), 3.98 ( dt,J=12.3,8.2Hz,4H),1.98-1.81(m,8H),1.65(q,J=7.3Hz,4H),1.44-1.34(m,12H).

[0273]

[0274] (4): Under nitrogen protection, compound 6 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and then trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The reaction was quenched by stirring at room temperature for another 3 h. Part of the solvent was removed by rotary evaporation, and then methanol was added. Distilled water was then added dropwise until the solution became opaque. The mixture was stirred for 12 h, and the solid was collected by filtration and washed with water to obtain product SAM1. The 1H NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.21 (s, 2H), 6.72 (s, 4H), 4.28 (t, J = 7.1Hz, 4H), 1.93-1.82 (m, 8H), 1.69 (q, J = 7.3, 6.8Hz, 4H).

[0275]

[0276] Example 2

[0277] The preparation method of the organic compound SAM2 in this embodiment specifically includes the following steps:

[0278] (1): Compound 5 (1 mmol) was dissolved in N,N-dimethylformamide (DMF, 15 ml). Under nitrogen protection, N-chlorosuccinimide (NCS, 2 mmol) was slowly added to the mixture of compound 5 and DMF. The mixture was stirred at room temperature for 12 h. The reaction process was monitored by TLC. After separation by silica gel chromatography, compound 7 was obtained with a yield of approximately 76%. The 1H NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ6.99 (s, 2H), 4.32 (t, J = 7.0Hz, 4H), 4.23-4.09 (m, 4H), 4.01 ( dp,J=12.6,8.1Hz,4H),1.98-1.79(m,8H),1.65(q,J=7.2Hz,4H),1.42-1.33(m,12H).

[0279]

[0280] (2): Under nitrogen protection, compound 7 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and then trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The mixture was stirred at room temperature for another 3 h to quench the reaction. Part of the solvent was removed by rotary evaporation, and then methanol was added again. Distilled water was then added dropwise until the solution became opaque. The mixture was stirred for 12 h, filtered to collect the solid, and washed with water to obtain product SAM2. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ6.99 (s, 2H), 6.72 (s, 4H), 4.28 (t, J = 7.1Hz, 4H), 1.93-1.80 (m, 8H), 1.74-1.63 (m, 4H).

[0281]

[0282] Example 3

[0283] The preparation method of the organic compound SAM3 in this embodiment specifically includes the following steps:

[0284] (1): Compound 5 (1 mmol) was dissolved in N,N-dimethylformamide (DMF, 15 ml). Under nitrogen protection, N-iodosuccinimide (NIS, 2 mmol) was slowly added to the mixture of compound 5 and DMF. The mixture was stirred at room temperature for 12 h. The reaction process was monitored by TLC. After separation by silica gel chromatography, compound 8 was obtained with a yield of approximately 68%. The 1H NMR spectrum was measured. 1H NMR(400MHz, DMSO-d6)δ7.35(s,2H),4.33(t,J=7.1Hz,4H),4.15(dp,J=12.3,8.0Hz,4H),3 .98(dp,J=12.3,8.1Hz,4H),1.98-1.82(m,8H),1.65(q,J=7.3Hz,4H),1.43-1.31(m,12H).

[0285]

[0286] (2): Under nitrogen protection, compound 8 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and then trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The mixture was stirred at room temperature for another 3 h to quench the reaction. Part of the solvent was removed by rotary evaporation, and then methanol was added again. Distilled water was then added dropwise until the solution became opaque. The mixture was stirred for 12 h, filtered to collect the solid, and washed with water to obtain product SAM3. The 1H NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.35 (s, 2H), 6.72 (s, 4H), 4.28 (t, J = 7.1Hz, 4H), 1.94-1.82 (m, 8H), 1.74-1.62 (m, 4H).

[0287]

[0288] Example 4

[0289] The preparation method of the organic compound SAM4 in this embodiment specifically includes the following steps:

[0290] (1): Under nitrogen protection, anhydrous N,N-dimethylformamide (DMF, 1.00 mL) was added to a 50 mL double-necked round-bottom flask. The flask was placed at 0 °C, and phosphorus oxychloride (0.10 mL, 1.7 mmol) was slowly added dropwise. The mixture was stirred at this temperature for 30 min. Compound 5 (0.17 mmol) was dissolved in 20 mL of 1,2-dichloroethane solution and added to the reaction flask. The reaction system was stirred at 90 °C for 12 h. After cooling to room temperature, the mixture was poured into 100 mL of saturated sodium bicarbonate solution and stirred for 2 h, followed by extraction with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated by vacuum evaporation, and separated by silica gel chromatography to obtain compound 9 with a yield of approximately 82%. The 1H NMR spectrum was measured. 1H NMR (400MHz, DMSO-d6) δ9.85(s,2H),7.68(s,2H),4.33(t,J=7.1Hz,4H),4.15(dp,J=12.3,8.1Hz ,4H),3.97(dp,J=12.6,8.1Hz,4H),1.97-1.81(m,8H),1.65(q,J=7.3Hz,4H),1.41-1.31(m,12H).

[0291]

[0292] (2): Under nitrogen protection, compound 9 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and then trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The mixture was stirred at room temperature for another 3 h to quench the reaction. Part of the solvent was removed by rotary evaporation, and then methanol was added again. Distilled water was then added dropwise until the solution became opaque. The mixture was stirred for 12 h, filtered to collect the solid, and washed with water to obtain product SAM4. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ9.85 (s, 2H), 7.70 (s, 2H), 6.72 (s, 4H), 4.30 (t, J = 7.0Hz, 4H), 1.95-1.81 (m, 8H), 1.69 (q, J = 7.3, 6.9Hz, 4H).

[0293]

[0294] Example 5

[0295] The method for preparing the organic compound in this embodiment includes the following steps:

[0296] (1): Compound 6 (1 mmol) was dissolved in 15 mL of 1,4-dioxane, and then pinacol diboronate (1 mmol), palladium dichloride ferrocene (PdCl2 (dppf), 0.05 mmol), and potassium acetate (KOAc, 1 mmol) were added. The mixture was reacted at 80 °C for 16 h, and compound 10 was obtained by separation by silica gel chromatography. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.58 (s, 1H), 7.21 (s, 1H), 4.33 (td, J = 7.2, 4.4Hz, 4H), 4.22-3.89 (m,8H),1.99-1.78(m,8H),1.73-1.56(m,4H),1.38(td,J=7.9,0.8Hz,12H),1.23(s,12H).

[0297]

[0298] (2): Compound 6 (1 mmol) and compound 10 (1 mmol) were dissolved in 20 mL of toluene, and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.05 mmol) and 20 mL of K2CO3 aqueous solution (2 mol / mL) were added. The mixture was heated to 110 °C for 24 h under nitrogen protection. After separation by silica gel chromatography, compound 11 was obtained. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.29 (s, 2H), 7.21 (s, 2H), 4.33 (td, J = 7.1, 0.9Hz, 8H), 4.2 2-3.89(m,16H),1.97-1.80(m,16H),1.65(q,J=6.8Hz,8H),1.38(t,J=8.0Hz,24H).

[0299]

[0300] (3): Under nitrogen protection, compound 11 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The reaction was continued at room temperature for 3 h to quench the reaction. Part of the solvent was removed by rotary evaporation, followed by the addition of methanol, and then distilled water was added dropwise until the solution became opaque. The mixture was stirred for 12 h, filtered to collect the solid, and washed with water to obtain compound 12. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.29 (s, 2H), 7.21 (s, 2H), 6.72 (s, 8H), 4.30 (td, J = 7.0, 3.6Hz, 8H), 1.98-1.77 (m, 16H), 1.75-1.58 (m, 8H).

[0301]

[0302] Example 6

[0303] The method for preparing the organic compound in this embodiment specifically includes the following steps:

[0304] (1): Compound 6 (1 mmol) and compound 10 (2 mmol) were dissolved in 20 mL of toluene, and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.05 mmol) and 20 mL of K2CO3 aqueous solution (2 mol / mL) were added. The mixture was heated to 110 °C for 24 h under nitrogen protection, and compound 13 was obtained after separation by silica gel chromatography. The proton NMR spectrum was measured. 1H NMR (400MHz, DMSO-d6) δ7.30 (s, 4H), 7.21 (s, 2H), 4.33 (td, J = 7.2, 1.7Hz, 12H), 4.24-3 .85(m,24H),2.00-1.79(m,24H),1.66(q,J=6.9Hz,12H),1.38(td,J=7.9,0.9Hz,36H).

[0305]

[0306]

[0307] (2): Under nitrogen protection, compound 13 (1 mmol) was dissolved in anhydrous 1,4-dioxane, and trimethylbromosilane (15 mmol) was added dropwise. The reaction was carried out at room temperature for 24 h, followed by the addition of methanol. The reaction was continued at room temperature for 3 h to quench the reaction. Part of the solvent was removed by rotary evaporation, followed by the addition of methanol, and then distilled water was added dropwise until the solution became opaque. The mixture was stirred for 12 h, filtered to collect the solid, and washed with water to obtain compound 14. The proton NMR spectrum was measured. 1 H NMR (400MHz, DMSO-d6) δ7.30 (s, 4H), 7.21 (s, 2H), 6.72 (d, J = 1.0Hz, 12H), 4.30 (td, J = 7.0, 4.4Hz, 12H), 1.94-1.78 (m, 24H), 1.73-1.63 (m, 12H).

[0308]

[0309] Example 7

[0310] The perovskite solar cell of this embodiment, such as Figure 3 As shown, the perovskite solar cell 100, from bottom to top, includes a first electrode layer 110, a hole transport layer 120, a perovskite layer 130, an electron transport layer 150, a hole blocking layer 160, and a second electrode layer 140 stacked together. The specific fabrication method of the perovskite solar cell includes the following steps:

[0311] 1) Take an FTO conductive glass with dimensions of 2.0cm*2.0cm*0.2cm, where the thickness of the FTO layer is 500nm. Remove 0.35cm of FTO from each end by laser etching to expose the glass substrate.

[0312] 2) Use water, acetone, and isopropanol to ultrasonically clean the etched FTO conductive glass in sequence.

[0313] 3) Use a nitrogen gun to blow dry the solvent from the FTO conductive glass, and then place it in an ultraviolet ozone generator for further cleaning, which will serve as the first electrode layer.

[0314] 4) Spin-coat the FTO conductive glass surface obtained in step 3) with a methanol solution of nano-nickel oxide (the concentration of nano-nickel oxide is 10 mg / mL) at 2000 rpm, anneal at 150 °C for 30 minutes to remove the solvent and form a 50 nm nickel oxide thin film layer (NiOx).

[0315] 5) The self-assembled molecule SAM1 obtained in Example 1 was dissolved in methanol to obtain a self-assembled molecule solution with a concentration of 0.3 mg / mL; the self-assembled molecule was spin-coated on the surface of a nickel oxide film at 3000 rpm, and a 5 nm thick self-assembled molecule layer was obtained by vacuuming or annealing; the nickel oxide film layer and the self-assembled molecule layer were used together as a hole transport layer.

[0316] 6) Weigh out lead iodide (726 mg), formamidinium iodide (240 mg), cesium iodide (19 mg), and lead bromide (11 mg) and dissolve them in 1 mL of a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) with a volume ratio of 4:1. Stir for 3 h, filter through a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. Spin-coat the perovskite precursor solution onto the obtained self-assembled molecular layer at 3000 rpm, anneal at 100 °C for 30 min, and cool to room temperature to form an 800 nm perovskite layer. The active material of the perovskite layer is a CsFA system, and the component is Cs. 0.05 FA 0.95 PbI 2.94 Br 0.06 .

[0317] 7) Spin-coat PC onto the perovskite layer at a speed of 1500 rpm. 61 BM is annealed at 100°C for 10 min to form an electron transport layer with a thickness of 35 nm. Then, copper bath (BCP) is spin-coated on the electron transport layer at a speed of 5000 rpm to form a hole blocking layer with a thickness of 15 nm.

[0318] 8) Place the wafer obtained in step 7) into a vapor deposition machine, and vapor deposit Cu as the second electrode layer. The thickness of the second electrode layer is 80 nm to obtain a perovskite solar cell.

[0319] Examples 8-12

[0320] The perovskite solar cells of Examples 8-12 were prepared according to the method in Example 7. The difference from Example 7 is that in Examples 8-10, SAM1 was replaced with SAM2, SAM3, SAM4, compound 12, and compound 14, respectively, as detailed in Table 1. The remaining parameters and steps were performed according to the method in Example 1.

[0321] Example 13

[0322] The perovskite solar cell of this embodiment was prepared according to the method in Example 7. The difference from Example 1 is that step 4) is omitted in this embodiment, and the self-assembled molecular layer is used as the hole transport layer; the remaining experimental conditions and steps are the same as those in Example 1.

[0323] Comparative Example 1

[0324] The perovskite solar cell of this comparative example was prepared according to the method in Example 7. The difference from Example 1 is that step 5) is omitted in this comparative example, and a nickel oxide thin film layer (NiOx) is used as the hole transport layer; the rest of the method is the same as in Example 1.

[0325] Test case

[0326] The perovskite solar cells obtained in Examples 7-13 and Comparative Example 1 were tested, and the test procedures are as follows:

[0327] 1. Using a solar simulator from Guangyan, tests were conducted according to the national standard IEC61215. A crystalline silicon solar cell was used to correct the light intensity to achieve a solar intensity of AM 1.5. The cell was connected to a digital source meter, and its photoelectric conversion efficiency was measured under illumination to obtain P. out P in V mpp J mpp Open circuit voltage (V) OC) Short-circuit current (J) SC The parameters are calculated based on the following formula:

[0328] FF = V OC ×J SC / (V mpp ×J mpp );

[0329] PCE = P out / P in =V OC ×J SC ×FF / P in ;

[0330] Among them, P out P in V mpp J mpp , , and FF represent the battery's operating output power, incident light power, battery's maximum power point voltage, battery's maximum power point current, and fill factor, respectively. The experimental results are shown in Table 1.

[0331] 2. Uses a 600*600mm long-life LED aging light source, with the calibrated light source intensity set to one sun (AM 1.5G, 100mW / cm²). 2Simultaneously, a hot plate was used to heat the battery. The fixture's built-in temperature and humidity acquisition module displayed a temperature of 75℃ and a humidity of <5%RH, at which point the MPPT (Multi-Modulation Testing) was initiated. This was recorded as the percentage of the perovskite solar cell retaining its initial PCE after 200 hours of heating at 75℃. The experimental results are shown in Table 1.

[0332] Table 1

[0333]

[0334]

[0335] As shown in Table 1, compared with the comparative example, using the organic compound of the present invention alone as a hole transport layer, or together with nickel oxide as a hole transport layer, can improve the efficiency and stability of perovskite solar cells.

[0336] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Furthermore, in the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0337] For the sake of brevity, this article only discloses some specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0338] In the description of the embodiments of this invention, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0339] Those skilled in the art will understand that, in the method of a specific embodiment, the order in which the steps are written does not imply a strict execution order and does not constitute any limitation on the implementation process. The specific execution order of each step should be determined by its function and possible internal logic.

[0340] 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 invention pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the invention, are intended to cover non-exclusive inclusion.

[0341] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," "some implementations," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0342] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A perovskite solar cell, characterized in that, include: First electrode layer; A hole transport layer is disposed on one side of the first electrode layer; A perovskite layer is disposed on the side of the hole transport layer opposite to the first electrode layer; The second electrode layer is disposed on the side of the perovskite layer opposite to the hole transport layer. The hole transport layer comprises the compound shown in Formula I; Formula I: A1-(CH2) m -A2-(CH2) m -A3; In Equation I, m is any integer between 0 and 10; A1 and A3 independently include oxyacid groups or their salts; A2 includes A 21 Or A 22 ; n 21 n 22 Independently, it can be any integer between 1 and 3; R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino. The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

2. The perovskite solar cell according to claim 1, characterized in that, A1 includes any one of -COOH or its salt, -PO(OH)2 or its salt, -PHO(OH) or its salt, -SO2(OH) or its salt, -B(OH)2 or its salt, and -SO3H or its salt.

3. The perovskite solar cell according to claim 1, characterized in that, The substituents in the substituted alkyl group, the substituted carboxyl group, the substituted aldehyde group, the substituted aryl group, the substituted thiophene group, the substituted ester group, and the substituted amino group independently include at least one of O, S, ester group, halogen, hydroxyl group, carboxyl group, sulfonic acid group, and phosphate group.

4. The perovskite solar cell according to claim 3, characterized in that, R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, -COOH, -CHO, R', -N(R')2; R' independently includes any one of substituted or unsubstituted phenyl, substituted or unsubstituted thiophene, or substituted or unsubstituted alkyl with 1 to 10 carbon atoms.

5. The perovskite solar cell according to claim 4, characterized in that, The substituents in the substituted phenyl group, the substituted thiophene group, and the substituted alkyl group with 1-10 carbon atoms may independently include at least one of halogen, O, S, and ester group.

6. The perovskite solar cell according to claim 5, characterized in that, In n 21 When A is 1, 21 Including any of the following: In n 22 When A is 1, 22 Including any of the following:

7. The perovskite solar cell according to claim 1, characterized in that, m is any integer between 1 and 5.

8. The perovskite solar cell according to claim 1, characterized in that, The compound represented by Formula I includes any one of the following:

9. The perovskite solar cell according to any one of claims 1-8, characterized in that, The hole transport layer includes: A first hole transport layer is disposed on one side of the first electrode layer; The second hole transport layer is disposed on the side of the first hole transport layer opposite to the first electrode layer; The second hole transport layer comprises the compound shown in Formula I.

10. The perovskite solar cell according to claim 9, characterized in that, The thickness of the second hole transport layer is 0.1-5 nm.

11. The perovskite solar cell according to claim 9, characterized in that, The thickness of the first hole transport layer is 5-100 nm.

12. The perovskite solar cell according to claim 9, characterized in that, The first hole transport layer comprises one or more of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiazole, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiazole-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiazole):poly(styrene sulfonate), polythiazole, nickel oxide, molybdenum oxide, cuprous iodide, cuprous oxide), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid.

13. An organic compound, characterized in that, The structure of the organic compound is shown in Formula I; Formula I: A1-(CH2) m -A2-(CH2) m -A3; In Equation I, m is any integer between 0 and 10; A1 and A3 independently include oxyacid groups or their salts; A2 includes A 21 Or A 22 ; n 21 n 22 Independently, it can be any integer between 1 and 3; R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted aldehyde, substituted or unsubstituted aryl, substituted or unsubstituted thiophene, substituted or unsubstituted ester, or substituted or unsubstituted amino. The dashed lines represent A2 and -(CH2) in expression I. m - The key to the connection.

14. The organic compound according to claim 13, characterized in that, A1 includes any one of -COOH or its salt, -PO(OH)2 or its salt, -PHO(OH) or its salt, -SO2(OH) or its salt, -B(OH)2 or its salt, -SO3H or its salt, and / or, R 211 R 212 R 221 R 222 Independently includes any one of H, F, Cl, Br, I, -COOH, -CHO, R', -N(R')2; R' independently includes any one of substituted or unsubstituted phenyl, substituted or unsubstituted thiophene, or substituted or unsubstituted alkyl with 1 to 10 carbon atoms.

15. The organic compound according to claim 14, characterized in that, The substituents in the substituted phenyl group, the substituted thiophene group, and the substituted alkyl group with 1-10 carbon atoms may independently include at least one of halogen, O, S, and ester group.

16. The organic compound according to any one of claims 13 to 15, characterized in that, The compound represented by Formula I includes any one of the following:

17. A method for preparing an organic compound, characterized in that, Includes the following steps: The compound shown in Formula II and the compound shown in Formula III are reacted to obtain the compound shown in Formula VI; Formula II includes Formula II-1 and / or Formula II-2; Formula III: X-(CH2) m -A4; In Formula III, X includes any one of F, Cl, Br, and I; A4 includes oxyesters; In n 21 and n 22 When the value is 1, the compound shown in formula VI is subjected to a substitution reaction to obtain the compound shown in formula I; In n 21 and n 22 In the case of 2 or 3, the compound shown in Formula VI is subjected to the first substitution reaction, coupling reaction and second substitution reaction in sequence to obtain the compound shown in Formula I; Formula VI includes Formula VI-1 and / or Formula VI-2; 18. A stacked battery, characterized in that, include: One or more of the following: the perovskite solar cell according to any one of claims 1 to 11; the organic compound according to any one of claims 13 to 15; and the organic compound prepared by the method of the organic compound according to claim 17.

19. A photovoltaic module, characterized in that, include: One or more of the following: the perovskite solar cell according to any one of claims 1 to 11; the organic compound according to any one of claims 13 to 15; and the organic compound prepared by the method of the organic compound according to claim 17.

20. A power generation device, characterized in that, include: One or more of the following: the perovskite solar cell according to any one of claims 1 to 11; the organic compound according to any one of claims 13 to 15; and the organic compound prepared by the method of the organic compound according to claim 17.

21. An electrical appliance, characterized in that, include: One or more of the following: the perovskite solar cell according to any one of claims 1 to 11; the organic compound according to any one of claims 13 to 15; and the organic compound prepared by the method of the organic compound according to claim 17.

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