Organic compound, electron transport material, electron transport thin film, perovskite solar cell, and electric device

Abstract

The invention provides an organic compound, an electron transport material, an electron transport film, a perovskite solar cell and an electric device. In the organic compound, M can be used as an electron acceptor unit, Z can be used as an electron donor unit, and Z comprises a helical structure group, so that M can be positioned in different planes, and electrons can be transmitted in multiple directions. When the organic compound is applied to the perovskite solar cell, the transmission capability of electrons can be improved, and the photoelectric conversion efficiency of the perovskite solar cell is further improved.

Description

Technical Field

[0001] The present application relates to the technical field of perovskite solar cells, and in particular to an organic compound, an electron transport material, an electron transport film, a perovskite solar cell and an electrical device. Background Art

[0002] The statements herein merely provide background information related to the present application and do not necessarily constitute prior art.

[0003] In perovskite solar cells, the electron transport capability has a significant impact on the photoelectric conversion efficiency of the cell. However, when traditional electron transport materials are applied to perovskite solar cells, the electron transport capability is poor. Summary of the invention

[0004] In order to achieve the above object, the present application provides an organic compound, characterized in that it has a structure shown in formula (1):

[0005]

[0006] Wherein, Z includes a helical structure group; when M appears multiple times, it is independently selected from any one of (M-1) to (M-3):

[0007]

[0008] n is an integer ≥ 2; 0≤m1≤4, 0≤m2≤4, 0≤m3≤4, 0≤m4≤2, and m1, m2, m3, m4 are each independently an integer;

[0009] Each occurrence of R is independently selected from any one of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms;

[0010] R 1 , R 2 , R 3 , R 4 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted thienyl group, and a substituted or unsubstituted phenyl group.

[0011] In the above organic compound, M can be used as an electron acceptor unit and Z can be used as an electron donor unit. Since Z includes a helical structure group, M can be placed in different planes, so that electrons can be transmitted in multiple directions. When the organic compound is applied to a perovskite solar cell, the electron transmission capacity can be improved, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0012] In some embodiments, Z is selected from any one of (Z-1) to (Z-8):

[0013]

[0014] Wherein, each occurrence of Y is independently selected from O, S, Se, NR 5 , C(R 6 ) 2 and Si(R 7 ) 2 Any of the following:

[0015] R 5 , R 6 , R 7 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted thienyl group.

[0016] In some embodiments, formula (1) is selected from any one of the following structures:

[0017]

[0018]

[0019] In some embodiments, formula (1) is selected from any one of the following structures:

[0020]

[0021] In some embodiments, n is 2, 3, or 4.

[0022] In some embodiments, the substituent of the substituted alkyl group having 1 to 20 carbon atoms includes a basic group.

[0023] In some embodiments, the substituent of the substituted cycloalkyl group having 3 to 20 carbon atoms includes a basic group.

[0024] In some embodiments, the substituents of the substituted thienyl group include a basic group.

[0025] In some embodiments, the substituents of the substituted phenyl group include a basic group.

[0026] In some embodiments, the basic group comprises NR 8 , PR 9 and at least one of pyridyl; wherein R 8 , R 9They are independently selected from H, D, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms.

[0027] In some embodiments, the basic group includes at least one of a dimethylamino group, a dimethylphosphino group, and a dibutylphosphino group.

[0028] The present application also provides an electron transport material, comprising the organic compound.

[0029] The present application also provides an electron transport film, comprising the electron transport material.

[0030] The present application also provides a perovskite solar cell. The perovskite solar cell comprises a stacked perovskite film and the electron transport film.

[0031] In some embodiments, the electron transport film further includes an N-type doping material.

[0032] In some embodiments, the N-type doping material includes at least one of an organic amine, an organic phosphine, an amino metal salt, an alkyl metal salt, a quaternary ammonium hydrohalide, a quaternary ammonium tetrafluoroborate, a quaternary ammonium hexafluorophosphate, a quaternary phosphonium hydrohalide, a quaternary phosphonium tetrafluoroborate, a quaternary phosphonium hexafluorophosphate, a polymer containing a quaternary ammonium group, and a polymer containing a quaternary phosphonium group.

[0033] In some embodiments, the N-type doping material includes at least one of the following materials:

[0034]

[0035] In some embodiments, the mass percentage of the N-type doping material is 0.01% to 10% based on the mass percentage of the electron transport film.

[0036] In some embodiments, the mass percentage of the N-type doping material is 0.05% to 1%.

[0037] In some embodiments, the electron transport thin film has a thickness of 5 nm to 100 nm.

[0038] In some embodiments, the perovskite solar cell further includes a hole transport film, and the hole transport film is located on a side of the perovskite film away from the electron transport film.

[0039] The present application also provides an electrical device, comprising the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on the drawings without creative work.

[0041] Figure 1 Schematic diagram of the structure of an inverted perovskite solar cell in one embodiment of the present application.

[0042] Figure 2 This is a schematic structural diagram of a formal perovskite solar cell in another embodiment of the present application.

[0043] Figure 3 It is a schematic diagram of an electrical device in one embodiment of the present application.

[0044] 100. Perovskite solar cell; 101. Base layer; 102. Transparent electrode layer; 103. Hole transport layer; 104. Perovskite layer; 105. Electron transport layer; 106. Metal electrode layer; 200. Perovskite solar cell; 201. Base layer; 202. Transparent electrode layer; 203. Hole transport layer; 204. Perovskite layer; 205. Electron transport layer; 206. Metal electrode layer; 300. Electrical device.

[0045] In order to better describe and illustrate the embodiments and / or examples of the inventions disclosed herein, reference may be made to one or more drawings. The additional details or examples used to describe the drawings should not be considered to limit the scope of the disclosed inventions, the embodiments and / or examples currently described, and any of the best modes of these inventions currently understood. DETAILED DESCRIPTION

[0046] The following is a further detailed description of the perovskite solar cell and its preparation method and electrical device of the present application in conjunction with specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0047] The details of one or more embodiments of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0049] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0050] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0051] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0052] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0053] If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0054] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true or exists, and B is false or does not exist; A is false or does not exist, and B is true or exists; or both A and B are true, or both A and B exist.

[0055] If not otherwise specified, in the present application, the term "room temperature" generally refers to 4°C to 30°C, preferably 25±5°C.

[0056] Unless otherwise stated, the terms used in this application have the well-known meanings commonly understood by those skilled in the art. Unless otherwise stated, the numerical values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art. For example, the test can be performed according to the method provided in the examples of this application.

[0057] An embodiment of the present application provides an organic compound. The organic compound has a structure shown in formula (1):

[0058]

[0059] Wherein, Z includes a helical structure group; when M appears multiple times, it is independently selected from any one of (M-1) to (M-2):

[0060]

[0061] n is an integer ≥ 2; 0≤m1≤4, 0≤m2≤4, 0≤m3≤4, 0≤m4≤2, and m1, m2, m3, m4 are each independently an integer;

[0062] Each occurrence of R is independently selected from any one of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms;

[0063] R 1 , R 2 , R 3 , R 4 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted thienyl group, and a substituted or unsubstituted phenyl group.

[0064] It can be understood that the helical structure group means that the group has structures that are not in the same plane, that is, the group has structures located in multiple planes.

[0065] In the organic compound of this embodiment, M can be used as an electron acceptor unit and Z can be used as an electron donor unit. Since Z includes a helical structure group, M can be placed in different planes, so that electrons can be transmitted in multiple directions. When the organic compound is applied to a perovskite solar cell, the electron transmission capacity can be improved, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0066] It is understood that n represents the number of M in the organic compound. m1 represents the number of R in (M-1). 1 m2 represents the number of R in (M-2) 2 m3 represents the number of R in (M-2) 3 m4 represents the number of R in (M-3) 4 The number of

[0067] Furthermore, in (M-1), (R 1 ) m1 The connection mode with the condensed ring indicates R 1 It can be connected to the m1 substitution sites on the corresponding fused ring. For example, (M-1) can be any of the following structures:

[0068]

[0069] Furthermore, in (M-2), (R 2 ) m2 , (R 3 ) m3 The connection mode with the condensed ring indicates R 2 and R 3 They can be connected to the m2 and m3 substitution sites on the corresponding fused rings. For example, (M-2) can be any of the following structures:

[0070]

[0071]

[0072] Furthermore, in (M-3), (R 4 ) m4 The connection mode with the condensed ring indicates R 4 It can be connected to the m4 substitution sites on the corresponding fused ring. For example, (M-3) can be any one of the following structures:

[0073]

[0074] In some embodiments, m1 is 0, 1, 2, 3, or 4. m2 is 0, 1, 2, 3, or 4. m3 is 0, 1, 2, 3, or 4. m4 is 0, 1, or 2.

[0075] It is understood that alkyl refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or combinations thereof. Phrases containing this term, for example, "alkyl having 1 to 20 carbon atoms" means an alkyl group containing 1 to 20 carbon atoms, and each occurrence can be independently an alkyl having 1 carbon atom, an alkyl having 2 carbon atoms, an alkyl having 3 carbon atoms, an alkyl having 4 carbon atoms, an alkyl having 5 carbon atoms, an alkyl having 6 carbon atoms, an alkyl having 7 carbon atoms, an alkyl having 8 carbon atoms, an alkyl having 9 carbon atoms, an alkyl having 10 carbon atoms, an alkyl having 11 carbon atoms, an alkyl having 12 carbon atoms, an alkyl having 13 carbon atoms, an alkyl having 14 carbon atoms, an alkyl having 15 carbon atoms, an alkyl having 16 carbon atoms, an alkyl having 17 carbon atoms, an alkyl having 18 carbon atoms, an alkyl having 19 carbon atoms, or an alkyl having 20 carbon atoms. For another example, "C 1 ~C 20 "Alkyl" refers to an alkyl group containing 1 to 20 carbon atoms, each occurrence of which can be independently C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl, C 9 Alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl, C 13 Alkyl, C 14 Alkyl, C 15 Alkyl, C 16 Alkyl, C 17 Alkyl, C 18 Alkyl, C 19 Alkyl or C 20 alkyl.

[0076] Cycloalkyl refers to a non-aromatic hydrocarbon containing ring carbon atoms, and may be a monocyclic alkyl, a spirocyclic alkyl, or a bridged cycloalkyl. A phrase containing this term, for example, "cycloalkyl having 3 to 20 carbon atoms" refers to a cycloalkyl having 3 to 20 carbon atoms, and each occurrence may be independently a cycloalkyl having 3 carbon atoms, a cycloalkyl having 4 carbon atoms, a cycloalkyl having 5 carbon atoms, a cycloalkyl having 6 carbon atoms, a cycloalkyl having 7 carbon atoms, a cycloalkyl having 8 carbon atoms, a cycloalkyl having 9 carbon atoms, a cycloalkyl having 10 carbon atoms, a cycloalkyl having 11 carbon atoms, a cycloalkyl having 12 carbon atoms, a cycloalkyl having 13 carbon atoms, a cycloalkyl having 14 carbon atoms, a cycloalkyl having 15 carbon atoms, a cycloalkyl having 16 carbon atoms, a cycloalkyl having 17 carbon atoms, a cycloalkyl having 18 carbon atoms, a cycloalkyl having 19 carbon atoms, or a cycloalkyl having 20 carbon atoms. For example, "C 3 ~C 20 "Cycloalkyl" refers to a cycloalkyl group containing 3 to 9 carbon atoms, each occurrence of which can be independently C 3 Cycloalkyl, C 4 Cycloalkyl, C 5 Cycloalkyl, C 6 Cycloalkyl, C 7 Cycloalkyl, C 8 Cycloalkyl, C 9 Cycloalkyl, C 10 Cycloalkyl, C 11 Cycloalkyl, C 12 Cycloalkyl, C 13 Cycloalkyl, C 14 Cycloalkyl, C 15 Cycloalkyl, C 16 Cycloalkyl, C 17 Cycloalkyl, C 18 Cycloalkyl, C 19 Cycloalkyl or C 20 Cycloalkyl. Alternatively, suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutadienyl.

[0077] Aryl refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. Phrases containing this term, for example, "aryl having 6 to 20 carbon atoms" refers to an aromatic group containing 6 to 20 carbon atoms. Each time it appears, it can be independently an aromatic group having 6 carbon atoms, an aromatic group having 10 carbon atoms, an aromatic group having 14 carbon atoms, an aromatic group having 18 carbon atoms, or an aromatic group having 20 carbon atoms. For another example, "C6 ~C 20 "Aryl" refers to an aromatic group containing 6 to 20 carbon atoms, each occurrence of which can be independently C 6 Aryl, C 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Alternatively, suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene and derivatives thereof.

[0078] It should be noted that "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, heteroalkyl, heterocyclyl, amino, halogen.

[0079] In some embodiments, n is an integer ≥3, or n is an integer ≥4, or n is an integer ≥5, or n is an integer ≥6, or n is an integer ≥7, or n is an integer ≥8, or n is an integer ≥9, or n is an integer ≥10. Optionally, 2≤n≤10. Further optionally, n is 2, 3 or 4.

[0080] In some embodiments, Z is selected from any one of (Z-1) to (Z-8):

[0081]

[0082] Wherein, each occurrence of Y is independently selected from O, S, Se, NR 5 , C(R 6 ) 2 and Si(R 7 ) 2 Any one of R 5 , R 6 , R 7 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted thienyl group.

[0083] In some embodiments, formula (1) is selected from any one of the following structures:

[0084]

[0085] It is understood that the connection mode of M to the ring or condensed ring means that M can be connected to any substitution site on the corresponding ring or condensed ring.

[0086] Optionally, formula (1) is selected from any one of the following structures:

[0087]

[0088] In some embodiments, the substituent of the substituted alkyl group having 1 to 20 carbon atoms includes a basic group. By introducing a basic group, the electron transport performance of the organic compound can be further improved, and the photoelectric conversion efficiency of the perovskite solar cell can be further improved when the organic compound is applied to the perovskite solar cell. Optionally, the basic group is located at the end of the alkyl group. It is understood that when the alkyl group is a straight-chain alkyl group, the basic group is located at the end of the straight-chain alkyl group. When the alkyl group is a branched alkyl group, the basic group is located at the end of at least one branch. Further, when the alkyl group is a branched alkyl group, the basic group can also be located at the end of the main chain.

[0089] In some embodiments, the substituent of the substituted cycloalkyl group having 1 to 20 carbon atoms includes a basic group. By introducing the basic group, the electron transport performance of the organic compound can be further improved, and the photoelectric conversion efficiency of the perovskite solar cell can be further improved when the organic compound is applied to the perovskite solar cell.

[0090] In some embodiments, the substituent of the substituted thienyl group includes a basic group. By introducing the basic group, the electron transport performance of the organic compound can be further improved, and the photoelectric conversion efficiency of the perovskite solar cell can be further improved when the organic compound is applied to the perovskite solar cell.

[0091] In some embodiments, the substituent of the substituted phenyl group includes a basic group. By introducing the basic group, the electron transport performance of the organic compound can be further improved, and the photoelectric conversion efficiency of the perovskite solar cell can be further improved when the organic compound is applied to the perovskite solar cell.

[0092] In some embodiments, the basic group comprises NR 8 , PR 9 and at least one of pyridyl; wherein R 8 , R 9 Independently selected from H, D, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms. Optionally, the basic group includes at least one of dimethylamino, dimethylphosphino and dibutylphosphino.

[0093] In some embodiments, the organic compound has any one of the following structures (A-1) to (A-11):

[0094]

[0095] In (A-1), R can be selected from

[0096] In (A-2), R can be selected from

[0097] In (A-3), R can be selected from

[0098] In (A-4), R can be selected from

[0099] In (A-5), R can be selected from

[0100] In (A-6), R can be selected from

[0101]

[0102] In (A-7), R can be selected from

[0103]

[0104] In (A-8), R can be selected from R 5 Optional

[0105]

[0106] In (A-9), R can be selected from R 4 Optional

[0107] In (A-10), R can be selected from R 5 Optional

[0108]

[0109] In (A-11), R can be selected from

[0110] Another embodiment of the present application provides an electron transport material. The electron transport material includes the above-mentioned organic compound. Introducing the above-mentioned organic compound into the electron transport material can make the electron transport material have a higher electron transport capacity. Applying the electron transport material to a perovskite solar cell can improve the photoelectric conversion efficiency of the perovskite solar cell.

[0111] Another embodiment of the present application provides an electron transport film. The electron transport film comprises the above-mentioned electron transport material. Optionally, the electron transport film can be prepared by a solution method. Further optionally, the above-mentioned electron transport material can be dissolved in an organic solvent to obtain a solution. The solution is then transferred to the surface of the perovskite film by spin coating, spraying, scraping, slit coating, or roll-to-roll printing, and the solvent is removed by annealing or vacuum to obtain the electron transport film. Further optionally, the organic solvent can be one or more of dichloromethane, chloroform, carbon tetrachloride, chlorobenzene and dichlorobenzene. Further optionally, the concentration of the electron transport material in the solution is 1 mg / mL to 40 mg / mL.

[0112] Another embodiment of the present application provides a perovskite solar cell. The perovskite solar cell includes a stacked perovskite film and the above-mentioned electron transport film.

[0113] In some embodiments, the electron transport film further comprises an N-type doping material. Optionally, the N-type doping material comprises at least one of an organic amine, an organic phosphine, an amino metal salt, an alkyl metal salt, a quaternary ammonium halide, a quaternary ammonium borate, a quaternary ammonium phosphate, a phosphine hydrogen halide, a phosphine hydrogen borate, a phosphine hydrogen phosphate, a polymer containing a quaternary ammonium group, and a polymer containing a phosphine hydrogen group. When the electron transport film further comprises an N-type doping material, the transmission of electrons can be further promoted, and the photoelectric conversion efficiency of the perovskite solar cell can be further improved.

[0114] In some embodiments, the mass percentage of the N-type doping material is 0.01% to 10% in terms of the mass percentage of the electron transport film. Optionally, the mass percentage of the N-type doping material is 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. Optionally, the mass percentage of the N-type doping material is 0.05% to 1%. If the mass percentage of the N-type doping material is too small, the improvement effect is poor. If the mass percentage of the N-type doping material is too large, the amount of the electron transport material will be reduced accordingly, which may limit the effect of the electron transport material.

[0115] In some embodiments, the N-type doping material includes at least one of the following materials:

[0116]

[0117] Here, n is any integer from 1 to 200.

[0118] In some embodiments, the thickness of the electron transport film is 5nm to 100nm. Optionally, the thickness of the electron transport film is 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc. If the thickness of the electron transport film is too small, the effect of the electron transport film may be poor. If the thickness of the electron transport film is too large, the thickness of the perovskite solar cell may increase, and the volume and weight of the perovskite solar cell may increase.

[0119] In some embodiments, the perovskite solar cell further includes a hole transport film, which is located on a side of the perovskite film away from the electron transport film.

[0120] It is understood that the perovskite film includes a chemical formula of ABX 3 or A 2 CDX 6 Materials, including:

[0121] A is an inorganic or organic or organic-inorganic mixed cation, comprising at least one of an organic amine cation, a Cs cation, a K cation, a Rb cation and a Li cation; the organic amine cation is selected from (NR1R2R3R4) + 、(R1R2N=CR3R4) + 、(R1R2N-C(R5)=NR3R4) + or (R1R2N-C(NR5R6)=R3R4) + , wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, substituted or unsubstituted C1-20 alkyl or substituted or unsubstituted aryl; A is optionally methylamino (CH 3 NH 3 + )(MA + ), carboxamidino (HC(NH 2 ) 2 + )(FA + ), cesium ion (Cs + ) and rubidium (Rb + ), and further optionally methylamino (CH 3 NH 3 + ) or carboxamidino (HC(NH 2 ) 2+ ).

[0122] B is an inorganic or organic or organic-inorganic mixed cation, including at least one of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium, and optionally a divalent metal ion Pb 2+ and Sn 2+ At least one of .

[0123] C is an inorganic or organic or organic-inorganic mixed cation, optionally a monovalent metal ion Ag. + wait.

[0124] D is an inorganic or organic or organic-inorganic mixed cation, optionally a trivalent metal ion bismuth cation Bi 3+ 、Antimony cation Sb 3+ 、Indium cation In 3+ wait.

[0125] X is an inorganic or organic or organic-inorganic mixed anion, optionally one or more of a halogen anion and a carboxylate anion, and further optionally a bromide ion (Br - ) or iodide ion (I - ).

[0126] In some embodiments, the thickness of the perovskite film is 100nm-1000nm; as an example, the thickness of the perovskite film can be but is not limited to 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm or a range between any two of the above values.

[0127] In some embodiments, the band gap of the perovskite film is 1.2 eV to 2.3 eV. As an example, the band gap of the perovskite film is 1.2 eV, 1.3 eV, 1.4 eV, 1.5 eV, 1.6 eV, 1.7 eV, 1.8 eV, 1.9 eV, 2 eV, 2.1 eV, 2.2 eV, 2.3 eV, or a range between any two of the above values. When the band gap of the perovskite film is within the above range, it can have a higher visible light absorption efficiency.

[0128] In some embodiments, the material of the electron transport film may also include but is not limited to one or more of the following materials and their derivatives: imide compounds, quinone compounds, fullerenes and their derivatives, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), calcium titanate (CaTiO 3 ), lithium fluoride (LiF), calcium fluoride (CaF 2), poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides, silicon oxide (SiO 2 ), SrTiO 3 ), cuprous thiocyanate (CuSCN), etc.; wherein the metal elements may include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr.

[0129] In some embodiments, the material of the hole transport film may include, but is not limited to, one or more of the following materials and their derivatives: 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), nickel oxide (NiO x ), molybdenum oxide (MoO x )tungsten oxide (WO x ), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS) and other materials can transport holes and block electrons. Optionally, the thickness of the hole transport film is 0.1nm to 100nm.

[0130] It is understandable that the perovskite solar cell also includes a transparent electrode layer and a metal electrode layer, the transparent electrode layer is located on the side of the perovskite film away from the electron transport film, and the metal electrode layer is located on the side of the electron transport film away from the perovskite film.

[0131] Optionally, the transparent electrode layer is selected from at least one of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO) and indium tungsten oxide (IWO). Optionally, the thickness of the transparent electrode layer is 10nm to 1000nm, and further optionally 300nm to 800nm.

[0132] Optionally, the metal electrode layer is selected from at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof. Optionally, the thickness of the metal electrode layer is 20nm to 200nm, optionally 60nm to 100nm, and further optionally 70nm to 90nm.

[0133] It is understood that the perovskite solar cell also includes a substrate layer. A transparent electrode layer is formed on the substrate layer. The substrate layer includes a glass substrate and a flexible substrate. The material of the flexible substrate layer may be, for example, (but not limited to) an organic polymer material. Further, the material of the flexible substrate layer may be mixed by 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), etc.

[0134] It is understood that perovskite solar cells include formal perovskite solar cells and inverted perovskite solar cells. For formal perovskite solar cells, formal perovskite solar cells include a transparent electrode layer and an electron transport film, a perovskite film, a hole transport film and a metal electrode layer stacked sequentially on the transparent electrode layer. For inverted perovskite solar cells, inverted perovskite solar cells include a transparent electrode layer and a hole transport film, a perovskite film, an electron transport film and a metal electrode layer stacked sequentially on the transparent electrode layer.

[0135] It is understandable that other functional layers, such as a buffer layer, can be introduced into the perovskite solar cell as required.

[0136] In some embodiments, a perovskite solar cell may be provided with a buffer layer with a suitable energy level, which may play one or more of the following roles: reducing energy level barriers, promoting energy level matching, improving carrier extraction efficiency, passivating interface defect states, protecting the light absorption layer, inhibiting water molecules, oxygen oxidation and decomposition of the battery, improving photoelectric conversion efficiency, and improving the stability of the perovskite solar cell. Depending on the location of the buffer layer, the types of buffer layers may include four types: a buffer layer between a hole transport film and a metal electrode layer, a buffer layer between an electron transport film and a transparent electrode layer, a buffer layer between a hole transport film and a perovskite film, and a buffer layer between an electron transport film and a perovskite film. The materials that can be used for the buffer layer in a perovskite solar cell may include, but are not limited to: Cu 2 O, NiO, AZO, TiO 2 wait.

[0137] See also Figure 1 , which shows the structure of an inverted perovskite solar cell 100 in one embodiment of the present application. The perovskite solar cell 100 includes a substrate layer 101, a transparent electrode layer 102, a hole transport film 103, a perovskite film 104, an electron transport film 105 and a metal electrode layer 106 stacked in sequence. The electron transport film may be the electron transport film in the above embodiment of the present application.

[0138] See also Figure 2, which shows the structure of a formal perovskite solar cell 200 in another embodiment of the present application. The perovskite solar cell 200 includes a substrate layer 201, a transparent electrode layer 202, an electron transport film 203, a perovskite film 204, a hole transport film 205 and a metal electrode layer 206 stacked in sequence. The electron transport film can be the electron transport film in the above embodiment of the present application.

[0139] Another embodiment of the present application provides an electrical device, characterized in that it includes the above-mentioned perovskite solar cell.

[0140] In some embodiments, the perovskite solar cell can be used as a power generation device of an electrical device. The type of the power generation device can include but is not limited to integrated power generation. The location of the power generation device can include but is not limited to the roof, back panel, etc. of a car.

[0141] Furthermore, the above-mentioned electrical devices may include mobile devices, such as mobile phones, laptop computers, etc., electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited thereto.

[0142] Figure 3 The power consumption device 300 is an automobile, and may further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0143] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0144] As another example, the power-consuming device may be a wearable device, such as a watch.

[0145] Example

[0146] In order to make the technical problems, technical solutions and beneficial effects solved by the present application clearer, the present application will be further described in detail below in conjunction with the embodiments and drawings. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present application and its applications. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.

[0147] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0148] Example 1

[0149] The preparation method of the organic compound in this embodiment is:

[0150] Step 1: 6.27 g of compound 1, 10.16 g of compound 2, 2.8 g of Pd(PPh 3 )Cl 2 , and 13.0 g of sodium acetate (NaOAc) were dissolved in 100 mL of 1,4-dioxane. After stirring at 80° C. for 12 h, 8.15 g of compound 3 was obtained by separation through a chromatography silica gel column with a yield of 99%.

[0151]

[0152] Step 2: Dissolve 4.11 g of compound 3, 13.6 g of compound 4 and 13.6 g of potassium carbonate in 100 mL of a mixed solvent of toluene and water, with a volume ratio of toluene to water of 3:2. After heating under reflux for 48 h, separate the mixture through a chromatographic silica gel column to obtain 5.21 g of compound A-1 with a yield of 51%.

[0153]

[0154] Example 2

[0155] Compared with Example 1, the difference of this example is that the compound 4 in step 2 is replaced by 12.5 g of compound 5, wherein the difference between compound 4 and compound 5 is that R is different. 8.10 g of compound A-2 is obtained, and the yield is 65%.

[0156]

[0157] Example 3

[0158] Compared with Example 1, the difference of this example is that compound 4 in step 2 is replaced by 15.6 g of compound 6.

[0159] 9.18 g of compound A-3 was obtained with a yield of 59%.

[0160]

[0161] Example 4

[0162] Compared with Example 1, the difference of this example is that compound 4 in step 2 is replaced by 15.3 g of compound 7.

[0163] 7.91 g of compound A-4 was obtained with a yield of 52%.

[0164]

[0165] Example 5

[0166] Compared with Example 1, the difference of this example is that compound 4 in step 2 is replaced by 17.7 g of compound 8.

[0167] 6.02 g of compound A-5 was obtained with a yield of 34%.

[0168]

[0169] Example 6

[0170] Compared with Example 4, the difference of this example is that compound 3 in step 2 is replaced by 4.18 g of compound 9.

[0171] 6.88 g of compound A-6 was obtained with a yield of 45%.

[0172]

[0173] Example 7

[0174] Compared with Example 4, the difference of this example is that compound 3 in step 2 is replaced by 4.18 g of compound 10.

[0175] 6.74 g of compound A-7 was obtained with a yield of 44%.

[0176]

[0177] Example 8

[0178] Compared with Example 4, the difference of this example is that compound 3 in step 2 is replaced by 3.22 g of compound 11.

[0179] 5.53 g of compound A-8 was obtained with a yield of 63%.

[0180]

[0181] Example 9

[0182] Compared with Example 4, the difference of this example is that compound 3 in step 2 is replaced by 2.66 g of compound 12.

[0183] 4.77 g of compound A-9 was obtained with a yield of 58%.

[0184]

[0185] Example 10

[0186] Compared with Example 4, the difference of this example is that compound 3 in step 2 is replaced by 3.28 g of compound 13.

[0187] 3.45 g of compound A-10 was obtained with a yield of 39%.

[0188]

[0189] Preparation of perovskite solar cells.

[0190] Embodiment 11

[0191] Compared with Example 1, the difference of this example is that compound 4 in step 2 is replaced by 11.5 g of compound 14.

[0192] 3.87 g of compound A-11 was obtained with a yield of 36%.

[0193]

[0194] Battery 1

[0195] The preparation method of battery 1 is as follows:

[0196] (1) Take 20 pieces of FTO conductive glass with a size of 2.0×2.0 cm, remove 0.35 cm of FTO at both ends by laser etching, and expose the glass substrate.

[0197] (2) Ultrasonic cleaning of the etched FTO conductive glass was performed several times using water, acetone, and isopropanol in turn.

[0198] (3) The FTO conductive glass was blown dry of solvent under a nitrogen gun and placed in a UV ozone machine for further cleaning.

[0199] (4) 10 mg / mL nickel oxide nanoparticles (water as solvent) were spin-coated on the FTO substrate after UV-ozone treatment at a rate of 4000 rpm, and annealed on a hot plate at 100° C. for 30 minutes to obtain a hole transport film.

[0200] (5) Weigh lead iodide, iodoformamidine, cesium iodide, and lead bromide and dissolve them in a mixed solution of DMF and DMSO, stir for 3 hours, and filter with a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. Spin-coat the perovskite precursor solution on the hole transport film at 3000 rpm, anneal at 100° C. for 30 minutes, and cool to room temperature to obtain a perovskite film.

[0201] (6) The organic compound A-1 in Example 1 was weighed and dissolved in chlorobenzene, and the mixture was spin-coated on the perovskite film at a rotation speed of 1500 rpm. The mixture was annealed at 100° C. for 10 min to obtain an electron transport film.

[0202] (7) A metal electrode Ag is evaporated on the electron transport film to obtain a battery 1.

[0203] Battery 2

[0204] Compared with battery 1, the preparation method of battery 2 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-2 in Example 2.

[0205] Battery 3

[0206] Compared with battery 1, the preparation method of battery 3 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-3 in Example 3.

[0207] Battery 4

[0208] Compared with battery 1, the preparation method of battery 4 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-4 in Example 4.

[0209] Battery 5

[0210] Compared with battery 1, the preparation method of battery 5 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-5 in Example 5.

[0211] Battery 6

[0212] Compared with the battery 1, the preparation method of the battery 6 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-6 in Example 6.

[0213] Battery 7

[0214] Compared with battery 1, the preparation method of battery 7 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-7 in Example 7.

[0215] Battery 8

[0216] Compared with battery 1, the preparation method of battery 8 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-8 in Example 8.

[0217] Battery 9

[0218] Compared with battery 1, the preparation method of battery 9 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-9 in Example 9.

[0219] Battery 10

[0220] Compared with the battery 1, the preparation method of the battery 10 is different in that the organic compound A-1 in Example 1 is replaced by the organic compound A-10 in Example 10.

[0221] Battery 11

[0222] Compared with battery 1, the preparation method of battery 11 is different in that compound 15 is added to chlorobenzene in step (6) for doping to obtain battery 11. The mass percentage of compound 15 in terms of mass percentage of the electron transport film is 0.5%.

[0223] Battery 12

[0224] Compared with battery 2, the preparation method of battery 12 is different in that compound 16 is added to chlorobenzene in step (6) for doping to obtain battery 12. The mass percentage of compound 16 in terms of mass percentage of the electron transport film is 0.5%.

[0225] Battery 13

[0226] Compared with battery 4, the preparation method of battery 13 is different in that compound 17 is added to chlorobenzene in step (6) for doping to obtain battery 13. The mass percentage of compound 17 in terms of mass percentage of the electron transport film is 0.5%.

[0227] Battery 14

[0228] Compared with battery 4, the preparation method of battery 14 is different in that compound 18 is added to chlorobenzene in step (6) for doping to obtain battery 14. The mass percentage of compound 18 in terms of mass percentage of the electron transport film is 0.5%.

[0229] Battery 15

[0230] Compared with battery 4, the preparation method of battery 15 is different in that compound 19 is added to chlorobenzene in step (6) for doping to obtain battery 15. The mass percentage of compound 19 in terms of mass percentage of the electron transport film is 0.5%.

[0231] Battery 16

[0232] Compared with battery 5, the preparation method of battery 16 is different in that compound 20 is added to chlorobenzene in step (6) for doping to obtain battery 16. The mass percentage of compound 20 in terms of mass percentage of the electron transport film is 0.5%.

[0233] Battery 17

[0234] Compared with battery 1, the preparation method of battery 17 is different in that the organic compound A-1 in Example 1 is replaced by PC 61 BM.

[0235] Battery 18

[0236] Compared with battery 1, the preparation method of battery 18 is different in that the organic compound A-1 in Example 1 is replaced by PC 61 BM, and adding compound 18 to the chlorobenzene in step (6) for doping to obtain battery 18. Wherein, the mass percentage of compound 18 is 0.5% based on the mass percentage of the electron transport film.

[0237] The structural formulas of compounds 15 to 20 are as follows:

[0238]

[0239] Test Case

[0240] The photoelectric conversion efficiency of cells 1 to 19 was tested. A solar simulator was used to test in accordance with the national standard IEC61215, and a crystalline silicon solar cell was used to calibrate the light intensity to reach one sun intensity, AM1.5. The test results are shown in Table 1.

[0241] Table 1

[0242]

[0243]

[0244] It can be seen from Table 1 that compared with battery 18 and battery 18, battery 1 to battery 17 have higher photoelectric conversion efficiency, and the attenuation of the photoelectric conversion efficiency on the 30th day is significantly lower. This shows that battery 1 to battery 17 have higher photoelectric conversion efficiency and the photoelectric conversion efficiency has higher stability. In addition, when the electron transport film contains N-type doping material, the photoelectric conversion rate of the battery is higher.

[0245] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0246] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. An organic compound, It is characterized in that It has the structure shown in formula (1): Wherein, Z includes a helical structure group; when M appears multiple times, it is independently selected from any one of (M-1) to (M-3): n is an integer ≥ 2; 0≤m1≤4, 0≤m2≤4, 0≤m3≤4, 0≤m4≤2, and m1, m2, m3, m4 are each independently an integer; Each occurrence of R is independently selected from any one of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; R 1 , R 2 , R 3 , R 4 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted thienyl group, and a substituted or unsubstituted phenyl group.

2. The organic compound according to claim 1, It is characterized in that Z is selected from any one of (Z-1) to (Z-8): Wherein, each occurrence of Y is independently selected from O, S, Se, NR 5 , C(R 6 ) 2 and Si(R 7 ) 2 Any of the following; R 5 , R 6 , R 7 Any one independently selected from the group consisting of H, D, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted thienyl group.

3. The organic compound according to claim 2, It is characterized in that Formula (1) is selected from any one of the following structures:

4. The organic compound according to claim 3, It is characterized in that Formula (1) is selected from any one of the following structures:

5. The organic compound according to any one of claims 1 to 4, It is characterized in that n is 2, 3 or 4.

6. The organic compound according to any one of claims 1 to 5, It is characterized in that The substituent of the substituted alkyl group having 1 to 20 carbon atoms includes a basic group; and / or, The substituent of the substituted cycloalkyl group having 3 to 20 carbon atoms includes a basic group; and / or, The substituent of the substituted thienyl group comprises a basic group; and / or, Substituents of the substituted phenyl group include basic groups.

7. The organic compound according to claim 6, It is characterized in that The basic groups include NR 8 , PR 9 and at least one of pyridyl; wherein R 8 , R 9 independently selected from H, D, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; Optionally, the basic group includes at least one of a dimethylamino group, a dimethylphosphino group and a dibutylphosphino group.

8. An electron transport material, It is characterized in that The organic compound according to any one of claims 1 to 7.

9. An electron transport film, It is characterized in that Contains the electron transport material according to claim 8.

10. A perovskite solar cell, It is characterized in that The perovskite solar cell comprises a stacked perovskite film and the electron transport film according to claim 9.

11. The perovskite solar cell according to claim 10, It is characterized in that The electron transport film further comprises an N-type doping material; Optionally, the N-type doping material includes at least one of an organic amine, an organic phosphine, an amino metal salt, an alkyl metal salt, a quaternary ammonium hydrohalide, a quaternary ammonium tetrafluoroborate, a quaternary ammonium hexafluorophosphate, a quaternary phosphonium hydrohalide, a quaternary phosphonium tetrafluoroborate, a quaternary phosphonium hexafluorophosphate, a polymer containing a quaternary ammonium group, and a polymer containing a quaternary phosphonium group; Optionally, the N-type doping material includes at least one of the following materials:

12. The perovskite solar cell according to claim 11, It is characterized in that The mass percentage of the N-type doping material is 0.01% to 10% based on the mass percentage of the electron transport film; Optionally, the mass percentage of the N-type doping material is 0.05% to 1%.

13. The perovskite solar cell according to any one of claims 10 to 12, It is characterized in that The thickness of the electron transport film is 5nm-100nm.

14. The perovskite solar cell according to any one of claims 10 to 13, It is characterized in that The perovskite solar cell further comprises a hole transport film, and the hole transport film is located on a side of the perovskite film away from the electron transport film.

15. An electrical device, It is characterized in that A perovskite solar cell comprising the perovskite solar cell according to any one of claims 10 to 14.

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