Oligomer and organic electronic device containing same

Abstract

The invention relates to the field of organic photovoltaic cell materials, in particular to an oligomer which connects three non-fullerene acceptor small molecule units through flexible units, so that on one hand, the rigidity of a main chain can be reduced, and the blending degree between a donor and an acceptor is enhanced; on the other hand, separation of appropriate donor or acceptor nanobelt phases can be promoted, so that dissociation and transmission of charges are improved. When the compound is applied to an organic photovoltaic cell device, the photoelectric conversion efficiency of the device can be improved.

Description

Technical Field

[0001] The invention relates to the field of organic photovoltaic cell materials, in particular to an oligomer and an organic electronic device containing the oligomer. Background Art

[0002] Solar energy, like other clean energy sources such as wind energy and tidal energy, produces almost no pollution when it is developed and utilized. In addition, its reserves are unlimited, making it an ideal alternative energy source for mankind. As an emerging photovoltaic technology, organic solar cells are an ideal photoelectric conversion technology currently used in wearable electronic devices, Internet of Things devices, building photovoltaic integration and other scenarios due to their low cost, high efficiency, flexibility, color, translucency, and solution processability. They have attracted great attention. In recent years, thanks to the rapid development of organic photovoltaic materials, the photoelectric conversion efficiency of its devices has made great progress, achieving a leap forward from basic research to industrialization.

[0003] The materials of the photoactive layer of organic photovoltaic cells are mainly divided into donor materials and acceptor materials. Depending on their different energy levels and absorption spectra, the absorbed light energy can be converted into electrical energy in the photoactive layer. Currently, the commonly used acceptor materials are based on the "Y" series non-fullerene acceptors with A-DA'DA configuration, such as Y6. This type of non-fullerene acceptor material is prone to molecular diffusion and self-aggregation under external stress such as light and heat, resulting in the formation of metastable morphology. Therefore, it is necessary to further develop new acceptor materials to optimize the morphology of the photoactive layer of organic photovoltaic cells.

[0004] Based on this, oligomer receptors are continuously developed. Researchers have developed oligomers containing 2 or 3 non-fullerene receptor small molecule units through single bonds, double bonds or thiophene π bridge connections, and used such oligomers as non-fullerene receptor materials to stabilize the morphology of the active layer. However, most of the current oligomer non-fullerene receptor materials use a rigid connection method to connect multiple non-fullerene small molecule units to increase the conjugated main chain of the oligomer receptor to achieve the purpose of regulating the crystallization behavior and morphology of the photoactive layer. However, there are few studies on the flexible connection of multiple non-fullerene receptors, which have not been effectively explored. Summary of the invention

[0005] The purpose of the present invention is to develop a new type of oligomer, which connects non-fullerene small molecule units through flexible connection units to form an oligomer non-fullerene acceptor material. The flexible connection can reduce the rigidity of the main chain to a certain extent, thereby enhancing the degree of mixing between the photoactive layer donor and the acceptor, thereby improving the photoelectric performance of the device.

[0006] To achieve the purpose of the present invention, the technical solution provided by the present invention is as follows:

[0007] An oligomer having a structure as shown in general formula (I):

[0008]

[0009] in:

[0010] Each occurrence of L is independently selected from Each occurrence of X1 is independently selected from one or a combination of -O-, -S-, -COO- or -CH2-, and m1 is selected from any integer from 1 to 10;

[0011] Ar1, at each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or

[0012] X is selected from CH, N or B; Ar3, each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms, a substituted or unsubstituted aromatic group having 6-20 carbon atoms;

[0013] Ar2 is independently selected at each occurrence from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms;

[0014] Each occurrence is independently selected from formula (II-1) or (II-2):

[0015]

[0016]

[0017] Ar4 and Ar5 are each independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms;

[0018] Each occurrence of M is independently selected from O or C(CN)2;

[0019] Each occurrence of Z is independently selected from O, S, Se or NR6;

[0020] R1, R4, R6 are independently selected from substituted or unsubstituted straight chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkylthio having 3 to 30 carbon atoms;

[0021] R2 and R5, at each occurrence, are independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0022] R3, at each occurrence, is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a cyclic alkoxy group having 3-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a cyclic alkylthio group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups;

[0023] The term "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups;

[0024] * indicates the attachment site.

[0025] The present invention further relates to a mixture comprising the oligomer as described above and at least another organic functional material.

[0026] The present invention further relates to a composition comprising the oligomer or mixture as described above, and at least one organic solvent.

[0027] The present invention further relates to an organic electronic device, which comprises at least a cathode, an anode and a photoactive layer located between the cathode and the anode, wherein the photoactive layer comprises the oligomer or mixture as described above, or is prepared from the composition as described above.

[0028] Compared with the prior art, the present invention has the following significant advantages: the oligomer provided by the present invention connects three non-fullerene acceptor small molecule units through flexible units, which can reduce the rigidity of the main chain on the one hand, thereby adjusting the blending between the binary donor and the acceptor; on the other hand, it can promote appropriate donor or acceptor nanophase separation, thereby improving the dissociation and transmission of charges. When applied to organic solar cell devices, the photoelectric conversion efficiency of the device can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the structure of an organic photovoltaic cell according to an embodiment of the device of the present invention. DETAILED DESCRIPTION

[0030] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0031] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0032] In the description of the present invention, it should be understood that the terms "upper", "lower", "between layers", etc., indicating orientations or positional relationships are based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which organic electronic devices are conventionally placed when in use, or are the orientations or positional relationships conventionally understood by those skilled in the art. These are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0033] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0034] In the present invention, organic photovoltaic device, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0035] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0036] In the present invention, when the same group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. The six Rs on the benzene ring may be the same as or different from each other.

[0037] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0038] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of a quinoline ring is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of a thienothiophene group is 8.

[0039] In the present invention, "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aromatic group, a condensed aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a condensed aromatic group conjugated by carbon-carbon bonds, and two or more condensed aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated by carbon-carbon bonds can also be regarded as aromatic groups of the present application. Preferably, the aromatic group is selected from aromatic groups having 6-30 C atoms; further, selected from aromatic groups having 6-20 C atoms; further, selected from aromatic groups having 6-10 C atoms; aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl and their derivatives.

[0040] In the present invention, "heteroaromatic group" refers to a monovalent heteroaromatic ring or a derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatom may be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group may be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated by carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocycle or a heteroaromatic condensed ring. Preferably, the heteroaromatic group is selected from heteroaromatic groups having 5-30 ring atoms; further, selected from heteroaromatic groups having 5-20 ring atoms; further, selected from heteroaromatic groups having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, and derivatives thereof.

[0041] In the present invention, alkyl refers to a straight chain alkyl, a branched chain alkyl or a cyclic alkyl. The number of carbon atoms of the straight chain alkyl may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms of the branched chain alkyl may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. The number of carbon atoms of the cyclic alkyl may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight chain alkyl include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 , -C14 H 29 , -C 15 H 31 , -C 16 H 33 . Non-limiting examples of branched alkyl groups include isopropyl, branched alkyl groups containing 4 C atoms, branched alkyl groups containing 5 C atoms, branched alkyl groups containing 6 C atoms, branched alkyl groups containing 7 C atoms, branched alkyl groups containing 8 C atoms, branched alkyl groups containing 9 C atoms, branched alkyl groups containing 10 C atoms, branched alkyl groups containing 11 C atoms, branched alkyl groups containing 12 C atoms, branched alkyl groups containing 13 C atoms, branched alkyl groups containing 14 C atoms, branched alkyl groups containing 15 C atoms, branched alkyl groups containing 16 C atoms. Non-limiting examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like.

[0042] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above connected to another group via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. The cyclic alkoxy group means that the alkyl group in "-O-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0043] The term "alkylthio" refers to a group with the structure "-S-alkyl", i.e., an alkyl group as defined above is connected to another group via a sulfur atom. The straight-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. The cyclic alkylthio group means that the alkyl group in "-S-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0044] In the present invention, when a linking site is not specified in a group, it means that any linking site in the group can be used as the linking site.

[0045] In the present invention, one or more groups "independently selected from" means that when one or more groups appear simultaneously and in multiple places in a compound, they are all independently selected and may be the same or different.

[0046] In the present invention, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0047] In the process of describing the structural elements of the present invention, the words "include" or "comprises" and the like used in the present invention mean that the devices or materials appearing before the word include the devices or materials listed after the word and their equivalents, but do not exclude other devices or materials.

[0048] The "combinations thereof", "any combinations thereof", "any combinations thereof", "combinations" and the like used in the present invention include all suitable combinations of any two, any three or more of the listed groups.

[0049] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0050] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0051] The oligomers, compositions, mixtures and organic electronic devices described in the present invention are exemplified herein, but are not limited thereto.

[0052] The present invention provides an oligomer having a structure as shown in the general formula (I):

[0053]

[0054] in:

[0055] Each occurrence of L is independently selected from Each occurrence of X1 is independently selected from one or a combination of -O-, -S-, -COO- or -CH2-;

[0056] m1 is any integer selected from 1 to 10;

[0057] Ar1, at each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or

[0058] X is selected from CH, N or B;

[0059] Ar3, at each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms;

[0060] Ar2 is independently selected at each occurrence from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms;

[0061] Each occurrence is independently selected from formula (II-1) or (II-2):

[0062]

[0063]

[0064] Ar4 and Ar5 are each independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms;

[0065] Each occurrence of M is independently selected from O or C(CN)2;

[0066] Each occurrence of Z is independently selected from O, S, Se or NR6;

[0067] R1, R4, R6 are independently selected from substituted or unsubstituted straight chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkylthio having 3 to 30 carbon atoms;

[0068] R2 and R5, at each occurrence, are independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0069] R3, at each occurrence, is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a cyclic alkoxy group having 3-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a cyclic alkylthio group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups;

[0070] The term "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups;

[0071] * indicates the attachment site.

[0072] In one embodiment, each occurrence of Ar1 is independently selected from the following groups, but is not limited thereto:

[0073]

[0074] Wherein: Each occurrence of V is independently selected from CR7 or N;

[0075] Each occurrence of Y is independently selected from O, S or Se;

[0076] Each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, cyclic alkylthio having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0077] Further, each occurrence of R7 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a cyclic alkoxy group having 3-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a cyclic alkylthio group having 3-10 carbon atoms, or a group formed by a combination of the above groups.

[0078] In one embodiment, each occurrence of Ar1 is independently selected from any of the following groups, but is not limited thereto:

[0079]

[0080]

[0081] In one embodiment, the m1 is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0082] In one embodiment, each occurrence of L is independently selected from wherein m2 is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and m3 is selected from 1, 2 or 3.

[0083] In a specific embodiment, each occurrence of L is independently selected from any of the following groups:

[0084]

[0085]

[0086] In one embodiment, each occurrence of Ar2 is independently selected from a A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or R a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms; said R a Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, cyclic alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, cyclic alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, cyclic alkylthio having 3-10 carbon atoms, or a group formed by a combination of the above groups.

[0087] Further, each occurrence of Ar2 is independently selected from R a A substituted or unsubstituted thienyl group.

[0088] In one embodiment, the Each occurrence is selected from the same group.

[0089] In a specific embodiment, the Selected from any of the following groups, but not limited to:

[0090]

[0091]

[0092] In one embodiment, each occurrence of Ar5 is independently selected from b A substituted or unsubstituted heteroaromatic group having 6 to 14 ring atoms, R b A substituted or unsubstituted aromatic group having 6 to 14 carbon atoms; R b Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, cyclic alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, cyclic alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, cyclic alkylthio having 3-10 carbon atoms, aromatic groups having 6-10 carbon atoms, heteroaromatic groups having 5-10 ring atoms, or groups formed by combinations of the above groups.

[0093] Further, each occurrence of Ar5 is independently selected from any of the following groups:

[0094]

[0095] in:

[0096] n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1 or 2; n3 is selected from 0 or 1; n4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0097] Furthermore, the structural formula (II-2) is selected from any one of the structures (III-1) to (III-4):

[0098]

[0099]

[0100] In one embodiment, the Rb Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched chain alkyl group having 3 to 10 carbon atoms.

[0101] Specifically, the R b Each occurrence is independently selected from -D, -F, -Cl, -Br, or -CF3.

[0102] In one embodiment, each occurrence of Z is independently selected from S or Se.

[0103] In one embodiment, each occurrence of R3 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight chain alkyl group having 1-10 carbon atoms, or a branched chain alkyl group having 3-10 carbon atoms.

[0104] In a preferred embodiment, each occurrence of R1 and R4 is independently selected from c Substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, c Substituted or unsubstituted branched alkyl having 3 to 30 carbon atoms, c Substituted or unsubstituted straight chain alkoxy having 1 to 30 carbon atoms, c Substituted or unsubstituted branched alkoxy having 3 to 30 carbon atoms, c Substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, or R c A substituted or unsubstituted branched alkylthio group having 3 to 30 carbon atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a cyclic alkyl group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

[0105] Further, each occurrence of R1 and R4 is independently selected from c Substituted or unsubstituted branched alkyl having 3 to 30 carbon atoms. Specifically, each occurrence of R1 is independently selected from:

[0106] In a preferred embodiment, each occurrence of R2 and R5 is independently selected from -H, -D, a straight-chain alkyl group having 1-20 carbon atoms, a branched-chain alkyl group having 3-20 carbon atoms, a straight-chain alkoxy group having 1-20 carbon atoms, a branched-chain alkoxy group having 3-20 carbon atoms, a straight-chain alkylthio group having 1-20 carbon atoms, or a branched-chain alkylthio group having 3-20 carbon atoms.

[0107] In one embodiment, the Selected from

[0108] Preferably, each occurrence of Ar4 is independently selected from R d A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or R d A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms; R d Each occurrence is independently selected from D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

[0109] In a specific embodiment, the Each occurrence is independently selected from any of the following groups:

[0110]

[0111] In a specific embodiment, the Each occurrence is independently selected from any of the following groups, but is not limited thereto:

[0112]

[0113]

[0114] It should be noted that the oligomers described in the present invention are and 3 The composition is connected by a connection site*. Preferably, 3 are selected from the same group.

[0115] In a specific embodiment, the oligomer according to the present invention is selected from the structures listed in Table 1, but is not limited thereto:

[0116] Table 1

[0117]

[0118]

[0119]

[0120]

[0121] The present invention further relates to a photoactive layer receptor material, wherein the photoactive layer receptor material is selected from the oligomers as described above.

[0122] The present invention further relates to a mixture comprising the oligomer as described above and at least one other organic functional material. Preferably, the other organic functional material is selected from a photoactive layer donor material and / or another photoactive layer acceptor material.

[0123] In one embodiment, the mixture comprises the oligomer as described above and another photoactive layer acceptor material; preferably, the another photoactive layer acceptor material is selected from a non-fullerene acceptor material or a fullerene derivative acceptor material.

[0124] In a specific embodiment, the other photoactive layer receptor material is selected from PC 61 BM([6,6]-phenyl C 61 Methyl butyrate), PC 71 BM([6,6]-phenyl C 71 butyrate), indene fullerene and any of the following structures, but not limited thereto:

[0125]

[0126]

[0127] In one embodiment, the mixture further comprises a photoactive layer donor material; preferably, the photoactive layer donor material is selected from a polymer donor material; further, the donor material can be selected from one, two or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TCl, PQM-Cl, J106, and J52-Cl.

[0128] The present invention further relates to a composition comprising the oligomer or mixture as described above, and at least one organic solvent.

[0129] Preferably, the organic solvent can be selected from one of dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indane, methyl benzoate, ethyl benzoate, and mesitylene, or a mixture of two or more thereof.

[0130] Preferably, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0131] In one embodiment, the composition may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from, but not limited to, 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, 1,4-diiodobenzene (DIB), 1,3-dibromo-5-chlorobenzene (DBCl), 3,5-dichlorobromobenzene (DCBB), 1-chloronaphthalene (1-CN), 1,3,5-tribromobenzene (TBB), etc., but are not limited thereto.

[0132] Furthermore, the present invention also provides an organic electronic device, comprising an anode, a cathode and a photoactive layer located between the anode and the cathode, wherein the photoactive layer comprises the oligomer or mixture as described above, or is prepared from the composition as described above. Preferably, the organic electronic device is selected from an organic photovoltaic cell (OPV), an organic light emitting diode (OLED), an organic field effect transistor (OFET), an organic laser, an organic photodetector (OPD), etc.

[0133] Preferably, the organic electronic device is selected from organic photovoltaic cells (OPV).

[0134] At least one of the anode and cathode is transparent or translucent to facilitate the incidence of light. The material used to prepare the electrode can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited thereto.

[0135] The photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material. The photoactive layer donor material is preferably one, two or more selected from PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TCl, PQM-Cl, J106, and J52-Cl, but is not limited thereto.

[0136] The photoactive layer receptor material at least comprises the oligomer as described above; further, the photoactive layer receptor material may further comprise another photoactive layer receptor, preferably, the another photoactive layer receptor material is selected from a non-fullerene receptor material or a fullerene derivative receptor material. Specifically, the another photoactive layer receptor material is selected from PC 61 BM([6,6]-phenyl C 61 Methyl butyrate), PC 71 BM([6,6]-phenyl C 71 butyrate methyl ester), indene-containing fullerene and compounds (A-1)-(A-21), but are not limited thereto.

[0137] Further, the photoactive layer can be prepared by dissolving the photoactive donor material in an organic solvent and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spraying, doctor blade, slit coating and inkjet printing, but not limited thereto.

[0138] The mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:0.8 to 1:1.5; further, the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1 to 1:1.5; the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1 to 1:1.2.

[0139] The concentration of the photoactive layer donor material in the organic solvent is preferably 3-15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4-10 mg / mL.

[0140] The organic solvent has the same meaning as described above.

[0141] In one embodiment, the organic solar cell further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the photoactive layer.

[0142] Preferably, the cathode buffer layer material can be selected from metal complexes, metal oxides, metal salts, etc. with low work function, such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited to this.

[0143] In one embodiment, the organic solar cell further comprises an anode buffer layer, wherein the anode buffer layer is located between the anode and the photoactive layer.

[0144] Preferably, the anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembly materials such as 2PACz, MeO-2PACz, etc., but not limited thereto.

[0145] It should be noted that, in order to improve the performance of the organic solar cell device, the organic solar cell may further include other functional layers, including but not limited to a charge blocking layer and a charge transport layer.

[0146] Furthermore, the organic solar cell further comprises a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the photoactive layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the photoactive layer.

[0147] In one embodiment, as a substrate, a substrate having excellent transparency, surface smoothness, ease of operation and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), polyparaxylene (Parylene), etc., but is not limited thereto, and a substrate commonly used for organic solar cells may also be used.

[0148] In a specific embodiment, the organic solar cell is stacked with an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer and a cathode in order from bottom to top, and the photoactive layer comprises the oligomer or mixture as described above, or is prepared from the above composition.

[0149] The organic solar cells provided by the present invention are mainly used in wearable devices, smart Internet of Things, smart homes, smart agriculture, building photovoltaics, new energy vehicles and other fields.

[0150] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0151] Here, the oligomer and organic electronic device provided by the present invention are exemplified, but the present invention is not limited to the following embodiments.

[0152] Oligomer Synthesis Example

[0153] Synthesis Example 1: Synthesis of Compound (3)

[0154]

[0155] Synthesis of compound 1-0: Under nitrogen atmosphere, compound A1 (5.2 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. After cooling to room temperature, the mixture was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over Na2SO4 and concentrated under reduced pressure to obtain a crude product; without purification, the crude product was dissolved in a mixed solution of EtOH and THF (40 mL, volume ratio 3:1), ethyl glyoxylate (2.5 g, 25.0 mmol) was added, and stirred at room temperature overnight. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography, and the eluent was PE:DCM = 1:3 (volume ratio) to obtain compound 1-0 (3.2 g, 61.7%). MADLI-TOF-MS: 1037.48.

[0156] Synthesis of compound 1-1: Under nitrogen atmosphere, compound 1-0 (3.1 g, 3.0 mmol) was dissolved in anhydrous POCl3 (9.2 g, 60.0 mmol), and DMF (0.2 g, 3.0 mmol) was added. The reaction was heated to 90°C and stirred overnight. After the reaction was completed, it was cooled to room temperature, and the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:5 (volume ratio) to obtain solid compound 1-1 (2.7 g, 85.2%). MADLI-TOF-MS: 1056.19.

[0157]

[0158] Synthesis of compound 1-2: Under nitrogen atmosphere, compound 1-1 (2.7 g, 2.5 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent PE:DCM = 1:2 (volume ratio) to obtain solid compound 1-3 (2.1 g, 75.5%).

[0159] MADLI-TOF-MS:1112.33.

[0160]

[0161] Synthesis of compound 1-4: Under nitrogen atmosphere, compound 1-2 (1.7 g, 1.5 mmol), compound 1-3 (0.5 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (20 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 1-4 (1.2 g, 65.2%). MADLI-TOF-MS: 3678.21

[0162]

[0163] Synthesis of compound (3): Compound 1-4 (368 mg, 0.1 mmol) and 5,6-dichloro-3-(dicyanomethylidene)indone (132 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (3) (414 mg, 80.4%). MADLI-TOF-MS: 5147.89.

[0164] Synthesis Example 2: Synthesis of Compound (11)

[0165]

[0166] Synthesis of compound 2-1: Under nitrogen atmosphere, compound A2 (6.0 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. After cooling to room temperature, the mixture was slowly added to ice water and extracted with dichloromethane. The organic phase was dried over Na2SO4 and concentrated under reduced pressure to obtain a crude product; the crude product was dissolved in chloroform (50 mL), and 2,3-dichloro-5,6-dicyano-p-benzoquinone (11.3 g, 50.0 mmol) and 4-bromo-5-fluorobenzene-1,2-diamine (1.3 g, 6.5 mmol) were added in sequence, and the reaction was stirred at room temperature for 12 h, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 2-1 (4.7 g, 70.3%). MADLI-TOF-MS: 1336.54.

[0167] Synthesis of compound 2-2: Under nitrogen atmosphere, compound 2-1 (4.0 g, 3.0 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography, the eluent was PE:DCM = 1:2 (volume ratio), and solid compound 2-2 (2.9 g, 69.4%) was obtained. MADLI-TOF-MS: 1392.25.

[0168]

[0169] Synthesis of compound 2-4: Under nitrogen atmosphere, compound 2-2 (2.1 g, 1.5 mmol), 1-3 (0.5 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (25 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 2-4 (1.7 g, 77.5%). MADLI-TOF-MS: 4386.74.

[0170]

[0171] Synthesis of compound (11). Compound 2-4 (439 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115.0 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (11) (473 mg, 83.5%). MADLI-TOF-MS: 5660.17.

[0172] Synthesis Example 3: Synthesis of Compound (57)

[0173]

[0174] Synthesis of compound 3-3-1: Weigh phloroglucinol (1.3 g, 10.0 mmol) and 2-(4-bromobutyl)thiophene (7.9 g, 36.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol), add 100 mL of DMF, evacuate three times, and heat to 100 ° C under nitrogen atmosphere for 36 hours. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane. The organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with petroleum ether and dichloromethane (volume ratio 4:1) as eluent to obtain compound 3-3-1 (4.9 g, 90.5%). MS: 541.36.

[0175] Synthesis of compound 3-3: Weigh compound 3-3-1 (1.6 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, then extracted with saturated sodium chloride aqueous solution and dichloromethane, the organic phase was dried with anhydrous Na2SO4, and concentrated under reduced pressure to obtain compound 3-3 (2.4 g, 77.7%). MS: 1029.53.

[0176]

[0177] Synthesis of compound 3-0: Under nitrogen atmosphere, compound A2 (6.0 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. After cooling to room temperature, the mixture was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over Na2SO4 and concentrated under reduced pressure to obtain a crude product; without purification, the crude product was dissolved in a mixed solution of EtOH and THF (40 mL, volume ratio 3:1), ethyl glyoxylate (2.5 g, 25.0 mmol) was added, and stirred at room temperature overnight. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography, and the eluent was PE:DCM = 1:3 (volume ratio) to obtain compound 3-0 (4.1 g, 68.0%). MADLI-TOF-MS: 1206.09.

[0178] Synthesis of compound 3-1: Under nitrogen atmosphere, compound 3-0 (3.6 g, 3.0 mmol) was dissolved in anhydrous POCl3 (9.2 g, 60.0 mmol), and DMF (0.2 g, 13.0 mmol) was added. The reaction was heated to 90°C and stirred overnight. After the reaction was completed, it was cooled to room temperature, and the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:5 (volume ratio) to obtain solid compound 3-1 (3.2 g, 87.2%). MADLI-TOF-MS: 1223.81.

[0179]

[0180] Synthesis of compound 3-2: Under nitrogen atmosphere, compound 3-1 (3.2 g, 2.6 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent PE:DCM=1:2 (volume ratio) to obtain solid compound 3-2 (2.5 g, 75.1%). MADLI-TOF-MS: 1280.53.

[0181]

[0182] Synthesis of compound 3-4: Under nitrogen atmosphere, compound 3-2 (1.9 g, 1.5 mmol), 3-3 (515 mg, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (20 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 3-4 (1.5 g, 70.2%). MADLI-TOF-MS: 4272.66.

[0183]

[0184] Synthesis of compound (57): Compound 3-4 (427 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, the mixture was poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (57) (451 mg, 81.3%). MADLI-TOF-MS: 5545.94.

[0185] Synthesis Example 4: Synthesis of Compound (72)

[0186]

[0187] Synthesis of compound 4-1-2: Weigh compound 4-1-1 (2.6 g, 10.0 mmol), 2-bromothiophene (5.9 g, 36.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol), add 100 mL of DMF, evacuate three times, and heat to 100 ° C under nitrogen atmosphere for 36 hours. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 4-1-2 (4.3 g, 85.1%). MS: 505.18.

[0188] Synthesis of compound 4-1: Weigh compound 4-1-2 (1.5 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane, and the organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure to obtain compound 4-1 (2.6 g, 87.3%). MS: 992.86.

[0189]

[0190] Synthesis of compound 4-2: Under nitrogen atmosphere, compound 2-2 (2.1 g, 1.5 mmol), 4-1 (497 mg, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (20 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 4-2 (1.5 g, 67.6%). MADLI-TOF-MS: 4440.51.

[0191]

[0192] Synthesis of compound (72). Compound 4-2 (444 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (72) (463 mg, 80.9%). MADLI-TOF-MS: 5713.42.

[0193] Synthesis Example 5: Synthesis of Compound (85)

[0194]

[0195] Synthesis of compound 5-3-1: Weigh 2,5,8-bromobenzo[1,2-b:3,4-b':5,6-b"]terthiophene (4.8 g, 10.0 mmol) and 4-(thiophen-2-yl)propane-1-ol (5.1 g, 36.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol), add 100 mL of DMF, evacuate three times, and heat to 100 ° C under nitrogen atmosphere for 36 hours. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with petroleum ether and dichloromethane (volume ratio 3:1) as eluent to obtain compound 5-3-1 (5.3 g, 79.4%). MS: 667.32.

[0196] Synthesis of compound 5-3: Weigh compound 5-3-1 (2.0 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure to obtain compound 5-3 (3.1 g, 89.4%). MS: 1155.91.

[0197]

[0198] Synthesis of compound 5-1: Under nitrogen atmosphere, compound A3 (7.1 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. After cooling to room temperature, the mixture was slowly added to ice water and extracted with dichloromethane. The organic phase was dried without Na2SO4 and concentrated under reduced pressure to obtain a crude product; the crude product was dissolved in chloroform (50 mL), and 2,3-dichloro-5,6-dicyano-p-benzoquinone (11.3 g, 50.0 mmol) and 4,5-dichlorobenzene-1,2-diamine (1.2 g, 6.5 mmol) were added in sequence, and the reaction was stirred at room temperature for 12 h, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 5-1 (5.8 g, 75.6%). MADLI-TOF-MS: 1533.78.

[0199] Synthesis of compound 5-2. Under nitrogen atmosphere, compound 5-1 (4.6 g, 3.0 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent PE:DCM = 1:2 (volume ratio) to obtain solid compound 5-2 (3.5 g, 73.4%). MADLI-TOF-MS: 1589.27.

[0200]

[0201] Synthesis of compound 5-4: Under nitrogen atmosphere, compound 5-2 (2.4 g, 1.5 mmol), 5-3 (0.6 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (25 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 5-4 (1.9 g, 71.4%). MADLI-TOF-MS: 5325.64.

[0202]

[0203] Synthesis of compound (85): Compound 5-4 (533 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, the mixture was poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (85) (544 mg, 82.4%). MADLI-TOF-MS: 6599.02.

[0204] Synthesis Example 6: Synthesis of Compound (119)

[0205]

[0206] Synthesis of compound 6-1-1: Weigh 4,4',4"-methylenetriphenol (2.9 g, 10.0 mmol) and 2-(4-bromobutyl)thiophene (7.9 g, 36.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol), add 100 mL of DMF, evacuate three times, and heat to 100 ° C under nitrogen atmosphere for 36 hours. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with petroleum ether and dichloromethane (volume ratio 3:1) as eluent to obtain compound 6-1-1 (5.2 g, 73.6%). MS: 706.45.

[0207] Synthesis of compound 6-1: Weigh compound 6-1-1 (2.1 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, then extracted with saturated sodium chloride aqueous solution and dichloromethane, the organic phase was dried with anhydrous Na2SO4, and concentrated under reduced pressure to obtain compound 6-1 (2.9 g, 80.8%). MADLI-TOF-MS: 1195.72.

[0208]

[0209] Synthesis of compound 6-2: Under nitrogen atmosphere, compound 2-2 (2.1 g, 1.5 mmol), 6-1 (0.6 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (25 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 6-2 (1.6 g, 68.9%). MADLI-TOF-MS: 4643.18.

[0210]

[0211] Synthesis of compound (119): Compound 6-2 (464 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated under reflux for 4 h. The reaction mixture was cooled to room temperature, the mixture was poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (119) (496 mg, 83.8%). MADLI-TOF-MS: 5916.44.

[0212] Synthesis Example 7: Synthesis of Compound (132)

[0213]

[0214] Synthesis of compound 7-3-1: Weigh tri(4-hydroxyphenyl)amine (2.9g, 10.0mmol) and 2-(4-bromobutyl)thiophene (7.9g, 36.0mmol) and potassium carbonate (5.5g, 40.0mmol), add 100mL of DMF, evacuate three times, and heat to 100°C under nitrogen atmosphere for 36 hours. The reaction was quenched with deionized water, and then extracted with saturated sodium chloride aqueous solution and dichloromethane. The organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with petroleum ether and dichloromethane (volume ratio 3:1) as eluent to obtain compound 7-3-1 (4.8g, 67.8%). MS: 707.60.

[0215] Synthesis of compound 7-3: Weigh compound 7-3-1 (2.1 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, then extracted with saturated sodium chloride aqueous solution and dichloromethane, the organic phase was dried with anhydrous Na2SO4, and concentrated under reduced pressure to obtain compound 7-3 (2.9 g, 80.8%). MADLI-TOF-MS: 1196.58.

[0216]

[0217] Synthesis of compound 7-1: Under nitrogen atmosphere, compound A4 (6.7 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. Cooled to room temperature, the mixture was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried without Na2SO4 and concentrated under reduced pressure to obtain a crude product; without purification, 3-bromophenanthrene-9,10-dione (1.4 g, 5.0 mmol) was added to the crude product, and 20 mL of chlorobenzene and 20 mL of acetic acid were added in sequence, heated to reflux, and stirred overnight under nitrogen protection. After cooling to room temperature, it was washed with water, extracted with dichloromethane, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography, and the eluent was PE:DCM = 2:1 (volume ratio) to obtain compound 7-1 (5.8 g, 74.4%). MADLI-TOF-MS:1559.81.

[0218] Synthesis of compound 7-2: Under nitrogen atmosphere, compound 7-1 (4.7 g, 3.0 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent PE:DCM=2:1 (volume ratio) to obtain solid compound 7-2 (2.6 g, 53.6%). MADLI-TOF-MS: 1615.47.

[0219]

[0220] Synthesis of compound 7-4: Under nitrogen atmosphere, compound 7-2 (2.4 g, 1.5 mmol), 7-3 (0.6 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (20 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:1 (volume ratio) to obtain solid compound 7-4 (1.9 g, 71.5%). MADLI-TOF-MS: 5311.28.

[0221]

[0222] Synthesis of compound (132): Compound 7-2 (531 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated to reflux for 4 h. The reaction mixture was cooled to room temperature, the mixture was poured into methanol and filtered, and the residue was purified by silica gel column chromatography with the eluent being PE:DCM=1:1 (volume ratio) to obtain compound (132) (504 mg, 76.5%). MADLI-TOF-MS: 6583.71.

[0223] Synthesis Example 8: Synthesis of Compound (136)

[0224]

[0225] Synthesis of compound 8-3-2: Add magnesium chips (1.1 g, 45 mmol) and 20 mL of tetrahydrofuran to a round-bottom flask and stir continuously. Under a nitrogen atmosphere, dissolve compound 8-3-1 (5.0 g, 10 mmol) in 20 mL of anhydrous tetrahydrofuran, add dropwise to the mixture of magnesium chips and tetrahydrofuran at 60°C, react for 2 hours, and use a syringe to separate the Grignard reagent solution from the remaining Mg for later use. In a 100mL two-necked round-bottom flask, 2-(4-bromobutyl)thiophene (7.8g, 36.0mmol and the above reaction solution, 20mL anhydrous tetrahydrofuran, under nitrogen protection and at -10°C, 0.1M dilithium tetrachlorocuprate (1.0mL, 0.1mmol) was added dropwise and reacted for 5 hours. The reaction was quenched with saturated ammonium chloride solution, extracted with saturated sodium chloride aqueous solution and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 8-3-2 (3.6g, 53.1%). MS: 677.38.

[0226] Synthesis of compound 8-3: Weigh compound 8-3-2 (2.0 g, 3.0 mmol), add 40 mL of anhydrous THF, add 2.5 M n-butyl lithium solution (5.4 mL, 13.5 mmol) dropwise under nitrogen atmosphere and -78 ° C, react for 2 h, add trimethyltin chloride (8.0 g, 40.5 mmol) solution, move to room temperature, and react overnight. The reaction was quenched with deionized water, then extracted with saturated sodium chloride aqueous solution and dichloromethane, the organic phase was dried with anhydrous Na2SO4, and concentrated under reduced pressure to obtain compound 8-3 (2.4 g, 68.7%). MADLI-TOF-MS: 1165.26.

[0227]

[0228] Synthesis of compound 8-1: Under nitrogen atmosphere, compound A2 (6.0 g, 5.0 mmol) was dissolved in anhydrous THF (50 mL), and a 1 M solution of LiAlH4 (50.0 mL, 50.0 mmol) was slowly added, and heated to reflux and stirred overnight. After cooling to room temperature, the mixture was slowly added to ice water and extracted with dichloromethane. The organic phase was dried over Na2SO4 and concentrated under reduced pressure to obtain a crude product; the crude product was dissolved in chloroform (50 mL), and 2,3-dichloro-5,6-dicyano-p-benzoquinone (10.3 g, 50.0 mmol) and 3-bromo-4-fluorobenzene-1,2-diamine (1.3 g, 6.5 mmol) were added in sequence, and the reaction was stirred at room temperature for 12 h, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 8-1 (4.7 g, 70.3%). MADLI-TOF-MS: 1337.25.

[0229] Synthesis of compound 8-2: Under nitrogen atmosphere, compound 8-1 (4.0 g, 3.0 mmol) was dissolved in 30 mL of anhydrous DMF, 1 mL of phosphorus oxychloride was added under ice-water bath, and then heated to 90 ° C for two hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was slowly added to ice water, and extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent PE:DCM=1:2 (volume ratio) to obtain solid compound 8-2 (2.7 g, 64.6%). MADLI-TOF-MS: 1392.34.

[0230]

[0231] Synthesis of compound 8-4: Under nitrogen atmosphere, compound 8-2 (2.1 g, 1.5 mmol), 8-3 (0.6 g, 0.5 mmol) and Pd(PPh3)4 (57.7 mg, 0.05 mmol) were added to a reaction bottle, and toluene (25 mL) was used as solvent, and the mixture was heated to reflux for 12 h. After cooling to room temperature, the mixture was extracted twice with saturated brine and dichloromethane, and the organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain solid compound 8-4 (1.7 g, 73.7%). MADLI-TOF-MS: 4612.88.

[0232]

[0233] Synthesis of compound (136): Compound 8-4 (461 mg, 0.1 mmol) and 5,6-difluoro-3-(dicyanomethylidene)indone (115 mg, 0.5 mmol) were dissolved in 30 mL of chloroform, 0.3 mL of pyridine was added, and the mixture was heated under reflux for 4 h. The reaction mixture was cooled to room temperature, the mixture was poured into methanol and filtered, and the residue was purified by silica gel column chromatography with an eluent of PE:DCM = 1:3 (volume ratio) to obtain compound (136) (509 mg, 86.4%). MADLI-TOF-MS: 5886.64.

[0234] Organic Photovoltaic Cell (OPV) Device Preparation and Characterization

[0235] This example illustrates the preparation, implementation and characterization of the OPV device provided by the present invention, but the present invention is not limited to the following examples.

[0236] like Figure 1 As shown, the OPV device structure is as follows: indium tin oxide ITO / anode buffer layer / photoactive layer / PNDIT-F3N / Ag.

[0237] Device Example 1:

[0238] 1) ITO substrate cleaning:

[0239] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0240] 2) Anode buffer layer preparation

[0241] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 4000 rpm for 30 s, and dried at 150° C. for 15 min to obtain an anode buffer layer.

[0242] 3) Preparation of photoactive layer

[0243] In a glove box (inert gas atmosphere), the photoactive layer material solvent is evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain a photoactive layer with a total thickness of about 100 nm.

[0244] The active layer material solvent preparation method is: dissolving the donor material and the acceptor material in chloroform to a total concentration of 16.5 mg / mL; wherein the donor material in the photoactive layer material is selected from polymer PM6, and the acceptor material is selected from compound (A-13) and compound (3), and the mass ratio of PM6: compound (A-13): compound (3) is 1:1:0.2.

[0245] 4) Preparation of cathode buffer layer

[0246] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the photoactive layer at a spin coating speed of 3000 rpm and a rotation time of 30 seconds to obtain a cathode buffer layer.

[0247] 5) Cathode layer preparation

[0248] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0249] 6) Packaging

[0250] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0251] Device Example 2:

[0252] The preparation method of device example 2 refers to the preparation method of device example 1, with the difference being that the selection of the acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (11), and the mass ratio of PM6: compound (A-13): compound (11) is 1:1:0.2.

[0253] Device Example 3:

[0254] The preparation method of device example 3 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (57), and the mass ratio of PM6: compound (A-13): compound (57) is 1:1:0.2.

[0255] Device Example 4:

[0256] The preparation method of device example 4 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (72), and the mass ratio of PM6: compound (A-13): compound (72) is 1:1:0.2.

[0257] Device Example 5:

[0258] The preparation method of device example 5 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (85), and the mass ratio of PM6: compound (A-13): compound (85) is 1:1:0.2.

[0259] Device Example 6:

[0260] The preparation method of device example 6 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (119), and the mass ratio of PM6: compound (A-13): compound (119) is 1:1:0.2.

[0261] Device Example 7:

[0262] The preparation method of device example 7 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (132), and the mass ratio of PM6: compound (A-13): compound (132) is 1:1:0.2.

[0263] Device Example 8:

[0264] The preparation method of device example 8 refers to the preparation method of device example 1, with the difference being that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (3) in device example 1 is replaced by compound (136), and the mass ratio of PM6: compound (A-13): compound (136) is 1:1:0.2.

[0265] Device Comparison Example 1:

[0266] The preparation method of device example 8 refers to the preparation method of device example 1, with the difference being that the selection of acceptor materials in the photoactive layer is different. Specifically, the acceptor material compound (A-13) and compound (3) in device example 1 are replaced by compound (A-13), and the mass ratio of PM6:compound (A-13) is 1:1.2.

[0267] The prepared organic photovoltaic cell device was subjected to a performance test. Under the irradiation of standard light from a solar simulator (AM 1.5G), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated, as shown in Table 2.

[0268] Table 2

[0269] Device Embodiment Photoactive layer donor and acceptor materials Photoelectric conversion efficiency (%) Device Example 1 PM6: Compound (A-13): Compound (3) 18.43 Device Example 2 PM6: Compound (A-13): Compound (11) 18.89 Device Example 3 PM6: Compound (A-13): Compound (57) 18.31 Device Example 4 PM6: Compound (A-13): Compound (72) 18.63 Device Example 5 PM6: Compound (A-13): Compound (85) 19.16 Device Example 6 PM6: Compound (A-13): Compound (119) 18.02 Device Example 7 PM6: Compound (A-13): Compound (132) 18.18 Device Example 8 PM6: Compound (A-13): Compound (136) 17.96 Device Comparative Example 1 PM6: Compound (A-13) 17.47

[0270] It can be seen from the data in Table 2 that when the oligomer shown in the present invention is used as the third component in an organic photovoltaic device, the photoelectric conversion efficiency of the device is significantly improved compared with the device comparative example 1. The reason is that the oligomer described in the present invention connects three non-fullerene acceptor small molecule units through a flexible unit. When it is used as the third component in the photoactive layer, on the one hand, it can reduce the voltage loss of the system and improve the open circuit voltage of the device; on the other hand, it can promote appropriate donor or acceptor nanophase separation, thereby improving the transmission and collection of charges.

[0271] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments. Within the technical concept of the present application, a variety of simple modifications can be made to the technical solution of the present application, and these simple modifications all belong to the protection scope of the present application.

Claims

1. An oligomer, characterized in that: The oligomer has a structure as shown in the general formula (I): in: Each occurrence of L is independently selected from X1 is independently selected from one or a combination of -O-, -S-, -COO- or -CH2- each time it occurs, and m1 is selected from any integer from 1 to 10; Ar1, at each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or X is selected from CH, N or B; Ar3, at each occurrence, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms; Ar2 is independently selected at each occurrence from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms; Each occurrence is independently selected from formula (II-1) or (II-2): Ar4 and Ar5 are each independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms; Each occurrence of M is independently selected from O or C(CN)2; Each occurrence of Z is independently selected from O, S, Se or NR6; R1, R4, R6 are independently selected from substituted or unsubstituted straight chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched chain alkylthio having 3 to 30 carbon atoms; R2 and R5, at each occurrence, are independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; R3, at each occurrence, is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a cyclic alkoxy group having 3-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a cyclic alkylthio group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; The term "substituted or unsubstituted" means that the group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups; * indicates the attachment site.

2. The oligomer according to claim 1, characterized in that: Each occurrence of Ar1 is independently selected from any of the following groups: Wherein: Each occurrence of V is independently selected from CR7 or N; Each occurrence of Y is independently selected from O, S or Se; Each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, cyclic alkylthio having 3-20 carbon atoms, or a group formed by a combination of the above groups.

3. The oligomer according to claim 1, characterized in that: Each time L appears, it is independently selected from wherein m2 is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and m3 is selected from 1, 2 or 3.

4. The oligomer according to claim 1, characterized in that: Each occurrence of Ar2 is independently selected from R a Substituted or unsubstituted thienyl; R a Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, cyclic alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, cyclic alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, cyclic alkylthio having 3-10 carbon atoms, or a group formed by a combination of the above groups.

5. The oligomer according to claim 1, characterized in that: Said Selected from any of the following groups:

6. The oligomer according to claim 1, characterized in that: Ar5 is independently selected from any of the following groups at each occurrence: in: R b Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, cyclic alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, cyclic alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, cyclic alkylthio having 3-10 carbon atoms, aromatic group having 6-10 carbon atoms, heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1 or 2; n3 is selected from 0 or 1; n4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

7. The oligomer according to claim 6, characterized in that: The structural formula (II-2) is selected from any one of the structures (III-1) to (III-4):

8. The oligomer according to claim 7, characterized in that: Said Selected from Each occurrence of Ar4 is independently selected from R d A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or R d A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms; R d Each occurrence is independently selected from D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

9. The oligomer according to claim 1, characterized in that: Said Each occurrence is independently selected from any of the following groups:

10. A mixture, characterized in that: The mixture comprises the oligomer according to any one of claims 1 to 9 and at least another organic functional material.

11. An organic electronic device, characterized in that: The organic electronic device comprises at least a cathode, an anode and a photoactive layer located between the cathode and the anode, wherein the photoactive layer comprises the oligomer according to any one of claims 1 to 9 or the mixture according to claim 10.

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