Polymers, mixtures and their use in organic electronic devices

Abstract

The invention relates to a polymer and a mixture, the polymer and the mixture contain a third unit polymer donor structure # imgabs0 #, the energy level and the absorption spectrum of an active layer donor material are optimized, the energy level and the absorption spectrum of the active layer donor material are better matched with those of a non-fullerene acceptor material, and the polymer and the mixture serve as the donor material to be applied to organic electronic devices. And the photoelectric property of an organic electronic device can be further improved.

Description

Technical Field

[0001] The invention relates to the field of organic solar cell materials, in particular to a polymer, a mixture and applications thereof in organic electronic devices. Background Art

[0002] Solar energy, as an inexhaustible, widely distributed, green and harmless renewable clean energy, has always received great attention. Compared with inorganic solar cells, organic solar cells have the advantages of being light, thin, flexible, solution processable and low-cost printed and manufactured. They can be applied to wearable electronic devices, the Internet of Things, electronic price tags, building photovoltaic integration, new energy vehicles and other scenarios, and have broad market prospects.

[0003] Organic solar cells generally consist of five parts: anode, anode buffer layer, active layer, cathode buffer layer and cathode. Among them, the active layer material plays a vital role in the development of organic solar cells and is the key to absorbing sunlight to complete photoelectric conversion. The active layer materials mainly include donor materials and acceptor materials. Photoelectric efficiency is generated by forming a PN junction at the interface of the donor and acceptor materials. Therefore, designing and synthesizing new high-performance donor / acceptor materials combined with device optimization is the most effective way to improve the performance of organic solar cells. With the innovation of active layer donor / acceptor materials, polymer donor materials have developed from early polythiophene systems (such as P3HT) to DA alternating copolymer systems (such as PM6, D18, etc.), and acceptor materials have developed from early fullerenes and their derivatives to non-fullerene acceptors based on ADA and A-DA′DA systems (such as Y6, L8-BO, ITIC, etc.). The continuous innovation of the active layer has enabled the efficiency of organic solar cell devices to develop from less than 1% at the beginning to nearly 20% now, which has greatly promoted the development of organic solar cells.

[0004] However, compared with the booming development of active layer acceptor materials, the development of polymer donors that match and are excellent with non-fullerene acceptor materials is relatively lagging. Currently, only a few donor polymers paired with non-fullerene acceptor materials have a photoelectric conversion efficiency of more than 17%.

[0005] Therefore, it is necessary to develop new high-performance conjugated polymer donor materials to further improve the photovoltaic performance and realize the practical application of organic solar cells. Summary of the invention

[0006] The object of the present invention is to provide a polymer, a mixture and a composition, which, when used as a donor material, can be used in a photoactive layer of an organic solar cell in combination with a non-fullerene acceptor material to improve the photoelectric performance of the organic solar cell device.

[0007] To achieve the purpose of the present invention, the technical solution is:

[0008] A polymer having a structure as shown in general formula (I):

[0009]

[0010] in:

[0011] Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic heterocyclic group having 5 to 30 ring atoms;

[0012] Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N;

[0013] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0014] x, y are the mole fractions of each unit, 0 <y≤1,0≤x<1,x+y=1;

[0015] n is the number of repeating units, and n is an integer greater than 1.

[0016] The present invention further provides a mixture, the mixture comprising at least one polymer 1 represented by the general formula (II) and at least one polymer 2 represented by the general formula (III):

[0017]

[0018] in:

[0019] Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic heterocyclic group having 5 to 30 ring atoms;

[0020] Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N;

[0021] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0022] n is the number of repeating units, and n is an integer greater than 1.

[0023] The present invention further provides a composition comprising the polymer or mixture as described above, and at least one organic solvent.

[0024] The present invention further relates to an organic electronic device, comprising a cathode, an anode and at least one functional layer, wherein the at least one functional layer comprises the polymer or the mixture as described above, or is prepared from the composition as described above.

[0025] The beneficial effects of the technical solution described in the present invention are as follows:

[0026] The present invention creatively develops the third unit polymer donor structure By copolymerizing or mixing the third unit polymer donor material with The energy level and absorption spectrum of the active layer donor material are optimized to better match the energy level and spectrum of the non-fullerene acceptor material.

[0027] At the same time, the two donor structural units have similar chemical structures and good compatibility, which is conducive to fine-tuning the photon collection and morphology of the ternary blend film, effectively adjusting the molecular orientation and aggregation of the polymer, thereby improving the photoelectric conversion efficiency of the device. Furthermore, the introduction of the third unit polymer donor material allows the ternary system to have more coupling relationships, thereby providing richer multi-dimensional charge transfer channels, thereby further improving the photoelectric performance of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0029] Figure 1Schematic diagram of the structure of an organic solar cell in an embodiment of the device of the present invention.

[0030] In the figure, 101 is a substrate, 102 is an anode, 103 is an anode buffer layer, 104 is a photoactive layer, 105 is a cathode buffer layer, and 106 is a cathode. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] 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").

[0033] In the present invention, organic photovoltaic device, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0034] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0035] In the present invention, when a 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.

[0036] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0037] 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.

[0038] 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 (such as phenyl) or a polycyclic aromatic group. In other words, the aromatic group can be a monocyclic aromatic group, a condensed aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, monocyclic aromatic groups and condensed aromatic groups 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 with 6-30 C atoms; further, selected from aromatic groups with 6-20 C atoms; further, selected from aromatic groups with 6-10 C atoms; aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and derivatives thereof.

[0039] In the present invention, "heteroaromatic group" refers to an aromatic 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 monocyclic heteroaromatic group or a polycyclic heteroaromatic group. In other words, 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 monocyclic ring 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, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

[0040] In the present invention, "non-aromatic heterocycle" includes a single ring system or a condensed ring, wherein the ring system includes at least 1, 2, 3, 4, 5, 6 or more heteroatoms, and the heteroatoms may be at least one of B, O, N, P, Si, Se and S. When the non-aromatic heterocycle is a monocyclic ring, the monocyclic ring does not belong to the ring system of the heteroaromatic group, and when the non-aromatic heterocycle is a polycyclic ring, the polycyclic ring includes at least one ring system without aromatic characteristics. Non-limiting examples: oxirane, oxetane, aziridine, azetidine, thietane, 1-oxidothietane, 1,1-dioxidothietane, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl.

[0041] In the present invention, "alkyl" may represent a straight chain, branched chain or cyclic alkyl group. The number of carbon atoms in a straight chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms in a branched chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the number of carbon atoms in a cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10 H 21 , -C 11 H23 , -C 12 H 25 , -C 13 H 27 , -C 14 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, and branched alkyl groups containing 16 C atoms. Non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclic alkyl groups containing 7 C atoms, cyclic alkyl groups containing 8 C atoms, cyclic alkyl groups containing 9 C atoms, cyclic alkyl groups containing 10 C atoms, cyclic alkyl groups containing 11 C atoms, cyclic alkyl groups containing 12 C atoms, cyclic alkyl groups containing 13 C atoms, cyclic alkyl groups containing 14 C atoms, cyclic alkyl groups containing 15 C atoms, and cyclic alkyl groups containing 16 C atoms.

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

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In the description of the present invention, it should be understood that the terms "upper", "lower", "between layers", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which the organic solar cell device is 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.

[0050] 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 items in the listed groups.

[0051] 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.

[0052] 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.

[0053] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0054] The first aspect of the present invention provides a polymer having a structure as shown in the general formula (I):

[0055]

[0056] in:

[0057] Ar1 and Ar2 are each independently selected from substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, and substituted or unsubstituted non-aromatic heterocyclic groups having 5 to 30 ring atoms;

[0058] Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N;

[0059] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0060] x, y are the mole fractions of each unit, 0 <y≤1,0≤x<1,x+y=1;

[0061] n is the number of repeating units, and n is an integer greater than 1.

[0062] In the present invention, the term "substituted or unsubstituted" means that the group is not substituted or is substituted with one or more substituents R * Replacement, R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups.

[0063] In one embodiment, each occurrence of Ar1 and Ar2 is independently selected from one or more R a Substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, replaced by one or more R a Substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, one or more R a A substituted or unsubstituted non-aromatic heterocyclic group having 5 to 20 ring atoms; R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0064] Furthermore, each occurrence of Ar1 and Ar2 is independently selected from any of the following groups:

[0065]

[0066] in:

[0067] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0068] * indicates the attachment site.

[0069] In a preferred embodiment, the R 101 Each occurrence is independently selected from a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms. 101 Each occurrence is independently selected from a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain or a cyclic alkyl group having 3 to 10 carbon atoms.

[0070] In a specific embodiment, the structural formula (A-1) is selected from

[0071] In a preferred embodiment, R 102 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, or a group formed by a combination of the above groups. Further, R 102 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, or a group formed by a combination of the above groups.

[0072] In a specific embodiment, the structural formula (A-3) is selected from

[0073] In a preferred embodiment, R 103 Each occurrence is independently selected from -H, -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, or a group formed by a combination of the above groups. Further, R 103 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched chain alkyl having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

[0074] In a specific embodiment, R 103 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, a straight chain alkyl group having 1-10 carbon atoms, or a branched chain alkyl group having 3-10 carbon atoms.

[0075] In one embodiment, R 104 Each occurrence is independently selected from a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms. 104 Each occurrence is independently selected from branched chain alkyl groups having 3 to 20 carbon atoms.

[0076] In a specific embodiment, the structural formula (A-4) is selected from

[0077] In a specific embodiment, the structural formula (A-5) is selected from

[0078] In one embodiment, R 105 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, or a group formed by a combination of the above groups.

[0079] In a specific embodiment, the structural formula (A-6) is selected from

[0080] In a preferred embodiment, R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain ester group having 1 to 10 carbon atoms, a branched or cyclic ester group having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

[0081] In a specific embodiment, the structural formula (A-8) is selected from the following groups:

[0082]

[0083] In one embodiment, each occurrence of Z is independently selected from N; further, each occurrence of X is independently selected from CR 10 .

[0084] In another embodiment, each occurrence of X is independently selected from N; further, each occurrence of Z is independently selected from CR 10 ; Further, Z is selected from CH.

[0085] Specifically, the polymer has any structure shown in the following general formula:

[0086]

[0087] In a preferred embodiment, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, or a group formed by a combination of the above groups.

[0088] In a preferred embodiment, Ar1 and Ar2 are selected from the same group each time they appear.

[0089] In a preferred embodiment, the polymer according to the present invention can be selected from any one of the structures of formula (I-1) to (I-10):

[0090]

[0091]

[0092]

[0093] Among them: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 101 , R 102 , R 106 The meanings of x, y, and n are the same as described above.

[0094] In one embodiment, R1, R2, R3, R4, R5, R 10Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, straight-chain alkyl having 1-16 carbon atoms, straight-chain alkoxy having 1-16 carbon atoms, straight-chain alkylthio having 1-16 carbon atoms, branched-chain alkyl having 3-16 carbon atoms, branched-chain alkoxy having 3-16 carbon atoms, and branched-chain alkylthio having 3-16 carbon atoms.

[0095] In one embodiment, each occurrence of R3 and R4 is independently selected from a straight chain alkyl group having 1-16 carbon atoms, a straight chain alkoxy group having 1-16 carbon atoms, a straight chain alkylthio group having 1-16 carbon atoms, a branched chain alkyl group having 3-16 carbon atoms, a branched chain alkoxy group having 3-16 carbon atoms, and a branched chain alkylthio group having 3-16 carbon atoms.

[0096] Furthermore, each occurrence of R3 and R4 is independently selected from a branched alkyl group having 3 to 16 carbon atoms, a branched alkoxy group having 3 to 16 carbon atoms, or a branched alkylthio group having 3 to 16 carbon atoms.

[0097] Furthermore, each occurrence of R3 and R4 is independently selected from any of the following groups:

[0098] In one embodiment, R1, R2, R5, R 10 Each occurrence is independently selected from --H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight chain alkyl group having 1-10 carbon atoms, or a branched chain alkyl group having 3-10 carbon atoms.

[0099] In a specific embodiment, the Each occurrence is independently selected from any of the following groups:

[0100]

[0101] In a specific embodiment, the Each occurrence is independently selected from any of the following groups:

[0102]

[0103] In a preferred embodiment, each occurrence of R6, R7, R8, and R9 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, a straight-chain ester group having 1 to 10 carbon atoms, a branched-chain ester group having 3 to 10 carbon atoms, or a group formed by combining the above groups.

[0104] Further, each occurrence of R6, R7, R8, and R9 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro,

[0105]

[0106] In a specific embodiment, the each occurrence is independently selected from any one of the following groups:

[0107]

[0108] In one embodiment, each occurrence is selected from the same group.

[0109] The polymer according to the present invention is selected from the following structures, but not limited thereto:

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] In one embodiment, y = 1 and x = 0.

[0116] In another embodiment, 0 < y ≤ 0.5, 0.5 ≤ x < 1, and x + y = 1; further, 0 < y ≤ 0.3, 0.7 ≤ x < 1, and x + y = 1; furthermore, 0 < y ≤ 0.2, 0.8 ≤ x < 1, and x + y = 1.

[0117] In one embodiment, y=0.1, x=0.9; in another embodiment, y=0.2, x=0.8; in another embodiment, y=0.25, x=0.75; in another embodiment, y=0.3, x=0.7; in another embodiment, y=0.05, x=0.95; in another embodiment, 7=0.4, x=0.6; in another embodiment, x=0.5, y=0.5.

[0118] In one embodiment, n is selected from an integer of 5 to 1000; further, n is selected from an integer of 5 to 300; further, n is selected from an integer of 10 to 100; further, n is selected from an integer of 15 to 100; in the most preferred embodiment, n is selected from an integer of 20 to 50.

[0119] The second aspect of the present invention provides a mixture, wherein the mixture comprises at least one polymer 1 represented by the general formula (II) and at least one polymer 2 represented by the general formula (III):

[0120]

[0121] in:

[0122] Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic heterocyclic group having 5 to 30 ring atoms;

[0123] Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N;

[0124] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0125] n is the number of repeating units and n is an integer greater than 1.

[0126] Ar1, Ar2, X, Z, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10The further limitations of and n are the same as described above.

[0127] In one embodiment, the polymer 1 represented by the general formula (II) is selected from any one of the structural formulas (II-1) to (II-5):

[0128]

[0129] Where: R 101 , R 102 , R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0130] About R 101 , R 102 , R 106 The further limitations are as described above.

[0131] In one embodiment, the polymer 2 represented by the general formula (III) is selected from any of the following general formulas:

[0132]

[0133] Further, the polymer 2 represented by the general formula (III) is selected from any one of the structural formulas (III-1) to (III-10):

[0134]

[0135] Among them, R4, R5, R8, R9, R 10 , R 101 , R 102 , R 106 The further limitations of and n are the same as described above.

[0136] In a specific embodiment, in the mixture of the present invention, polymer 1 is selected from the following structures, but is not limited thereto:

[0137]

[0138]

[0139] In a specific embodiment, in the mixture of the present invention, the polymer 2 is selected from the following structures, but is not limited thereto:

[0140]

[0141]

[0142] According to the mixture of the present invention, the mass ratio of polymer 1 to polymer 2 is selected from 20:1 to 1:1; further, the mass ratio of polymer 1 to polymer 2 is selected from 10:1 to 1:1.

[0143] In one embodiment, the mass ratio of polymer 1 to polymer 2 is selected from 9:1 to 7:3; further, the mass ratio of polymer 1 to polymer 2 is selected from 9:1 to 8:2.

[0144] The mixture of the present invention further comprises at least one active layer acceptor material, wherein the active layer acceptor material is selected from non-fullerene acceptor materials and / or fullerene acceptor materials.

[0145] Preferably, the non-fullerene acceptor material is selected from the following structures, but is not limited thereto:

[0146]

[0147] The fullerene derivative acceptor material is selected from C60 derivatives or C70 derivatives, and the fullerene derivative acceptor material includes but is not limited to: one, two or three or more of PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc.

[0148] The third aspect of the present invention relates to a composition, which comprises the polymer described in the first aspect or the mixture described in the second aspect, and at least one organic solvent.

[0149] 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.

[0150] Preferably, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0151] It should be noted that the above-mentioned organic solvent may be evaporated from the solvent system to form a thin film including the above-mentioned organic compound.

[0152] 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.

[0153] It should be noted that the present application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the above composition is used to prepare an organic electronic device by a printing or coating preparation method. The printing or coating preparation method can be, but is not limited to, inkjet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slit extrusion coating, etc. The preferred ones are slit coating, spin coating and inkjet printing.

[0154] The present invention further relates to an organic electronic device, comprising a cathode, an anode and at least one functional layer, wherein the at least one functional layer comprises the polymer or mixture as described above, or is prepared from the composition as described above. Preferably, the organic electronic device is selected from organic solar cells (OPV), organic light emitting diodes (OLED), organic field effect transistors (OFET), organic lasers, organic photodetectors (OPD), etc.

[0155] In a specific embodiment, the organic electronic device is selected from organic solar cells.

[0156] Furthermore, the organic solar cell at least comprises an anode, a cathode and a photoactive layer located between the anode and the cathode, and the photoactive layer comprises the polymer or mixture as described above, or is prepared from the composition as described above.

[0157] In one embodiment, the photoactive layer material comprises an active layer donor material and an active layer acceptor material; preferably, the active layer donor material is selected from a polymer as described in general formula (I) or a mixture of a polymer 1 described in general formula (II) and a polymer 2 described in general formula (III).

[0158] The active layer acceptor material is selected from non-fullerene acceptor materials and / or fullerene acceptor materials, wherein the further limitations of the non-fullerene acceptor materials and fullerene acceptor materials are the same as described above.

[0159] Preferably, the mass ratio of the active layer donor material to the active layer acceptor material is 2:1 to 1:2; further, the mass ratio of the active layer donor material to the active layer acceptor material is 0.8:1.8 to 1.8:0.8; preferably, the mass ratio is 1:1 to 1:1.8; more preferably, the mass ratio is 1:1 to 1:1.5; more preferably, the mass ratio is 1:1 to 1:1.2.

[0160] Further, the photoactive layer may be formed by dissolving the photoactive material in an organic solvent and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spray coating, doctor blade, slit coating, and inkjet printing, but is not limited thereto.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] It should be noted that, in order to improve the performance of the organic solar cell device, the functional layer may further include other functional layers, including but not limited to a charge blocking layer and a charge transport layer.

[0166] 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.

[0167] In one embodiment, as the 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 multi-layer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and at least one of the first electrode and the second electrode is transparent or translucent for the incident 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.

[0168] 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 sequence from bottom to top, and the photoactive layer comprises the polymer or mixture as described above, or is prepared from the above composition.

[0169] The organic solar cell described in the present invention also involves applications in various devices, including, but not limited to, automobiles and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0170] The present invention will be described below in conjunction with preferred preparation and device 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 realize 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.

[0171] The polymer and organic electronic device of the present invention are exemplified herein, but the present invention is not limited to the following embodiments.

[0172] Example 1: Synthesis of polymer (P1):

[0173]

[0174] Synthesis of compound P1-1:

[0175] Accurately weigh P1-a (12.44g, 33mmol), P1-b (5.25g, 15mmol), Pd(PPh3)2Cl2 (0.42g, 0.6mmol), add to a 500mL three-necked flask, add 80mL of toluene, 80mL of DMF, replace nitrogen three times, heat to 100℃ and react for 4 hours, cool to room temperature after the raw materials react completely, dilute with water and extract with ethyl acetate, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel, and purify by column chromatography, eluent is PE:EA=5:1 (volume ratio). 7.46g of compound P1-1 is obtained, yield: 80.6%. MS: 616.79.

[0176] Synthesis of compound P1-2:

[0177] Accurately weigh P1-1 (6.17 g, 10 mmol) and dissolve it in 150 mL of dry anhydrous tetrahydrofuran and stir it thoroughly. After replacing nitrogen three times, the reactant is cooled to -70 ° C, and LDA (2.0 M, 11 mL, 22 mmol) is slowly added dropwise. The reactant is stirred at -50 ° C for 2 hours, and then cooled to -70 ° C again. Under this condition, trimethyltin chloride (1.0 M, 25 mL, 25 mmol) is added once, and the mixture is stirred for 1 hour. Then it is naturally warmed to room temperature and stirred overnight. After the raw materials are completely reacted, the resulting reactant is poured into water and extracted with DCM. Finally, 6.52 g of compound P1-2 is obtained by concentration and drying. Yield: 69.2%. MS: 942.73.

[0178] Synthesis of polymer (P1):

[0179] Accurately weigh P1-2 (188 mg, 0.2 mmol), P1-c (752 mg, 0.8 mmol), P1-d (767 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol), purge with argon for another 15 minutes, and stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, n-hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then drip into 300 mL of methanol, filter and collect the filter cake and dry to obtain 601 mg of product polymer (P1). Yield: 49.2%. Mn = 31.6 kDa, PDI = 2.12.

[0180] Example 2: Synthesis of polymer (P2):

[0181]

[0182] Synthesis of compound P2-a:

[0183] Accurately weigh 5-bromothiazole (9.84g, 60mmol) in a 500mL three-necked flask, add 160mL anhydrous tetrahydrofuran to dissolve, replace nitrogen three times and heat to 60°C. (2-ethylhexyl) magnesium bromide (15.64g, 72mmol) tetrahydrofuran solution 72mL (1.0M / L, 72mmol). After the dropwise addition, keep at 60°C for two hours. Then use dichloromethane and water for liquid separation and extraction, spin dry the organic phase, and then use petroleum ether for column chromatography purification to finally obtain 9.89g product P2-a with a yield of 83.6%. MS: 197.10.

[0184] Synthesis of compound P2-1:

[0185] Accurately weigh P2-a (5.92 g, 30 mmol) and dissolve it in 150 mL of dry anhydrous tetrahydrofuran and stir it thoroughly. Replace nitrogen three times. Cool the reactant to -70 ° C, and slowly add LDA (2.0 M, 16.5 mL, 33 mmol). Stir the reactant at -50 ° C for 2 hours, then cool it to -70 ° C again. Under this condition, add Me3SnCl (1.0 M, 36 mL, 36 mmol) at a time and keep it warm and stir for 1 hour. Then naturally warm to room temperature and stir overnight. After the raw materials are completely reacted, pour the resulting reactant into water and extract it with DCM. Finally, concentrate and dry to obtain 7.61 g of compound P2-1. Yield: 70.4%. MS: 360.08.

[0186] Synthesis of compound P2-2:

[0187] Accurately weigh P2-1 (5.94g, 16.5mmol), P2-b (2.61g, 7.5mmol), Pd(PPh3)2Cl2 (0.21g, 0.3mmol), add to a 250mL three-necked flask, add 40mL toluene, 40mL DMF, replace nitrogen three times, heat to 100℃ and react for 4 hours, cool to room temperature after the raw materials react completely, dilute with water and extract with ethyl acetate, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel, and purify by column chromatography, eluent is PE:EA=6:1 (volume ratio). 3.55g compound P2-2 is obtained, yield: 81.5%. MS: 580.81.

[0188] Synthesis of compound P2-3:

[0189] Accurately weigh P2-2 (2.90 g, 5 mmol) and dissolve it in 75 mL of dry anhydrous tetrahydrofuran, stir thoroughly, and replace nitrogen three times. Cool the reactant to -70 ° C, and slowly drop LDA (2.0 M, 5.5 mL, 11 mmol). Stir the reactant at -50 ° C for 2 hours, then cool it to -70 ° C again, add Me3SnCl (1.0 M, 12.5 mL, 12.5 mmol) at a time under this condition, and keep warm and stir for 1 hour. Then naturally warm to room temperature and stir overnight. After the raw materials are completely reacted, pour the resulting reactant into water and extract with DCM. Finally, concentrate and dry to obtain 3.28 g of compound P2-3 with a yield of 72.4%. MS: 906.43.

[0190] Synthesis of polymer (P2):

[0191] Accurately weigh P2-3 (181.3 mg, 0.2 mmol), P1-c (752 mg, 0.8 mmol), P1-d (767 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours, cool to room temperature, and drop into 300 mL of methanol. Filter to obtain a solid, and extract with methane, n-hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then drop into 300 mL of methanol, collect the filter cake by filtration and dry to obtain 674 mg of product polymer (P2). Yield: 55.5%. Mn = 34.2 kDa, PDI = 2.45.

[0192] Example 3: Synthesis of polymer (P3):

[0193]

[0194] Synthesis of polymer (P3):

[0195] Accurately weigh P1-2 (94.2 mg, 0.1 mmol), P1-c (846.5 mg, 0.9 mmol), P3-a (907 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 ((35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 849 mg of product polymer (P3). Yield: 62.4%. Mn = 54.1 kDa, PDI = 1.93.

[0196] Example 4: Synthesis of polymer (P4):

[0197]

[0198] Synthesis of polymer (P4):

[0199] Accurately weigh P2-3 (90.6 mg, 0.1 mmol), P1-c (846.5 mg, 0.9 mmol), P3-a (907 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours, cool to room temperature, drop into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 786 mg of product polymer (P4). Yield: 57.9%. Mn = 58.0 kDa, PDI = 2.07.

[0200] Example 5: Synthesis of polymer (P5):

[0201]

[0202] Synthesis of compound P5-1:

[0203] Accurately weigh P5-a (6.92 g, 30 mmol) and dissolve it in 150 mL of dry anhydrous tetrahydrofuran and stir it thoroughly. Replace nitrogen three times. Cool the reactant to -70 ° C and slowly drop n-BuLi (2.5 M, 13.2 mL, 33 mmol). Stir the reactant at -50 ° C for 2 hours, then cool it to -70 ° C again. Under this condition, add Me3SnCl (1.0 M, 36 mL, 36 mmol) at a time and keep it warm and stir for 1 hour. Then naturally warm to room temperature and stir overnight. After the raw materials are completely reacted, pour the resulting reactant into water and extract it with DCM. Finally, concentrate and dry to obtain 8.13 g of product P5-1. Yield: 68.9%. MS: 393.45.

[0204] Synthesis of compound P5-2:

[0205] Accurately weigh P5-1 (6.50 g, 16.5 mmol), P1-b (2.63 g, 7.5 mmol), Pd(PPh3)2Cl2 (0.21 g, 0.3 mmol), add to a 250 mL three-necked flask, add 40 mL of toluene, 40 mL of DMF, replace nitrogen three times, heat to 100 ° C and react for 4 hours, cool to room temperature after the raw materials are completely reacted, dilute with water and extract with ethyl acetate, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel, and purify by column chromatography, the eluent is PE:EA=5:1 (volume ratio). 3.59 g of compound P5-2 is obtained, yield: 73.6%. MS: 649.53.

[0206] Synthesis of compound P5-3:

[0207] Accurately weigh P5-2 (3.25 g, 5 mmol) and dissolve it in 75 mL of dry anhydrous tetrahydrofuran and stir it thoroughly. Replace nitrogen three times. Cool the reactant to -70 ° C, and slowly add LDA (2.0 M, 5.5 mL, 11 mmol). Stir the reactant at -50 ° C for 2 hours, then cool it to -70 ° C again. Under this condition, add Me3SnCl (1.0 M, 12.5 mL, 12.5 mmol) at a time and keep it warm and stirred for 1 hour. Then naturally warm to room temperature and stir overnight. After the raw materials are completely reacted, pour the resulting reactant into water and extract it with DCM. Finally, concentrate and dry to obtain 3.01 g of product P5-3. Yield: 61.7%. MS: 975.63.

[0208] Synthesis of polymer (P5):

[0209] Accurately weigh P5-3 (195.1 mg, 0.2 mmol), P5-b (778.7 mg, 0.8 mmol), P5-c (901 mg, 1.0 mmol) and 15 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the mixture under reflux for 24 hours, cool to room temperature, and drop into 300 mL of methanol. Filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, collect the filter cake by filtration and dry it to obtain 713 mg of the product polymer (P5). Yield: 51.4%. Mn = 39.8 kDa, PDI = 2.86.

[0210] Example 6: Synthesis of polymer (P6):

[0211]

[0212] Synthesis of polymer (P6):

[0213] Accurately weigh P2-3 (181 mg, 0.2 mmol), P1-c (752 mg, 0.8 mmol), P5-c (901 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 751 mg of product polymer (P6). Yield: 55.8%. Mn = 42.5 kDa, PDI = 2.51.

[0214] Example 7: Synthesis of polymer (P7):

[0215]

[0216] Synthesis of polymer (P7):

[0217] Accurately weigh P1-2 (94 mg, 0.1 mmol), P1-c (846 mg, 0.9 mmol), P7-1 (660 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 768 mg of product polymer (P7). Yield: 69.3%. Mn = 65.9 kDa, PDI = 2.32.

[0218] Example 8: Synthesis of polymer (P8):

[0219]

[0220] Synthesis of polymer (P8):

[0221] Accurately weigh P2-3 (91 mg, 0.1 mmol), P1-c (846 mg, 0.9 mmol), P7-1 (660 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 794 mg of product polymer (P8). Yield: 71.6%. Mn = 59.2 kDa, PDI = 2.85.

[0222] Example 9: Synthesis of polymer (P-III-2):

[0223]

[0224] Synthesis of polymer (P-III-2):

[0225] Accurately weigh P1-2 (942 mg, 1.0 mmol), P1-d (767 mg, 1.0 mmol) and 20 mL of anhydrous toluene and combine in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 988 mg of the product polymer (P-III-2). Yield: 80.9%. Mn = 30.7 kDa, PDI = 2.47.

[0226] Example 10: Synthesis of polymer (P-III-4):

[0227]

[0228] Synthesis of polymer (P-III-4):

[0229] Accurately weigh P2-3 (907 mg, 1.0 mmol), P1-d (767 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 926 mg of the product polymer (P-III-4). Yield: 77.9%. Mn = 35.1 kDa, PDI = 1.82.

[0230] Example 11: Synthesis of polymer (P-III-7):

[0231]

[0232] Synthesis of polymer (P-III-7):

[0233] Accurately weigh P1-2 (942 mg, 1.0 mmol), P3-a (907 mg, 1.0 mmol) and 20 mL of anhydrous toluene and combine in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 885 mg of the product polymer (P-III-7). Yield: 64.9%. Mn = 53.6 kDa, PDI = 1.97.

[0234] Example 12: Synthesis of polymer (P-III-9):

[0235]

[0236] Synthesis of polymer (P-III-9):

[0237] Accurately weigh P2-3 (907 mg, 1.0 mmol), P3-a (907 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drop into 300 mL of methanol. Filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 868 mg of the product polymer (P-III-9). Yield: 65.5%. Mn = 48.9 kDa, PDI = 2.26.

[0238] Example 13: Synthesis of polymer (P-III-11):

[0239]

[0240] Synthesis of polymer (P-III-11):

[0241] Accurately weigh P5-3 (975 mg, 0.1 mmol), P5-c (901 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drop into 300 mL of methanol. Filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 773 mg of the product polymer (P-III-11). Yield: 55.6%. Mn = 37.8 kDa, PDI = 2.62.

[0242] Example 14: Synthesis of polymer (P-III-12):

[0243]

[0244] Synthesis of polymer (P-III-12):

[0245] Accurately weigh P2-3 (907 mg, 1.0 mmol), P5-c (901 mg, 1.0 mmol) and 20 mL of anhydrous toluene and combine in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 641 mg of the product polymer (P-III-12). Yield: 48.5%. Mn = 35.8 kDa, PDI = 2.34.

[0246] Example 15: Synthesis of polymer (P-III-15):

[0247]

[0248] Synthesis of polymer (P-III-15):

[0249] Accurately weigh P1-2 (942 mg, 1.0 mmol), P7-1 (661 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 698 mg of the product polymer (P-III-15). Yield: 62.6%. Mn = 26.3 kDa, PDI = 2.14.

[0250] Example 16: Synthesis of polymer (P-III-18):

[0251]

[0252] Synthesis of polymer (P-III-18):

[0253] Accurately weigh P2-3 (907 mg, 1.0 mmol), P7-1 (661 mg, 1.0 mmol) and 20 mL of anhydrous toluene in a 100 mL pressure tube. Purge the reactants with argon for 15 minutes, then quickly add Pd(PPh3)4 (35 mg, 0.03 mmol). After purging with argon for another 15 minutes, stir the reactants under reflux for 24 hours. After cooling to room temperature, drip into 300 mL of methanol, filter to obtain a solid, and extract with methane, hexane and chloroform in turn. Concentrate the extract obtained by extraction with chloroform, then add it to 300 mL of methanol, filter and collect the filter cake and dry it to obtain 709 mg of product polymer (P-III-18). Yield: 65.6%. Mn = 27.6 kDa, PDI = 1.88.

[0254] Preparation and characterization of organic solar cell OPV devices

[0255] The following examples illustrate the preparation, implementation and characterization of the OPV device in the organic electronic device provided by the present invention, but the present invention is not limited to the following examples.

[0256] Device Example 1:

[0257] The OPV device structure is as follows: indium tin oxide ITO / PEDOT:PSS / active layer / PNINN / Ag.

[0258] 1) ITO substrate cleaning:

[0259] 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.

[0260] 2) Anode buffer layer preparation

[0261] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 4300 rpm for 20 s, and dried at 150° C. for 20 min to obtain an anode buffer layer.

[0262] 3) Preparation of photoactive layer

[0263] In a glove box (inert gas atmosphere), the photoactive layer solution was 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.

[0264] Among them, the donor material in the photoactive layer material is selected from polymer (P1), the acceptor material is selected from A-11, the mass ratio of polymer (P1):A-11 is 1:1.2, the polymer (P1) and A-11 are dissolved in chloroform to form a solution with a concentration of 15.4 mg / mL, and 0.5% by volume of 1-CN is added to the solution as an additive to obtain a photoactive layer solution.

[0265]

[0266] 4) Preparation of cathode buffer layer

[0267] After thermal annealing on a hot plate at 80°C for 10 minutes, the cathode buffer layer material PNINN (PNINN was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the active layer at a spin coating speed of 3000 rpm and a spin time of 20 seconds to obtain a cathode buffer layer.

[0268] 5) Cathode layer preparation

[0269] 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.

[0270] 6) Packaging

[0271] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0272] Device Example 2

[0273] The preparation method of device example 2 is the same as that of device example 1, except that the donor material polymer (P1) is replaced by polymer (P2).

[0274] Device Example 3

[0275] The preparation method of device example 3 is the same as that of device example 1, except that the donor material polymer (P1) is replaced by polymer (P-II-2) and polymer (P-III-2), wherein the mass ratio of polymer (P-II-2) and polymer (P-III-2) is selected from 0.8:0.2.

[0276] Device Example 4

[0277] The preparation method of device example 4 is the same as that of device example 1, except that the donor material polymer (P1) is replaced by polymer (P-II-2) and polymer (P-III-4), wherein the mass ratio of polymer (P-II-2) and polymer (P-III-4) is selected from 0.8:0.2.

[0278] Device Comparative Example 1

[0279] The preparation method of device comparison example 1 is the same as that of device example 1, except that the donor material polymer (P1) is replaced by polymer (P-II-2).

[0280] The prepared organic solar cell device was subjected to a performance test under sunlight. Under the irradiation of AM 1.5G standard light of a solar simulator (SS-F5-3A), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated, as shown in Table 1.

[0281] Table 1

[0282]

[0283] It can be seen from the data in Table 1 that according to the polymer device embodiments with the same components, the effect of the copolymerized device is better than that of the blended device. The possible reason is that the film prepared by the copolymerized polymer has a better microscopic morphology than the blended mixture blended with the acceptor material, thereby improving the photoelectric conversion efficiency of the device.

[0284] It can be seen from the data in Table 1 that the polymer or mixture provided by the present invention as a donor material is applied to the OPV device (device examples 1-4) and the device effect is better than that of a single component polymer (device comparison example 1), because: the introduction of the third component optimizes the energy level and absorption spectrum of the active layer donor material, making it more compatible with the energy level and spectrum of the non-fullerene acceptor material. In particular, the two donor structural units have similar chemical structures and good compatibility, which is conducive to fine-tuning the morphology of photon collection and the ternary blend film, effectively adjusting the molecular orientation and aggregation of the polymer, thereby improving the photoelectric conversion efficiency of the device.

[0285] Device Example 5:

[0286] The OPV device structure is as follows: indium tin oxide ITO / PEDOT:PSS / active layer / PNDIT-F3N / Ag.

[0287] 1) ITO substrate cleaning:

[0288] 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.

[0289] 2) Anode buffer layer preparation

[0290] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 4300 rpm for 20 s, and dried at 150° C. for 20 min to obtain an anode buffer layer.

[0291] 3) Preparation of photoactive layer

[0292] In a glove box (inert gas atmosphere), the photoactive layer solution was 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.

[0293] Among them, the donor material in the photoactive layer material is selected from polymer (P3), the acceptor material is selected from A-13, the mass ratio of polymer (P3): A-13 is 1:1.2, the polymer (P3) and A-13 are dissolved in chloroform to form a solution with a concentration of 8.8 mg / mL, and 4 mg / mL of additive DIB is added to the solution to obtain a photoactive layer solution.

[0294]

[0295] 4) Preparation of cathode buffer layer

[0296] After thermal annealing on a hot plate at 80°C for 10 min, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 0.5 mg / mL, and 0.5% by volume acetic acid was added to the solution) was evenly spin-coated on the active layer at a spin coating speed of 3000 rpm and a rotation time of 30 s to obtain a cathode buffer layer.

[0297] 5) Cathode layer preparation

[0298] 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.

[0299] 6) Packaging

[0300] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0301] Device Example 6

[0302] The preparation method of device example 6 is the same as that of device example 5, except that the donor material polymer (P3) is replaced by polymer (P4).

[0303] Device Example 7

[0304] The preparation method of device example 7 is the same as that of device example 5, except that the donor material polymer (P3) is replaced by polymer (P-II-4) and polymer (P-III-7), wherein the mass ratio of polymer (P-II-4) and polymer (P-III-7) is selected from 0.9:0.1.

[0305] Device Example 8

[0306] The preparation method of device example 8 is the same as that of device example 5, except that the donor material polymer (P3) is replaced by polymer (P-II-4) and polymer (P-III-9), wherein the mass ratio of polymer (P-II-2) and polymer (P-III-9) is selected from 0.9:0.1.

[0307] Device Comparative Example 2

[0308] The preparation method of device comparison example 2 is the same as that of device example 5, except that the donor material polymer (P3) is replaced by polymer (P-II-4).

[0309] The prepared organic solar cell device was subjected to a performance test under sunlight. Under the irradiation of AM 1.5G standard light of a solar simulator (SS-F5-3A), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated, as shown in Table 2.

[0310] Table 2

[0311]

[0312] It can be seen from the data in Table 2 that the copolymer or blend shown in the present invention is used as a donor material in an OPV device (device examples 5-8) and the device effect is better than that of a single component polymer (device comparison example 2).

[0313] 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. A polymer, characterized in that: The polymer has a structure as shown in general formula (I): in: Ar1 and Ar2 are each independently selected from substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, and substituted or unsubstituted non-aromatic heterocyclic groups having 5 to 30 ring atoms; Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; x, y are the mole fractions of each unit, 0 <y≤1,0≤x<1,x+y=1; n is the number of repeating units, and n is an integer greater than 1; The term "substituted or unsubstituted" means that the group is not substituted or is substituted with one or more substituents R * Replacement, R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups.

2. The polymer according to claim 1, characterized in that: Ar1, Ar2 each occurrence is independently selected from one or more R a Substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, replaced by one or more R a Substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, one or more R a A substituted or unsubstituted non-aromatic heterocyclic group having 5 to 20 ring atoms; R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

3. The polymer according to claim 1, characterized in that: Ar1 and Ar2 are each independently selected from any of the following groups: in: R 101 , R 102 , R 103 , R 104 , R 105 , R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; * indicates the attachment site.

4. The polymer according to claim 3, characterized in that: The polymer is selected from any one of the structures of formula (I-1) to (I-10):

5. The polymer according to claim 4, characterized in that: R1, R2, R3, R4, R5, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, straight chain alkyl having 1-16 carbon atoms, straight chain alkoxy having 1-16 carbon atoms, straight chain alkylthio having 1-16 carbon atoms, branched chain alkyl having 3-16 carbon atoms, branched chain alkoxy having 3-16 carbon atoms, branched chain alkylthio having 3-16 carbon atoms; R6, R7, R8, R9, each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, straight-chain ester having 1-10 carbon atoms, branched-chain ester having 3-10 carbon atoms, or a group formed by a combination of the above groups; R 101 Each occurrence is independently selected from a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain or a cyclic alkyl group having 3 to 10 carbon atoms; R 102 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, or a group formed by a combination of the above groups; R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain ester group having 1 to 10 carbon atoms, a branched or cyclic ester group having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

6. The polymer according to claim 1, characterized in that: The polymer is selected from any of the following structures:

7. A mixture, characterized in that: The mixture comprises at least one polymer 1 represented by the general formula (II) and at least one polymer 2 represented by the general formula (III): in: Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic heterocyclic group having 5 to 30 ring atoms; Each time X and Z appear, they are independently selected from CR 10 or N, and at least one of X and Z is selected from N; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; n is the number of repeating units and n is an integer greater than 1; The term "substituted or unsubstituted" means that the group is not substituted or is substituted with one or more substituents R * Replacement, R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups.

8. The mixture according to claim 7, characterized in that: The polymer 1 is selected from any one of the structural formulas (II-1) to (II-5): Where: R 101 , R 102 , R 106 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched or cyclic ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; And / or, polymer 2 is selected from any one of the structural formulas (III-1) to (III-10):

9. The mixture according to claim 7, characterized in that: Polymer 1 is selected from any of the following structures: And / or, polymer 2 is selected from any of the following structures:

10. The mixture according to claim 7, characterized in that: The mass ratio of polymer 1 to polymer 2 is selected from 20:1 to 1:

1.

11. The mixture according to claim 7, characterized in that: The mixture further comprises at least one active layer acceptor material, wherein the active layer acceptor material is selected from non-fullerene acceptor materials and / or fullerene acceptor materials.

12. An organic electronic device comprising a cathode, an anode and at least one functional layer, characterized in that: The at least one functional layer comprises a polymer as claimed in claims 1 to 6 or a mixture as claimed in any one of claims 7 to 11.

Images