A side chain polymer and its use in organic electronic devices

Abstract

The application provides a side chain polymer and application thereof in organic electronic devices, and belongs to the field of organic photoelectric materials. The side chain polymer provided by the application is selected from non-fullerene acceptor materials, has good thermal stability and film forming property, and when the side chain polymer is matched with a donor material to prepare an organic solar cell device, effective intermolecular charge transfer can occur between the donor and the acceptor, so that the device exhibits excellent device performance.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials, and more particularly to a side-chain polymer and its application in organic electronic devices. Background Technology

[0002] Organic solar cells have attracted much attention due to their advantages of being lightweight, flexible, semi-transparent, and solution-processable. The active layer, fabricated from a blend of donor and acceptor materials, is the core component of polymer solar cells, responsible for key tasks such as photon-to-charge conversion and charge transport. In recent years, polymer solar cells based on polymer donor:non-fullerene acceptor blends have developed rapidly, with energy conversion efficiencies exceeding 19%. Compared to polymer donor:non-fullerene acceptor organic solar cells, the development of all-polymer solar cells based on polymer donor:polymer acceptor systems has lagged behind, mainly due to the scarcity of high-efficiency polymer acceptor types.

[0003] Currently, polymer receptor development is mainly based on The system comprises SMA selected from non-fullerene small molecule acceptor materials, primarily those based on the Y6 or ITIC framework; Q is the modification unit, mainly selected from structures such as thiophene, bithiophene, thiophene-2-thiophene, and benzodithiophene. However, currently, the variety of polymer acceptor materials is extremely limited, and research directions are restricted. Therefore, it is necessary to develop novel polymer receptor materials and promote the diversification of polymer receptor material research and development routes. Summary of the Invention

[0004] The purpose of this invention is to provide a novel polymer acceptor material, wherein the polymer acceptor material is a side-chain polymer, and when it is used as an acceptor material in the photoactive layer of an organic solar cell, a superior photoelectric conversion efficiency can be obtained for the organic solar cell device.

[0005] The technical solution for achieving the objective of this invention is: a side-chain polymer having a structure as shown in general formula (I):

[0006]

[0007] in:

[0008] Each occurrence of L is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, unsubstituted or R-substituted. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted.* Substituted heteroaromatic groups having 5-20 ring atoms;

[0009] Each occurrence of Ar1 and Ar2 is independently selected from those that are not substituted or are replaced by R. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0010] Each time M appears, it is independently selected from O or C(CN)2;

[0011] Each occurrence of Ar3 and Ar4 is independently selected from unsubstituted or R-type components. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0012] R1 and R2, each time appearing independently, are selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, unsubstituted or R * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0013] R * Each occurrence is independently selected from -D, halogen, cyano, nitro, straight-chain alkyl with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, aromatic group with 6-20 carbon atoms, heteroaromatic group with 5-20 cyclic atoms, or a group formed by a combination of the above groups;

[0014] n is the number of repeating units and is an integer greater than or equal to 2.

[0015] Furthermore, the present invention also provides a mixture comprising the side-chain polymer as described above, and at least one other organic functional material; wherein the at least one other organic functional material is selected from an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material.

[0016] Furthermore, the present invention also provides an organic electronic device comprising at least one functional layer: the functional layer comprising the above-described side-chain polymer or the above-described mixture.

[0017] Compared with the prior art, the present invention has at least the following beneficial technical effects:

[0018] The photoactive layer polymer acceptor material of this invention creatively adopts a side-chain polymerization structure, which enables the prepared polymer acceptor material to maintain the basic photoelectric properties of small molecules on the one hand, and has better thermal stability and film-forming properties than small molecule materials on the other hand. When it is combined with donor materials to prepare organic solar cell devices, effective intermolecular charge transfer can occur between the donor and acceptor, thereby enabling the prepared device to exhibit excellent device performance. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the following detailed description is provided in conjunction with specific embodiments of the invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These 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 connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: 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, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0021] In this invention, organic photovoltaic devices, organic solar cells, and OPV have the same meaning and can be used interchangeably.

[0022] In this invention, the terms "photoactive layer" and "active layer" have the same meaning and can be used interchangeably.

[0023] In this invention, when the same substituent appears multiple times, it can be independently selected from the same or different groups.

[0024] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., a monocyclic compound, a fused-ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, the number of ring atoms in a benzene ring is 6, in a naphthalene ring it is 10, in a thiophene group it is 5, and in a thiophene-3-thiophene ring it is 8.

[0025] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0026] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0027] In this invention, "alkyl" can refer to straight-chain, branched, and / or cyclic alkyl groups. Straight-chain alkyl groups can have 1 to 20, 1 to 16, 1 to 10, or 1 to 6 carbon atoms; branched alkyl groups can have 3 to 20, 3 to 16, 1 to 10, or 3 to 6 carbon atoms; cyclic alkyl groups can have 3 to 20, 3 to 16, 1 to 10, or 3 to 6 carbon atoms. 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, and -C 10 H 21 -C 11 H 23 -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 carbon atoms, branched alkyl groups containing 5 carbon atoms, branched alkyl groups containing 6 carbon atoms, branched alkyl groups containing 7 carbon atoms, branched alkyl groups containing 8 carbon atoms, branched alkyl groups containing 9 carbon atoms, branched alkyl groups containing 10 carbon atoms, branched alkyl groups containing 11 carbon atoms, branched alkyl groups containing 12 carbon atoms, branched alkyl groups containing 13 carbon atoms, branched alkyl groups containing 14 carbon atoms, branched alkyl groups containing 15 carbon atoms, and branched alkyl groups containing 16 carbon atoms.

[0028] In this invention, the term "straight-chain alkoxy" refers to a group with the structure "-O-straight-chain alkyl", that is, a straight-chain alkyl group as defined above that is connected to other groups via an oxygen atom.

[0029] In this invention, the term "branched alkoxy" refers to a group with the structure "-O-branched alkyl", that is, a branched alkyl group as defined above that is connected to other groups via an oxygen atom.

[0030] In this invention, the term "straight-chain alkylthio" refers to a group with the structure "-S-straight-chain alkyl", that is, a straight-chain alkyl group as defined above that is connected to other groups via a sulfur atom.

[0031] In this invention, the term "branched alkylthio" refers to a group with the structure "-S-branched alkyl", that is, a branched alkyl group as defined above that is connected to other groups via a sulfur atom.

[0032] In this invention, "halogen" includes fluorine, chlorine, bromine, iodine, etc.

[0033] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbon ring. The aromatic group can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl; in other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated by carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated by carbon-carbon bonds can also be considered as the aromatic group of this application. Preferably, the aromatic group is selected from aromatic groups having 6-30 carbon atoms; further, it is selected from aromatic groups having 6-20 carbon atoms; further, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic group includes, but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthraceneyl, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives.

[0034] In this invention, a "heteroaromatic group" refers to a monovalent aromatic ring or its derivative containing one, two, three, four, five, six or more heteroatoms, wherein the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl or a polycyclic heteroaryl; in other words, the heteroaromatic group can be a single aromatic ring system or a system of multiple aromatic rings conjugated by carbon-carbon bonds, and any aromatic ring system can be a single aromatic monocyclic ring or a fused aromatic ring. Preferably, the heteroaromatic group is selected from heteroaromatic groups having 6-30 ring atoms; further, it is selected from heteroaromatic groups having 6-20 ring atoms; and further, it is selected from heteroaromatic groups having 6-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridinyl, bipyridinyl, pyrimidinyl, triazinyl, acridineyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrol, thienopyrrol, thienopyrrol, furanol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazole and their derivatives.

[0035] The terms “combinations thereof,” “any combination thereof,” “any combination thereof,” and “combination” used in this invention include all suitable combinations of any two, any three, or any three or more items of the listed groups.

[0036] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0037] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0038] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0039] A first aspect of the present invention provides a side-chain polymer having a structure as shown in general formula (I):

[0040]

[0041] in:

[0042] Each occurrence of L is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, unsubstituted or R-substituted. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0043] Each occurrence of Ar1 and Ar2 is independently selected from those that are not substituted or are replaced by R. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0044] Each time M appears, it is independently selected from O or C(CN)2;

[0045] Each occurrence of Ar3 and Ar4 is independently selected from unsubstituted or R-type components. * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0046] R1 and R2, each time appearing independently, are selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, unsubstituted or R * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-20 ring atoms;

[0047] R * Each occurrence is independently selected from -D, halogen, cyano, nitro, straight-chain alkyl with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, aromatic group with 6-20 carbon atoms, heteroaromatic group with 5-20 cyclic atoms, or a group formed by a combination of the above groups;

[0048] n is the number of repeating units and is an integer greater than or equal to 2.

[0049] In the present invention, "unreplaced or R" * "Substitution" indicates that the functional group specified after the term may not be substituted, or may be substituted by one, two, or more R groups. * replace.

[0050] In this invention, when one or more groups represented by the same letter appear simultaneously and in multiple places in the compound, they can be selected from the same group or from different groups. For example, in general formula I, M can be selected from the same group or from different groups.

[0051] In this invention, multiple groups are described simultaneously. "Independently selected" means that when one or more groups appear simultaneously, they are all independently selected, and they can be the same or different. For example, Ar1 and Ar2 are each independently selected, indicating that Ar1 and Ar2 are independently selected, and they can be the same or different.

[0052] In one embodiment, R * Each occurrence is independently selected from halogen, cyano, nitro, straight-chain alkyl with 1-10 carbon atoms, branched or cyclic alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, branched or cyclic alkoxy with 3-10 carbon atoms, straight-chain alkylthio with 1-10 carbon atoms, and branched or cyclic alkylthio with 3-10 carbon atoms.

[0053] In one embodiment, Ar1 and Ar2 are each independently selected from unsubstituted or R-substituted Ar1. * Substituted aromatic groups having 6-15 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-15 ring atoms. Furthermore, Ar1 and Ar2, each time appearing, are independently selected from unsubstituted or R-substituted groups. * Substituted heteroaromatic groups having 5-11 ring atoms.

[0054] In one specific embodiment, Ar1 and Ar2 are each independently selected from any of the following groups:

[0055]

[0056] in:

[0057] Each time Y appears, it is independently selected from O, S, or Se;

[0058] Each time R3 appears, it is independently selected from -H, -D, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched alkylthio with 3-20 carbon atoms, aromatic group with 6-20 carbon atoms, or heteroaromatic group with 5-20 cyclic atoms, or a group formed by combination of the above groups;

[0059] * indicates a confluent ring site;

[0060] # indicates a connection point.

[0061] It should be noted that when * indicates a fused ring site, the fusion site is selected from C atoms.

[0062] In one embodiment, each occurrence of Y is independently selected from S or Se.

[0063] Furthermore, each time Ar1 and Ar2 appear, they are independently selected from any of the following groups:

[0064]

[0065] In one embodiment, R3, each occurrence thereof, is selected, either identically or differently, from -H, -D, straight-chain alkyl groups having 1-16 carbon atoms, branched-chain alkyl groups having 3-16 carbon atoms, straight-chain alkoxy groups having 1-16 carbon atoms, branched-chain alkoxy groups having 3-16 carbon atoms, straight-chain alkylthio groups having 1-16 carbon atoms, branched-chain alkylthio groups having 3-16 carbon atoms, unsubstituted or R * Substituted phenyl, or unsubstituted or R * Substituted thiophene group.

[0066] Specifically, each time R3 appears, it is selected, either identically or differently, from straight-chain or branched alkyl groups having 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, or 11 carbon atoms. Straight-chain or branched alkoxy groups, straight-chain or branched alkoxy groups with 12 carbon atoms, straight-chain or branched alkoxy groups with 13 carbon atoms, straight-chain or branched alkoxy groups with 14 carbon atoms, straight-chain or branched alkoxy groups with 15 carbon atoms, straight-chain or branched alkoxy groups with 16 carbon atoms, straight-chain or branched alkathioyl groups with 6 carbon atoms, straight-chain or branched alkathioyl groups with 7 carbon atoms, and straight-chain or branched alkoxy groups with 8 carbon atoms. Thioyl group, straight-chain or branched alkylthioyl group with 9 carbon atoms, straight-chain or branched alkylthioyl group with 10 carbon atoms, straight-chain or branched alkylthioyl group with 11 carbon atoms, straight-chain or branched alkylthioyl group with 12 carbon atoms, straight-chain or branched alkylthioyl group with 13 carbon atoms, straight-chain or branched alkylthioyl group with 14 carbon atoms, straight-chain or branched alkylthioyl group with 15 carbon atoms, straight-chain or branched alkylthioyl group with 16 carbon atoms, and R * Substituted phenyl, R * Substituted thiophene group; wherein: the R * Preferably, it is selected from straight-chain or straight-chain alkyl groups having 6-12 C atoms.

[0067] Furthermore, each time Ar1 and Ar2 appear, they are independently selected from any of the following groups:

[0068]

[0069]

[0070] In a preferred embodiment, the side-chain polymer according to the present invention is selected from the following structures:

[0071]

[0072] Among them, L, R1, R2, R3, Y, M, Ar3, and Ar4 have the same meanings as described above.

[0073] In another preferred embodiment, the side-chain polymer according to the present invention is selected from the following structures:

[0074]

[0075] Among them, L, R1, R2, R3, Y, M, Ar3, and Ar4 have the same meanings as described above.

[0076] In one embodiment, each occurrence of R1 and R2 is independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms.

[0077] In one embodiment, each occurrence of R1 and R2 is independently selected from straight-chain alkyl groups having 1-16 carbon atoms or branched alkyl groups having 3-16 carbon atoms.

[0078] Specifically, each time R1 and R2 appear, they are independently selected from straight-chain or branched alkyl groups having 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, and 16 carbon atoms.

[0079] Furthermore, each time R1 and R2 appear, they are independently selected from the following groups:

[0080]

[0081] In one specific embodiment, R1 and R2 are selected from the same group.

[0082] In one embodiment, Independently selected

[0083] In one embodiment, Independently selected

[0084] In one embodiment, each occurrence of Ar3 and Ar4 is independently selected from unsubstituted or R-substituted Ar3. * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or R-substituted. * Substituted heteroaromatic groups having 5-10 ring atoms.

[0085] In one embodiment, Ar3 and Ar4 are each independently selected from any of the following groups:

[0086]

[0087] in:

[0088] Each time X appears, it is independently selected from N or CR4;

[0089] Each time W appears, it is independently selected from O, S, and Se;

[0090] Each time R4 appears, it is independently selected from -H, -D, halogen, cyano, nitro, straight-chain alkyl with 1-10 carbon atoms, branched or cyclic alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, branched or cyclic alkoxy with 3-10 carbon atoms, straight-chain alkylthio with 1-10 carbon atoms, branched or cyclic alkylthio with 3-10 carbon atoms, or a group formed by a combination of the above groups;

[0091] * indicates a fused ring site, and the fused site is selected from C atoms.

[0092] Furthermore, each time Ar3 and Ar4 appear, they are independently selected from any of the following groups:

[0093]

[0094] Furthermore, each occurrence of R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, -NO2, methyl, ethyl, isopropyl, tert-butyl, or butyl.

[0095] Furthermore, Each occurrence is independently selected from any of the following groups:

[0096]

[0097]

[0098] In one embodiment, each occurrence of L is independently selected from straight-chain alkyl groups having 1-16 carbon atoms, branched alkyl groups having 3-16 carbon atoms, straight-chain alkoxy groups having 2-16 carbon atoms, branched alkoxy groups having 3-16 carbon atoms, straight-chain alkylthio groups having 2-16 carbon atoms, branched alkylthio groups having 3-16 carbon atoms, phenyl groups, and R groups. * Substituted phenyl, thiophene, and R * Substituted thiophene group. Wherein: R * Preferably, it is derived from straight-chain alkyl groups having 2-15 carbon atoms, branched alkyl groups having 3-15 carbon atoms, straight-chain alkoxy groups having 2-15 carbon atoms, branched alkoxy groups having 3-15 carbon atoms, straight-chain alkylthio groups having 2-15 carbon atoms, or branched alkylthio groups having 3-15 carbon atoms.

[0099] Furthermore, L is selected from straight-chain alkyl groups having 1-16 carbon atoms; specifically, L is selected from -CH2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13 -、-(CH2) 14 -、-(CH2) 15 -、-(CH2) 16 -

[0100] The side-chain polymers provided by this invention can be selected from the following structural formulas, but are not limited thereto:

[0101]

[0102]

[0103]

[0104] It should be noted that in the above structural formula, -(CH2) m - indicates a straight-chain alkyl group with m carbon atoms, where m is an integer from 0 to 15.

[0105] In one embodiment, m = 0; in one embodiment, m = 1; in one embodiment, m = 2; in one embodiment, m = 3; in one embodiment, m = 4; in one embodiment, m = 5; in one embodiment, m = 6; in one embodiment, m = 7; in one embodiment, m = 8; in one embodiment, m = 9; in one embodiment, m = 10; in one embodiment, m = 11; in one embodiment, m = 12; in one embodiment, m = 13; in one embodiment, m = 14; in one embodiment, m = 15.

[0106] In one embodiment, n is selected from an integer from 2 to 10000; further, n is selected from an integer from 2 to 1000; further, n is selected from an integer from 4 to 500; further, n is selected from an integer from 5 to 100; further, n is selected from an integer from 5 to 20.

[0107] The side-chain polymer according to the first aspect of the present invention can be used as a photoactive layer acceptor material in organic solar cell devices.

[0108] A second aspect of the present invention relates to a mixture comprising a side-chain polymer as described in the first aspect, and at least one other organic functional material, wherein the at least one other organic functional material may be an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material; and the weight ratio of the at least one organic functional material to the other organic functional material is 1:99 to 99:1. In one embodiment, the photoactive layer comprises a donor material and an acceptor material, wherein the weight ratio of the donor material to the acceptor material is 1 / 1 to 1 / 1.5.

[0109] In one embodiment, the other organic functional material is selected from photoactive layer donor materials; preferably, the donor material is selected from one or more of PBDB-T, PM6, PM7, PBT1-C-2Cl, ES1, SZ1, SZ2, PTQ10, PTQ11, PB2, and PB2F.

[0110] A third aspect of the present invention relates to a composition comprising a side-chain polymer as described in the first aspect, or a mixture as described in the second aspect, and at least one organic solvent. The organic solvent is selected from aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers, and mixtures thereof.

[0111] In one embodiment, the organic solvent is selected from dichloromethane, trichloromethane, chlorobenzene, 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, acetophenone, tetrahydronaphthalene, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indene, methyl benzoate, ethyl benzoate, mesitylene, or mixtures thereof.

[0112] In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0113] It is understood that the organic solvent can evaporate from the solvent system to form a thin film comprising the organic compound.

[0114] In one embodiment, the composition is a solution. In other embodiments, the composition is a suspension. The solution or suspension may further include additives for adjusting viscosity, modifying film-forming properties, improving adhesion, etc. The additives may be selected from, but are not limited to, at least one of surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, and adhesives.

[0115] This invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices. In one embodiment, the composition is used to prepare organic electronic devices by a printing or coating method. The printing or coating method can be, but is not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, slot extrusion coating, etc. Slot coating, spin coating, and inkjet printing are preferred.

[0116] The present invention further relates to the use of a side-chain polymer as described in the first aspect, a mixture as described in the second aspect, and a composition as described in the third aspect in organic electronic devices. 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. In a specific embodiment, the organic electronic device is selected from organic solar cells.

[0117] The fourth aspect of the present invention relates to an organic electronic device comprising at least one functional layer, said functional layer comprising a side-chain polymer as described in the first aspect, or a mixture as described in the second aspect.

[0118] Furthermore, the organic electronic device includes a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode, wherein at least one of the one or more functional layers includes a side-chain polymer as described in the first aspect, or a mixture as described in the second aspect.

[0119] In one embodiment, the one or more functional layers include at least a photoactive layer, the photoactive layer material comprising a polymer as described in the first aspect, or a mixture as described in the second aspect.

[0120] In one embodiment, the one or more functional layers include at least an anode buffer layer, a photoactive layer, and a cathode buffer layer, wherein the photoactive layer material comprises a side-chain polymer as described in the first aspect, or a mixture as described in the second aspect.

[0121] It should be noted that, in order to improve the performance of organic solar cell devices, the one or more functional layers may further include other functional layers, including but not limited to charge injection layers and / or charge blocking layers.

[0122] In one embodiment, the organic electronic device is selected from organic solar cells.

[0123] Furthermore, the organic solar cell also includes a substrate. Specifically, the substrate may be disposed on one side of the first electrode and on a different side from the functional layer.

[0124] In one embodiment, the first electrode is an anode and the second electrode is a cathode; in another embodiment, the first electrode may be a cathode and the second electrode may be an anode.

[0125] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include, but is not limited to, single-layer or multi-layer films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), and polyimide (PI), and substrates commonly used in organic solar cells may also be used.

[0126] The anode electrode can be made of transparent or translucent materials, but is not limited to these. The anode electrode may include metals, such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; and conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxo)thiophene] (PEDOT), polypyrrole and polyaniline, but is not limited to these.

[0127] The cathode electrode can be made of a metal with a low work function. The cathode electrode may include metals such as silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd), or alloys thereof; and materials with multilayer structures such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al∶Li, Al∶BaF2, and Al∶BaF2∶Ba, but are not limited thereto.

[0128] The photoactive layer comprises electron donor materials and electron acceptor materials. Specifically, the electron donor materials can be various polymer materials or small molecule materials. Polymer materials can be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymer material systems, such as PF8BT, etc.; novel narrow-bandgap polymer material systems, such as benzothiadiazoles (BT, BBT), quinoxalines (QU, PQ), pyrazines (TP, PQ), and copolymers of electron-rich groups (such as thiophene derivatives), such as PCDTBT, PCPDTBT, PFO-DBT, PTB7, PM6, J52, etc. The small molecule material may be selected from one or more of the following: copper phthalocyanine (II), zinc phthalocyanine, tris[4-(5-dicyanomethylenemethyl-2-thienyl)phenyl]amine, 2,4-bis[4-(N,N-dibenzylamino)-2,6-dihydroxyphenyl]squamine, benzo[b]anthracene and pentabenzene, B8, B10, etc. Preferably, the donor material is selected from one or more of PBDB-T, PM6, PM7, PBT1-C-2Cl, ES1, SZ1, SZ2, PTQ10, PTQ11, PB2, PB2F. The electron acceptor material is selected from the side-chain polymers of general formula (I).

[0129] The photoactive layer can be formed by dissolving a photoactive material, such as an electron donor and / or an electron acceptor, 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 coating, slot coating, and inkjet printing, but not limited thereto.

[0130] The anode buffer layer material can be selected from poly(styrene sulfonic acid) PEDOT:PSS (poly(3,4-ethylenedioxythiophene)), molybdenum oxide (MoOx), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO4), etc. x， Preferably, x is selected from 2 or 3, etc., but is not limited thereto.

[0131] The cathode buffer layer material can be an electron-withdrawing metal oxide or polymer. The metal oxide can be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc., and the polymer can be PFN-Br, PFN, PDINN, or PNDIT-F3N-Br, etc., but is not limited to these.

[0132] This invention also relates to the application of organic solar cells according to the invention in various devices, including, but not limited to, building-integrated photovoltaics (BIPV), electronic shelf labels, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0133] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any 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.

[0134] Synthesis Example 1: Synthesis of Side-Chain Polymer (7)

[0135]

[0136] Synthesis of compound 7-1:

[0137] Accurately weigh 17.8 g (50 mmol) of compound 3,6-dibromo-4,5-dinitro-o-phenylenediamine into a 500 mL three-necked flask, add 200 mL of glacial acetic acid, and then slowly add an aqueous solution of sodium nitrite (4.14 g dissolved in 80 mL of deionized water) dropwise to the reaction system. React at room temperature for 1 hour. Filter under vacuum, and wash the filter cake several times with deionized water. Approximately 10.2 g of crude compound 7-1 was obtained. Yield: 56%.

[0138] Synthesis of compound 7-2:

[0139] Under nitrogen protection, compound 7-1 (7.34 g, 20.0 mmol) and potassium carbonate (5.53 g, 40.0 mmol) were dissolved in 180 mL of a mixed solvent of N,N-dimethylformamide (dehydrated with magnesium sulfate) and 5 mL of dimethyl sulfoxide. The reaction mixture was heated to 85 °C for 1 hour. Then, 10-bromo-1-decene (5.26 g, 24.0 mmol) was added under nitrogen protection, and the reaction mixture was heated to 90 °C for 8 hours. After cooling, the reaction mixture was poured into cold water, and the product was extracted with water and dichloromethane, repeated three times. Purification was performed by silica gel column chromatography to give approximately 6.6 g of compound 7-2, in a yield of 65%. MS: 505.71.

[0140] Synthesis of compound 7-3:

[0141] In a 100 mL round-bottom flask, 7-2 (2.5 g, 5 mmol) and tributyl(6-undecylthieno[3,2-b]thiophene-2-yl)stanane (6.42 g, 11 mmol) were weighed and dissolved in 30 mL of tetrahydrofuran. Under argon protection, bis(triphenylphosphine)palladium dichloride (0.16 g, 0.22 mmol) was added to the system. The mixture was refluxed at 80 °C for 20 hours. After cooling to actual temperature, the tetrahydrofuran was evaporated to dryness, extracted with dichloromethane, and the solvent was evaporated to dryness to obtain the crude product. The crude product was purified by silica gel column chromatography to give approximately 2.6 g of compound 7-3, in 56% yield. MS: 932.46.

[0142] Synthesis of compound 7-4:

[0143] In a 100 mL round-bottom flask, compound 7-3 (2.33 g, 2.5 mmol), triethyl phosphite (15 mL), and o-dichlorobenzene (5 mL) were added. Under argon protection, the mixture was reacted at 180 °C for 15 hours. After cooling to room temperature, the solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography to give approximately 1.23 g of compound 7-4, in 57% yield. MS: 868.54.

[0144] Synthesis of compound 7-5:

[0145] In a 250 mL flask, compound 7-4 (0.87 g, 1 mmol), potassium hydroxide (0.4 g, 7.13 mmol), isooctane bromo (0.58 g, 3 mmol), and dimethyl sulfoxide (30 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was evaporated, and the solution was purified by silica gel column chromatography to give approximately 0.51 g of compound 7-5, with a yield of 47%. MS: 1092.54.

[0146] Synthesis of compound 7-6:

[0147] In a 100 mL three-necked flask, compound 7-5 (0.50 g, 0.46 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was removed by vortexing, and the mixture was purified by silica gel column chromatography to give approximately 0.39 g of compound 7-6, with a yield of 74%. MS: 1148.58.

[0148] Synthesis of compound 7-7:

[0149] In a 250 mL round-bottom flask, compound 7-6 (0.35 g, 0.3 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (0.69 g, 3.0 mmol) were dissolved in 135 mL of chloroform. 3 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the solution was poured into 200 mL of anhydrous methanol, and the crude product was obtained by filtration. The crude product was purified by silica gel column chromatography to give approximately 0.33 g of compound 7-7, with a yield of 71%. MALDI-TOF MS: 1572.86.

[0150] Synthesis of side-chain polymer (7):

[0151] Under an argon atmosphere, 0.1572 g of compound 7-7 and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.091 g of polymer (7). Wherein: Mn = 14.1 K, PDI = 1.73.

[0152] Synthesis Example 2: Synthesis of Side-Chain Polymer (10)

[0153]

[0154] Synthesis of compound 10-1:

[0155] In a 100 mL round-bottom flask, compound 7-6 (0.115 g, 0.10 mmol) and 2-(2-bromo-4-oxo-4,5-dihydro-6H-cyclopentanonitrile[b]thiophene-6-ylidene)malononitrile (0.279 g, 1.00 mmol) were dissolved in 45 mL chloroform. 1 mL pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the mixture was poured into 200 mL anhydrous methanol and filtered to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain approximately 0.10 g of compound 10-1. MALDI-TOF MS: 1671.59.

[0156] Synthesis of side-chain polymer (10):

[0157] Under an argon atmosphere, 0.1 g of compound 10⁻¹ and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran (THF) was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.049 g of polymer (10). Wherein: Mn = 12.6 K, PDI = 1.85.

[0158] Synthesis Example 3: Synthesis of Side-Chain Polymer (14)

[0159]

[0160] Synthesis of compound 14-2:

[0161] In a 250 mL flask, compound 7-4 (0.87 g, 1 mmol), potassium hydroxide (0.4 g, 7.13 mmol), compound 14-1 (0.75 g, 3 mmol), and dimethyl sulfoxide (30 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was evaporated, and the solution was purified by silica gel column chromatography to give approximately 0.6 g of compound 14-2, with a yield of 50%. MS: 1205.46.

[0162] Synthesis of compound 14-3:

[0163] In a 100 mL three-necked flask, compound 14-2 (0.55 g, 0.46 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was removed by vortexing, and the mixture was purified by silica gel column chromatography to give approximately 0.45 g of compound 14-3, with a yield of 78%. MALDI-TOF MS: 1261.37. Synthesis of compound 14-4:

[0164] In a 250 mL round-bottom flask, compound 14-3 (0.38 g, 0.3 mmol) and 5,6-dichloro-3-(dicyanomethylene)indophenone (0.79 g, 3.0 mmol) were dissolved in 135 mL of chloroform. 3 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the solution was poured into 200 mL of anhydrous methanol, and the crude product was obtained by filtration. The crude product was purified by silica gel column chromatography to give approximately 0.4 g of compound 14-4, with a yield of 77%. MALDI-TOF MS: 1751.29.

[0165] Synthesis of side-chain polymer (14):

[0166] Under an argon atmosphere, 0.1 g of compound 14-4 and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.058 g of the side-chain polymer (14). Wherein: Mn = 17.5 K, PDI = 1.91.

[0167] Synthesis Example 4: Synthesis of Side-Chain Polymer (17)

[0168]

[0169] Synthesis of compound 17-1:

[0170] In a 250 mL round-bottom flask, compound 7-2 (10.06 g, 20 mmol) and (thieno[3,2-B]thieno-2-yl)tributyltinane (18.89 g, 44 mmol) were weighed and dissolved in 100 mL of tetrahydrofuran. Under argon protection, bis(triphenylphosphine)palladium dichloride (0.62 g, 0.88 mmol) was added to the system. The mixture was refluxed at 80 °C for 20 hours. After cooling to actual temperature, the tetrahydrofuran was evaporated to dryness, and the product was extracted with dichloromethane. The solvent was evaporated to dryness to obtain the crude product, which was purified by silica gel column chromatography to give approximately 7.6 g of compound 17-1, yield 61%, MS: 623.58.

[0171] Synthesis of compound 17-2:

[0172] In a 250 mL round-bottom flask, compound 17-1 (6.24 g, 10 mmol), triethyl phosphite (50 mL), and o-dichlorobenzene (20 mL) were added. The mixture was reacted at 180 °C for 15 hours under argon protection. After cooling to room temperature, the solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography to give approximately 3.73 g of compound 17-2, in 67% yield. MS: 559.90.

[0173] Synthesis of compound 17-3:

[0174] In a 250 mL flask, compound 17-2 (2.8 g, 5 mmol), potassium hydroxide (2 g, 35.64 mmol), isooctane bromo (2.90 g, 15 mmol), and dimethyl sulfoxide (120 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was evaporated, and the solution was purified by silica gel column chromatography to give approximately 2.19 g of compound 17-3, with a yield of 56%. MS: 784.45.

[0175] Synthesis of compound 17-4:

[0176] In a 100 mL three-necked flask, compound 17-3 (0.36 g, 0.46 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, and the organic solvent was evaporated to dryness. The mixture was purified by silica gel column chromatography to give approximately 0.30 g of compound 17-4, in 78% yield. MS: 840.14.

[0177] Synthesis of compound 17-5:

[0178] In a 250 mL round-bottom flask, compound 17-4 (0.251 g, 0.30 mmol) and thiophene indanone (0.60 g, 3.0 mmol) were dissolved in 45 mL of chloroform. 1 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the solution was poured into 200 mL of anhydrous methanol and filtered to obtain the crude product. The crude product was purified by silica gel column chromatography to give approximately 0.20 g of compound 17-5, with a yield of 55%. MALDI-TOF MS: 1204.42.

[0179] Synthesis of side-chain polymer (17):

[0180] Under an argon atmosphere, 0.1 g of compound 17-5 and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran (THF) was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.051 g of the side-chain polymer (17). Wherein: Mn = 14.4 K, PDI = 2.07.

[0181] Synthesis Example 5: Synthesis of Side-Chain Polymer (25)

[0182]

[0183]

[0184] Synthesis of compound 25-1:

[0185] Accurately weigh 3-bromothiopheno[3,2-b]thiophene (3.28 g, 15 mmol), tributyl(4-hexylphenyl)stanane (7.44 g, 16.5 mmol), and Pd(PPh3)2Cl2 (1.05 g, 1.5 mmol) into a 250 mL three-necked flask. Add 100 mL of anhydrous toluene, purge with nitrogen three times, and then heat to 110 °C. React for 20 hours. After the starting materials have completely reacted, cool to room temperature, dilute with water, extract with ethyl acetate, dry with anhydrous sodium sulfate, remove excess solvent by vacuum distillation, and purify by silica gel column chromatography with stirring to give 3.6 g of compound 25-1, yield: 80%, MS: 300.20.

[0186] Synthesis of compound 25-2:

[0187] Compound 25-1 (3.0 g, 10 mmol) was accurately weighed and dissolved in 100 mL of dry anhydrous tetrahydrofuran. The mixture was stirred thoroughly, purged with nitrogen three times, and then cooled to -70 °C. LDA (2 M, 5 mL, 10 mmol) was slowly added dropwise. The mixture was stirred at -70 °C for 2 hours, then Me3SnCl (1.0 M, 10 mL, 10 mmol) was added, and the mixture was stirred for 1 hour. The mixture was then allowed to rise naturally to room temperature and stirred overnight. After the starting material had completely reacted, the resulting mixture was poured into water and extracted with DCM. The final concentration and drying yielded approximately 3.93 g of compound 25-2. Yield: 85%. MS: 463.14.

[0188] Synthesis of compound 25-3:

[0189] In a 250 mL round-bottom flask, 1.82 g (3.6 mmol) of compound 7-2 and 3.7 g (8 mmol) of compound 25-2 were weighed and dissolved in 30 mL of tetrahydrofuran. Under argon protection, 0.05 g (0.072 mmol) of bis(triphenylphosphine)palladium dichloride was added to the system. The mixture was refluxed at 80 °C for 20 hours. After cooling to actual temperature, the tetrahydrofuran was evaporated to dryness, and the mixture was extracted with dichloromethane. The solvent was evaporated to dryness to obtain the crude product, which was purified by silica gel column chromatography to give approximately 1.9 g of compound 25-3 (yield: 56%). MS: 944.23. Synthesis of compound 25-4:

[0190] In a 250 mL round-bottom flask, compound 25-3 (1.89 g, 2 mmol), triethyl phosphite (10 mL), and o-dichlorobenzene (4 mL) were added. The mixture was reacted at 180 °C for 15 hours under argon protection. After cooling to room temperature, the solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography to give approximately 1.0 g of compound 25-4 (yield: 57%, MS: 880.45).

[0191] Synthesis of compound 25-5:

[0192] In a 250 mL flask, compound 25-4 (0.88 g, 1.0 mmol), potassium hydroxide (0.39 g, 7 mmol), isooctane bromo (0.58 g, 3 mmol), and dimethyl sulfoxide (30 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, separated, and the solvent was evaporated. The solution was then purified by silica gel column chromatography to give approximately 0.86 g of compound 25-5. Yield: 78%, MS: 1104.70.

[0193] Synthesis of compound 25-6:

[0194] In a 100 mL three-necked flask, compound 25-5 (0.507 g, 0.46 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, separated, and the organic solvent was evaporated. The mixture was then purified by silica gel column chromatography to give approximately 0.422 g of compound 25-6 (yield: 79%), MS: 1160.48.

[0195] Synthesis of compound 25-7:

[0196] In a 250 mL round-bottom flask, compound 25-6 (0.116 g, 0.10 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (0.230 g, 1.00 mmol) were dissolved in 45 mL of chloroform. 1 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the mixture was poured into 200 mL of anhydrous methanol and filtered to obtain the crude product. The crude product was purified by silica gel column chromatography to give approximately 0.10 g of compound 25-7, yield: 64%, MALDI-TOF MS: 1585.53.

[0197] Synthesis of side-chain polymer (25):

[0198] Under an argon atmosphere, 0.1 g of 25-7 and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.063 g of polymer (25). Wherein: Mn = 15.9 K, PDI = 1.60.

[0199] Synthesis Example 6: Synthesis of Side-Chain Polymer (28)

[0200]

[0201]

[0202] Synthesis of compound 28-1:

[0203] In a 250 mL round-bottom flask, compound 7-2 (10.06 g, 20 mmol) and tributyl(6-undecylselenophenyl[3,2-b]thiophen-2-yl)stanane (27.72 g, 44 mmol) were weighed and dissolved in 100 mL of tetrahydrofuran. Under argon protection, bis(triphenylphosphine)palladium dichloride (0.62 g, 0.88 mmol) was added to the system. The mixture was refluxed at 80 °C for 20 hours. After cooling to actual temperature, the tetrahydrofuran was evaporated to dryness, and the mixture was extracted with dichloromethane. The solvent was evaporated to dryness to obtain the crude product, which was purified by silica gel column chromatography to give approximately 10.54 g of compound 28-1. Yield: 51%, MS: 1026.22.

[0204] Synthesis of compound 28-2:

[0205] In a 250 mL round-bottom flask, compound 28-1 (10.26 g, 10 mmol), triethyl phosphite (50 mL), and o-dichlorobenzene (20 mL) were added. Under argon protection, the mixture was reacted at 180 °C for 15 hours. After cooling to room temperature, the solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography to give approximately 5.0 g of compound 28-2. Yield: 52%, MS: 962.32.

[0206] Synthesis of compound 28-3:

[0207] In a 250 mL flask, compound 28-2 (4.81 g, 5 mmol), potassium hydroxide (2 g, 35.64 mmol), isooctane bromo (2.90 g, 15 mmol), and dimethyl sulfoxide (120 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, separated, and the solvent was evaporated. The solution was then purified by silica gel column chromatography to give approximately 4.3 g of compound 28-3. Yield: 73%, MALDI-TOF MS: 1186.58.

[0208] Synthesis of compound 28-4:

[0209] In a 100 mL three-necked flask, compound 28-3 (0.546 g, 0.46 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, separated, and the organic solvent was evaporated. The mixture was then purified by silica gel column chromatography to give approximately 0.42 g of compound 28-4 (yield: 74%). MALDI-TOF MS: 1242.55.

[0210] Synthesis of compound 28-5:

[0211] In a 250 mL round-bottom flask, compound 28-4 (0.124 g, 0.10 mmol) and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (0.262 g, 1.00 mmol) were dissolved in 45 mL of chloroform. 1 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the solution was poured into 200 mL of anhydrous methanol, and the crude product was obtained by filtration. The crude product was purified by silica gel column chromatography to give approximately 0.11 g of compound 28-5. Yield: 64%, MALDI-TOF MS: 1732.55.

[0212] Synthesis of side-chain polymer (28):

[0213] Under an argon atmosphere, 0.1 g of 28-5 and 0.020 mmol of azobisisobutyronitrile (ADI) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.067 g of the side-chain polymer (28). Wherein: Mn = 22.5 K, PDI = 1.55.

[0214] Synthesis Example 7: Synthesis of Side-Chain Polymer (34)

[0215]

[0216] Synthesis of compound 34-1:

[0217] In a 250 mL round-bottom flask, compound 7-2 (10.06 g, 20 mmol) and tributyl(dithieno[3,2-B:2',3'-D]thienyl)tin (21.34 g, 44 mmol) were weighed and dissolved in 100 mL of tetrahydrofuran. Under argon protection, bis(triphenylphosphine)palladium dichloride (0.62 g, 0.88 mmol) was added to the system. The mixture was refluxed at 80 °C for 20 hours. After cooling to actual temperature, the tetrahydrofuran was evaporated to dryness, and the mixture was extracted with dichloromethane. The solvent was evaporated to dryness to obtain the crude product, which was purified by silica gel column chromatography to give approximately 10.54 g of compound 34-1. Yield: 72%, MS: 735.01.

[0218] Synthesis of compound 34-2:

[0219] In a 250 mL round-bottom flask, compound 34-1 (7.35 g, 10 mmol), triethyl phosphite (50 mL), and o-dichlorobenzene (20 mL) were added. Under argon protection, the mixture was reacted at 180 °C for 15 hours. After cooling to room temperature, the solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography to give approximately 5.0 g of compound 34-2 (yield: 74%, MS: 671.99).

[0220] Synthesis of compound 34-3:

[0221] In a 250 mL flask, compound 34-2 (3.36 g, 5 mmol), potassium hydroxide (2 g, 35.64 mmol), isooctane bromo (2.90 g, 15 mmol), and dimethyl sulfoxide (120 mL) were added. Under argon protection, the mixture was reacted at 80 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was evaporated, and the mixture was purified by silica gel column chromatography to give approximately 3.7 g of compound 34-3, yield: 83%, MS: 896.15.

[0222] Synthesis of compound 34-4:

[0223] In a 100 mL three-necked flask, compound 34-3 (0.822 g, 0.92 mmol) and anhydrous N,N-dimethylformamide (20 mL) were added. The temperature was lowered to 0 °C, and phosphorus oxychloride (1 mL) was added. The mixture was stirred for 2 hours. The temperature was then raised to 90 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was evaporated, and the mixture was purified by silica gel column chromatography to give approximately 0.58 g of compound 34-4. Yield: 66%, MS: 952.12.

[0224] Synthesis of compound 34-5:

[0225] In a 250 mL round-bottom flask, compound 34-4 (0.19 g, 0.20 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (0.46 g, 2.00 mmol) were dissolved in 45 mL of chloroform. 1 mL of pyridine was added, and the mixture was refluxed under argon protection for 12 hours. After cooling to room temperature, the solution was poured into 200 mL of anhydrous methanol, and the crude product was obtained by filtration. The crude product was purified by silica gel column chromatography to give approximately 0.18 g of compound 34-5. Yield: 67%, MALDI-TOF MS: 1376.35.

[0226] Synthesis of side-chain polymer (34):

[0227] Under an argon atmosphere, 0.1 g of compound 34-5 and 0.020 mmol of azobisisobutyronitrile (AIBN) were added to a 25 mL Schlenk flask. 10 mL of tetrahydrofuran was added to the flask, and the mixture was heated to 50 °C and stirred for 48 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried under vacuum, dissolved in dichloromethane, precipitated in methanol, and dried under vacuum again to obtain 0.061 g of the side-chain polymer (34). Wherein: Mn = 15.1 K, PDI = 1.78.

[0228] OPV device fabrication examples:

[0229] The fabrication process of the OPV device including the above-mentioned side-chain polymer will be described in detail below through specific embodiments.

[0230] The fabrication steps of device example 1 are as follows:

[0231] 1) ITO substrate cleaning:

[0232] Clean the ITO conductive glass with detergent, rinse it thoroughly, and then ultrasonically clean it for 15 minutes with deionized water, acetone, and isopropanol. After that, dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0233] 2) Preparation of the anode buffer layer

[0234] PEDOT:PSS (Clevios) in the air TM PVP Al 4083 was uniformly spin-coated onto ITO at a spin speed of 3000-4000 rpm / min and dried at 150℃ for 15 min to obtain an anodic modification layer with a thickness of 20 nm.

[0235] 3) Preparation of photoactive layer

[0236] In a glove box (inert gas atmosphere), the photoactive layer material (the concentration of the mixture of the donor material and the acceptor material in chloroform is 15.4 mg / mL) is uniformly spin-coated onto the anode buffer layer at a rotation speed of 1800-3000 rpm / min to obtain a photoactive layer with a total thickness of 100 nm; wherein the donor material in the photoactive layer material is selected from PM6; the acceptor material is selected from the side chain polymer (7); and the mass ratio of the donor material to the acceptor material is 1:1.2.

[0237]

[0238] 4) Preparation of cathode buffer layer

[0239] After annealing on a hot plate at 100°C for 10 min, the cathode buffer layer material PDINN (prepared by dissolving PDINN in methanol to form a solution with a concentration of 1 mg / mL) was uniformly spin-coated onto the active layer at a spin speed of 2000-4000 rpm / min to obtain a cathode buffer layer with a thickness of 5 nm.

[0240] 5) Cathode layer preparation

[0241] In high vacuum (1×10) -6 Ag is deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of 100 nm.

[0242] 6) Packaging

[0243] The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0244] The preparation methods of devices 2-7 are the same as those of device 1, except that the photoactive layer acceptor material is selected differently. The specific device structures are shown in Table 1.

[0245] Table 1 Structure of Organic Solar Cell Devices

[0246] Device Example 1 ITO PEDOT:PSS PM6: Side-chain polymer (7) PDINN Ag Device Example 2 ITO PEDOT:PSS PM6: Side-chain polymer (10) PDINN Ag Device Example 3 ITO PEDOT:PSS PM6: Side-chain polymer (14) PDINN Ag Device Example 4 ITO PEDOT:PSS PM6: Side-chain polymer (17) PDINN Ag Device Example 5 ITO PEDOT:PSS PM6: Side-chain polymer (25) PDINN Ag Device Example 6 ITO PEDOT:PSS PM6: Side-chain polymer (28) PDINN Ag Device Example 7 ITO PEDOT:PSS PM6: Side-chain polymer (34) PDINN Ag

[0247] The performance of the fabricated organic solar cell device was tested. Under AM1.5G standard light irradiation using a solar simulator (SS-F5-3A), the cell current-voltage curve was measured, and the photoelectric conversion efficiency was calculated as shown in Table 2.

[0248] Table 2

[0249] Device Example 1 PM6: Side-chain polymer (7) 16.62 Device Example 2 PM6: Side-chain polymer (10) 14.11 Device Example 3 PM6: Side-chain polymer (14) 16.35 Device Example 4 PM6: Side-chain polymer (17) 14.92 Device Example 5 PM6: Side-chain polymer (25) 15.56 Device Example 6 PM6: Side-chain polymer (28) 15.96 Device Example 7 PM6: Side-chain polymer (34) 15.07

[0250] As shown in Table 2, the side-chain polymer described in this invention exhibits excellent photoelectric conversion performance when used as an acceptor material in organic solar cell devices.

[0251] The above embodiments further illustrate the content of this application, but should not be construed as limiting this application. Modifications and substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are all within the scope of this application. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

Claims

1. A side-chain polymer, characterized in that: The side-chain polymer has a structure as shown in general formula (I): （I）； in: L is selected from -CH2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13 -、-(CH2) 14 -、-(CH2) 15 -、-(CH2) 16 -; Each occurrence of Ar1 and Ar2 is independently selected from those that are not substituted or are replaced by R. * The substituted heteroaromatic group having 5-20 ring atoms, wherein the heteroatoms in the heteroaromatic group are selected from O, S or Se; Each time M appears, it is independently selected from O or C(CN)2; Each occurrence of Ar3 and Ar4 is independently selected from any of the following groups: In this context, X is selected independently from CR4 each time it appears; W is selected independently from O, S, and Se each time it appears; R4 is selected independently from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, -NO2, methyl, ethyl, isopropyl, tert-butyl, or butyl each time it appears; * indicates a fused ring site, and the fused site is selected from the C atom. Each time R1 and R2 appear, they are independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms. R * Each occurrence is independently selected from -D, a straight-chain alkyl group having 1-20 carbon atoms, a branched or cyclic alkyl group having 3-20 carbon atoms, a straight-chain alkoxy group having 1-20 carbon atoms, a branched or cyclic alkoxy group having 3-20 carbon atoms, a straight-chain alkylthio group having 1-20 carbon atoms, a branched or cyclic alkylthio group having 3-20 carbon atoms, an aromatic group having 6-20 carbon atoms, or a group formed by a combination of the above groups; n is the number of repeating units and is an integer greater than or equal to 2.

2. The side-chain polymer according to claim 1, characterized in that: Each occurrence of Ar1 and Ar2 is independently selected from any of the following groups: ， Wherein: Y is selected independently from O, S, or Se each time it appears; R3 is selected independently from -H, -D, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched alkylthio with 3-20 carbon atoms, aromatic group with 6-20 carbon atoms, or a group formed by combination of the above groups; * indicates a fused ring site, and the fused site is selected from C atoms; # indicates a linking site.

3. The side-chain polymer according to claim 2, characterized in that: Each occurrence of Ar1 and Ar2 is independently selected from any of the following groups: 。 4. The side-chain polymer according to claim 2, characterized in that: The side-chain polymer is selected from structures such as those shown in general formula (II) or (III): (II)、 (III)。 5. The side-chain polymer according to any one of claims 1-4, characterized in that: Each occurrence of Ar3 and Ar4 is independently selected from any of the following groups: 。 6. The side-chain polymer according to claim 1, characterized in that: In general formula (I) and Each occurrence is independently selected from any of the following groups: ； Where: # represents the connection site.

7. The side-chain polymer according to any one of claims 1-4, characterized in that: Each occurrence of R1 and R2 is independently selected from the following groups: 。 8. The side-chain polymer according to claim 1, characterized in that: The side-chain polymer is selected from the following structural formulas: ； Wherein: in the above structural formula -(CH2) m - indicates a straight-chain alkyl group with m carbon atoms, where m is an integer from 0 to 15.

9. A mixture, characterized in that: The mixture comprises a side-chain polymer as described in any one of claims 1-8, and at least one other organic functional material; the at least one other organic functional material is selected from an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material.

10. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer comprises the side-chain polymer of any one of claims 1-8 or the mixture of claim 9.

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