CN117659243A - Side chain polymer and application thereof in organic electronic device - Google Patents

Side chain polymer and application thereof in organic electronic device Download PDF

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CN117659243A
CN117659243A CN202311677674.0A CN202311677674A CN117659243A CN 117659243 A CN117659243 A CN 117659243A CN 202311677674 A CN202311677674 A CN 202311677674A CN 117659243 A CN117659243 A CN 117659243A
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carbon atoms
group
branched
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atoms
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李冬云
龙志飞
裘伟明
谭鸿霖
陈佳
肖立清
张静
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Guangzhou Zhuoguang Technology Co ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The invention provides a side chain polymer and application thereof in an organic electronic device, belonging to the field of organic photoelectric materials. The side chain polymer provided by the invention has good thermal stability and film forming property, and when the side chain polymer is prepared from a non-fullerene acceptor material and a donor material, effective intermolecular charge transfer can occur between acceptors, so that the device has excellent device performance.

Description

Side chain polymer and application thereof in organic electronic device
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to a side chain polymer and application thereof in an organic electronic device.
Background
Organic solar cells have the advantage of being lightweight, flexible, translucent and solution processable. The active layer prepared by blending the donor material and the acceptor material is a core component of the polymer solar cell and is responsible for core tasks such as conversion from photons to charges and charge transport. In recent years, based on polymer donors: polymer solar cells of non-fullerene acceptor blend systems are rapidly developing, and the energy conversion efficiency has exceeded 19%. Compared to the polymer donor: non-fullerene acceptor system organic solar cells based on polymer donors: the development of all-polymer solar cells with polymer acceptors is relatively late, mainly due to the lack of efficient polymer acceptor species.
Currently, polymer receptor development is largely based onA system wherein the SMA is selected from non-fullerene small molecule acceptor materials, primarily selected from non-fullerene acceptor materials based on Y6 or ITIC backbones; q is a modification unit, and mainly adopts structures such as thiophene, bithiophene, thienothiophene, benzodithiophene and the like. However, the polymer acceptor materials are currently of very few kinds and the direction of development is limited by +>A system. There is therefore a need to develop novel polymer acceptor materials that promote diversification of polymer acceptor material development routes.
Disclosure of Invention
The invention aims to provide a novel polymer acceptor material, which is a side chain polymer, and can be used as an acceptor material to be applied to an organic solar cell photoactive layer to obtain excellent photoelectric conversion efficiency of an organic solar cell device.
The technical solution for realizing the purpose of the invention is as follows: a side chain polymer having a structure represented by the general formula (I):
wherein:
l is independently selected from the group consisting of, for each occurrence, a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, a straight chain alkoxy group having 1 to 20 carbon atoms, a branched chain alkoxy group having 3 to 20 carbon atoms, a straight chain alkylthio group having 1 to 20 carbon atoms, a branched alkylthio group having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
Ar 1 、Ar 2 each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
m is independently selected from O or C (CN) for each occurrence 2 ；
Ar 3 、Ar 4 Each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R 1 、R 2 independently selected for each occurrence from the group consisting of straight chain alkyl groups having 1 to 20 carbon atoms, branched chain alkyl groups having 3 to 20 carbon atoms, straight chain alkoxy groups having 1 to 20 carbon atoms, branched chain alkoxy groups having 3 to 20 carbon atoms, straight chain alkylthio groups having 1 to 20 carbon atoms, branched chain alkylthio groups having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R * each occurrence is independently selected from the group consisting of-D, halogen, cyano, nitro, straight chain alkyl having 1 to 20 carbon atoms, branched or cyclic alkyl having 3 to 20 carbon atoms, straight chain alkoxy having 1 to 20 carbon atoms, branched or cyclic alkoxy having 3 to 20 carbon atoms, and having 1 to 20 carbon atoms A linear alkylthio group of a child, a branched or cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a combination thereof;
n is the number of repeating units and n is an integer of 2 or more.
Further, the present invention also provides a mixture: the mixture comprises a side chain polymer as described above, 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.
Further, the present invention also provides an organic electronic device comprising at least one functional layer: the functional layer comprises the above side chain polymer or the above mixture.
Compared with the prior art, the invention has at least the following beneficial technical effects:
the photoactive layer polymer acceptor material creatively adopts a side chain polymerization structure, so that the prepared polymer acceptor material can keep the basic photoelectric performance of small molecules on one hand and has better thermal stability and film forming property than the small molecule material on the other hand; when the organic solar cell device is prepared by mixing the organic solar cell device with a donor material, effective intermolecular charge transfer can occur between donors and acceptors, so that the prepared device shows excellent device performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is provided in connection with specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, the organic photovoltaic device, the organic solar cell, and the OPV have the same meaning and are interchangeable.
In the present invention, the photoactive layer and the active layer have the same meaning and are interchangeable.
In the present invention, the same substituent may be independently selected from the same or different groups when the same substituent appears multiple times.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, the number of ring atoms of the thienyl group is 5, and the number of ring atoms of the thienothiophene ring is 8.
In the present invention, when no attachment site is specified in a group, an optionally attachable site in the group is represented as an attachment site.
In the present invention, the single bond to which the substituent is attached runs throughCorresponding rings, it being stated that the substituents may be attached to optional positions of the ring, e.g. R in (C) is connected with any substitutable site of benzene ring.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the linear alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched alkyl group may have a carbon number of 3 to 20, 3 to 16, 1 to 10, or 3 to 6; the cyclic alkyl group may have a carbon number of 3 to 20, 3 to 16, 1 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 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 having 4C atoms, branched alkyl having 5C atoms, branched alkyl having 6C atoms, branched alkyl having 7C atoms, branched alkyl having 8C atoms, branched alkyl having 9C atoms, branched alkyl having 10C atoms, branched alkyl having 11C atoms, branched alkyl having 12C atoms, branched alkyl having 13C atoms, branched alkyl having 14C atoms, branched alkyl having 15C atoms, branched alkyl having 16C atoms.
In the present invention, the term "linear alkoxy" refers to a group of the structure "-O-linear alkyl", i.e. a linear alkyl group as defined above is attached to other groups via an oxygen atom.
In the present invention, the term "branched alkoxy" refers to a group of the structure "-O-branched alkyl", i.e. branched alkyl as defined above is attached to other groups via an oxygen atom.
In the present invention, the term "linear alkylthio" refers to a group of the structure "-S-linear alkyl", i.e. a linear alkyl group as defined above is linked to other groups via a sulfur atom.
In the present invention, the term "branched alkylthio" refers to a group of the structure "-S-branched alkyl", i.e. branched alkyl as defined above is attached to other groups via a sulfur atom.
In the present invention, "halogen" includes fluorine, chlorine, bromine, iodine, and the like.
In the present invention, "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group may be a monocyclic aromatic group (e.g., phenyl) or a polycyclic aromatic group, in other words, the aromatic group may be a monocyclic aromatic group, a condensed ring aromatic group, two or more monocyclic aromatic groups connected by a carbon-carbon bond conjugate, a monocyclic aromatic group and a condensed ring aromatic group connected by a carbon-carbon bond conjugate, two or more condensed ring aromatic groups connected by a carbon-carbon bond conjugate. That is, two or more aromatic groups conjugated through carbon-carbon bonds may also be considered aromatic groups herein unless otherwise indicated. Preferably, said aromatic group is selected from aromatic groups having 6 to 30C atoms; further, an aromatic group selected from the group consisting of having 6 to 20C atoms; further, an aromatic group selected from the group consisting of having 6 to 10C atoms; aromatic groups include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl and derivatives thereof.
In the present invention, the "heteroaromatic group" means a monovalent aromatic ring containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring or a derivative thereof, and the heteroatoms may be at least one of B, O, N, P, si, se and S. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or may be a plurality of aromatic ring systems connected by carbon-carbon bond conjugation, and either aromatic ring system is an aromatic monocyclic ring or an aromatic condensed ring. Preferably, the said heteroaromatic group is selected from the group consisting of heteroaromatic groups having 6 to 30 ring atoms; further, a heteroaromatic group selected from the group consisting of having 6 to 20 ring atoms; further, it is selected from heteroaromatic groups having 6 to 10 ring atoms. Heteroaromatic groups include, but are not limited to: thienyl, furyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiophenoyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
As used in the present invention, "a combination thereof", "any combination thereof", "combination", and the like include all suitable combinations of any two, any three, or any three or more of the listed groups.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
The first aspect of the present invention provides a side chain polymer having a structure as shown in the general formula (I):
wherein:
l eachAnd is independently selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, a linear alkylthio group having 1 to 20 carbon atoms, a branched alkylthio group having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
Ar 1 、Ar 2 each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
m is independently selected from O or C (CN) for each occurrence 2 ；
Ar 3 、Ar 4 Each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R 1 、R 2 independently selected for each occurrence from the group consisting of straight chain alkyl groups having 1 to 20 carbon atoms, branched chain alkyl groups having 3 to 20 carbon atoms, straight chain alkoxy groups having 1 to 20 carbon atoms, branched chain alkoxy groups having 3 to 20 carbon atoms, straight chain alkylthio groups having 1 to 20 carbon atoms, branched chain alkylthio groups having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R * independently for each occurrence-D, halogen, cyano, nitro, straight chain alkyl having 1 to 20 carbon atoms, branched or cyclic alkyl having 3 to 20 carbon atoms, straight chain alkoxy having 1 to 20 carbon atoms, branched or cyclic alkoxy having 3 to 20 carbon atoms, straight chain alkylthio having 1 to 20 carbon atoms, branched or cyclic alkylthio having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or a combination thereof;
n is the number of repeating units and n is an integer of 2 or more.
In the present invention, "unsubstituted or R * Substituted "means that the functional group defined later in the term may be unsubstituted or may be substituted with one, two or more R * And (3) substitution.
In the present invention, one or more groups represented by the same letter may be selected from the same group or may be selected from different groups when they occur simultaneously and at plural places in the compound. For example, in formula I, M may be selected from the same group or may be selected from different groups.
In the present invention, the expression "independently selected" means that one or more groups are independently selected when they are simultaneously present, and may be the same or different. For example, ar 1 、Ar 2 Each occurrence is independently selected from, and represents Ar 1 、Ar 2 Independently selected, may be the same or different.
In one embodiment, R * Independently for each occurrence, a halogen, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms
In one embodiment, ar 1 、Ar 2 Each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-15 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 15 ring atoms. Further, ar 1 、Ar 2 Each occurrence is independently selected from unsubstituted or substituted * Substituted heteroaromatic groups having 5 to 11 ring atoms.
In a specific embodiment, ar 1 、Ar 2 Each occurrence is independently selected from any one of the following groups:
wherein:
y is independently selected from O, S, or Se for each occurrence;
R 3 independently selected from the group consisting of-H, -D, a straight chain alkyl group having 1-20 carbon atoms, a branched chain alkyl group having 3-20 carbon atoms, a straight chain alkoxy group having 1-20 carbon atoms, a branched chain alkoxy group having 3-20 carbon atoms, a straight chain alkylthio group having 1-20 carbon atoms, a branched alkylthio group having 3-20 carbon atoms, an aromatic group having 6-20 carbon atoms, and a heteroaromatic group having 5-20 ring atoms, or a combination thereof;
* Represents a condensed ring site;
# represents the ligation site.
When the condensed ring site is represented, the condensed ring site is selected from a C atom.
In one embodiment, each occurrence of Y is independently selected from S or Se.
Further, ar 1 、Ar 2 Each occurrence is independently selected from any one of the following groups:
in one embodiment, R 3 The radicals are selected identically or differently for each occurrence from-H, -D, straight-chain alkyl radicals having 1 to 16 carbon atoms, branched alkyl radicals having 3 to 16 carbon atoms, straight-chain alkoxy radicals having 1 to 16 carbon atoms, branched alkoxy radicals having 3 to 16 carbon atoms, straight-chain alkylthio radicals having 1 to 16 carbon atoms, branched alkylthio radicals having 3 to 16 carbon atoms, unsubstituted or substituted by R * Substituted phenyl, or unsubstituted or substituted by R * Substituted thienyl.
Specifically, R 3 The same or different for each occurrence is selected from the group consisting of a linear or branched alkyl group having 6C atoms, a linear or branched alkyl group having 7C atoms, a linear or branched alkyl group having 8C atoms, a linear or branched alkyl group having 9C atomsA branched alkyl group, a linear or branched alkyl group having 10C atoms, a linear or branched alkyl group having 11C atoms, a linear or branched alkyl group having 12C atoms, a linear or branched alkyl group having 13C atoms, a linear or branched alkyl group having 14C atoms, a linear or branched alkyl group having 15C atoms, a linear or branched alkyl group having 16C atoms, a linear or branched alkoxy group having 6C atoms, a linear or branched alkoxy group having 7C atoms, a linear or branched alkoxy group having 8C atoms, a linear or branched alkoxy group having 9C atoms, a linear or branched alkoxy group having 10C atoms, a linear or branched alkoxy group having 11C atoms, a linear or branched alkoxy group having 12C atoms, a linear or branched alkoxy group having 13C atoms a linear or branched alkoxy group having 14C atoms, a linear or branched alkoxy group having 15C atoms, a linear or branched alkoxy group having 16C atoms, a linear or branched alkylthio group having 6C atoms, a linear or branched alkylthio group having 7C atoms, a linear or branched alkylthio group having 8C atoms, a linear or branched alkylthio group having 9C atoms, a linear or branched alkylthio group having 10C atoms, a linear or branched alkylthio group having 11C atoms, a linear or branched alkylthio group having 12C atoms, a linear or branched alkylthio group having 13C atoms, a linear or branched alkylthio group having 14C atoms, a linear or branched alkylthio group having 15C atoms, a linear or branched alkylthio group having 16C atoms, a linear or branched alkylthio group having R * Substituted phenyl, substituted by R * Substituted thienyl; wherein: the R is * Preferably from a linear or straight-chain alkyl group having 6 to 12C atoms.
Further, ar 1 、Ar 2 Each occurrence is independently selected from any one of the following groups:
in a preferred embodiment, the side chain polymers according to the invention are selected from the following structures:
wherein: l, R 1 、R 2 、R 3 、Y、M、Ar 3 、Ar 4 The meaning is as described above.
In another preferred embodiment, the side chain polymers according to the invention are selected from the following structures:
wherein: l, R 1 、R 2 、R 3 、Y、M、Ar 3 、Ar 4 The meaning is as described above.
In one embodiment, R 1 、R 2 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms.
In one embodiment, R 1 、R 2 Each occurrence is independently selected from a straight chain alkyl group having 1 to 16 carbon atoms, or a branched alkyl group having 3 to 16 carbon atoms.
Specifically, R 1 、R 2 Each occurrence is independently selected from the group consisting of a linear or branched alkyl group having 6C atoms, a linear or branched alkyl group having 7C atoms, a linear or branched alkyl group having 8C atoms, a linear or branched alkyl group having 9C atoms, a linear or branched alkyl group having 10C atoms, a linear or branched alkyl group having 11C atoms, a linear or branched alkyl group having 12C atoms, a linear or branched alkyl group having 13C atoms, a linear or branched alkyl group having 14C atoms, a linear or branched alkyl group having 15C atoms, a linear or branched alkyl group having 16C atoms.
Further, R 1 、R 2 Each occurrence is independently selectedFrom the following groups:
in a specific embodiment, R 1 、R 2 Selected from the same groups.
In one embodiment of the present invention, in one embodiment,independently selected from->
In one embodiment of the present invention, in one embodiment,independently selected from->
In one embodiment, ar 3 、Ar 4 Each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 10 ring atoms.
In one embodiment, ar 3 、Ar 4 Each occurrence is independently selected from any one of the following groups:
wherein:
x is independently selected from N or CR for each occurrence 4 ；
Each occurrence of W is independently selected from O, S, se;
R 4 each occurrence is independently selected from the group consisting of-H, -D, halogen, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight chain alkyl having 1 to 10 carbon atomsAlkoxy, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a combination thereof;
* Represents a fused ring site selected from the group consisting of C atoms.
Further, ar 3 、Ar 4 Each occurrence is independently selected from any one of the following groups:
Further, R 4 Each occurrence is independently selected from the group consisting of-H, -D, -F, -Cl, -Br, -I, -CF 3 、-CN、-NO 2 Methyl, ethyl, isopropyl, tert-butyl or butyl.
Further, the method comprises the steps of,each occurrence is independently selected from any one of the following groups:
in one embodiment, each occurrence of L is independently selected from the group consisting of a straight chain alkyl group having 1 to 16 carbon atoms, a branched chain alkyl group having 3 to 16 carbon atoms, a straight chain alkoxy group having 2 to 16 carbon atoms, a branched chain alkoxy group having 3 to 16 carbon atoms, a straight chain alkylthio group having 2 to 16 carbon atoms, a branched alkylthio group having 3 to 16 carbon atoms, a phenyl group, and a substituted alkyl group having 2 to 16 carbon atoms * Substituted phenyl, thienyl, and R * Substituted thienyl. Wherein: r is R * Preferably selected from the group consisting of linear alkyl groups having 2 to 15 carbon atoms, branched alkyl groups having 3 to 15 carbon atoms, linear alkoxy groups having 2 to 15 carbon atoms, branched alkyl groups having 3 to 15 carbon atomsA chain alkoxy group, a straight chain alkylthio group having 2 to 15 carbon atoms, a branched chain alkylthio group having 3 to 15 carbon atoms.
Further, L is selected from straight chain alkyl groups having 1 to 16 carbon atoms; in particular, L is selected from the group consisting of-CH 2 -、-(CH 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 4 -、-(CH 2 ) 5 -、-(CH 2 ) 6 -、-(CH 2 ) 7 -、-(CH 2 ) 8 -、-(CH 2 ) 9 -、-(CH 2 ) 10 -、-(CH 2 ) 11 -、-(CH 2 ) 12 -、-(CH 2 ) 13 -、-(CH 2 ) 14 -、-(CH 2 ) 15 -、-(CH 2 ) 16 -。
The side chain polymers provided by the present invention may be selected from the following structural formulas, but are not limited thereto:
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in the above structural formula, - (CH) 2 ) m -represents a linear alkyl group having m carbon atoms, m being an integer from 0 to 15.
In a certain embodiment, m=0; in a certain embodiment, m=1; in a certain embodiment, m=2; in a certain embodiment, m=3; in a certain embodiment, m=4; in a certain embodiment, m=5; in a certain embodiment, m=6; in a certain embodiment, m=7; in a certain embodiment, m=8; in a certain embodiment, m=9; in a certain embodiment, m=10; in a certain embodiment, m=11; in a certain embodiment, m=12; in a certain embodiment, m=13; in a certain embodiment, m=14; in a certain embodiment, m=15.
In one embodiment, n is selected from integers from 2 to 10000; further, n is selected from integers from 2 to 1000; further, n is selected from integers from 4 to 500; further, n is selected from integers from 5 to 100; further, n is selected from integers from 5 to 20.
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.
A second aspect of the invention relates to a mixture comprising a side chain polymer according to the first aspect, and at least one further organic functional material, which is selected from the group consisting of an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material; the weight ratio of the organic functional material to the other organic functional material is 1:99-99:1. In one embodiment, the photoactive layer comprises a donor material and an acceptor material in a weight ratio of donor material/acceptor material = 1/1 to 1/1.5.
In an embodiment, the another 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, SZ2, PTQ10, PTQ11, PB 2F.
A third aspect of the 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 the group consisting of aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers, and mixtures thereof.
In one embodiment, the organic solvent is selected from the group consisting of methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2, 4-dimethyl anisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, N-butyl acetate, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide 1, 5-dimethyltetrahydrofuran, acetophenone, tetrahydronaphthalene, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene or mixtures thereof.
In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.
It is understood that the organic solvent may be evaporated from the solvent system to form a film comprising the organic compound.
In one embodiment, the composition is a solution. In other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film forming properties, improving adhesion, etc. The additive may be selected from at least one of, but not limited to, a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobizing agent, and a binder.
The invention also relates to the use of said composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the composition is used in the preparation of organic electronic devices by a print or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roller printing, offset printing, flexography, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Preferred are slot coating, spin coating and ink jet printing.
The invention further relates to the use of a side chain polymer according to the first aspect, a mixture according to the second aspect, a composition according to the third aspect in an organic electronic device. Preferably, the organic electronic device is selected from the group consisting of organic solar cells (OPV), organic Light Emitting Diodes (OLED), organic Field Effect Transistors (OFET), organic lasers, organic Photodetectors (OPD), and the like. In a specific embodiment, the organic electronic device is selected from organic solar cells.
A fourth aspect of the invention relates to an organic electronic device comprising at least one functional layer comprising a side chain polymer as described in the first aspect or a mixture as described in the second aspect.
Further, the organic electronic device comprises a first electrode, a second electrode, and one or more functional layers between the first electrode and the second electrode, at least one of the one or more functional layers comprising a side chain polymer as described in the first aspect, or a mixture as described in the second aspect.
In an embodiment, the one or more functional layers comprise at least one photoactive layer, the photoactive layer material comprising a polymer according to the first aspect, or a mixture according to the second aspect.
In a certain embodiment, the one or more functional layers comprise at least an anode buffer layer, a photoactive layer and a cathode buffer layer, the photoactive layer material comprising a side chain polymer as described in the first aspect, or a mixture as described in the second aspect.
It should be noted that, in order to improve the performance of the organic solar cell device, the one or more functional layers may further include other functional layers, including, but not limited to, a charge injection layer and/or a charge blocking layer.
In an embodiment, the organic electronic device is selected from organic solar cells.
Further, the organic solar cell further includes a substrate. In particular, the substrate may be disposed on one side of the first electrode and on a different side from the functional layer.
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.
In one embodiment, as the substrate, a substrate having excellent transparency, surface smoothness, ease of handling, and water repellency may be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate may be used. The plastic substrate may include a film in the form of a single layer or a plurality of layers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), etc., but is not limited thereto, and a substrate commonly used for an organic solar cell may be used.
The anode electrode may be made of a transparent or translucent material, but is not limited thereto. The anode electrode may comprise a metal such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ZnO: al or SnO 2: sb; and conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDOT), polypyrrole, polyaniline, and the like, but are not limited thereto.
The cathode electrode may be made of a low work function metal. The cathode electrode may include a metal such as silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd), or an alloy thereof; and materials having a multi-layer structure, e.g. LiF/Al, liO 2 /Al、LiF/Fe、MoO 3 /Al、Al∶Li、Al∶BaF 2 Al: baF 2 Ba, but not limited thereto.
The photoactive layer comprises an electron donor material and an electron acceptor material. In particular, the electron donor material may be a variety of polymeric materials or small molecule materials. The polymeric material may be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymeric material systems, such as PF8BT and the like; new structure narrow band gap polymer material systems, such as benzothiadiazole (BT, BBT), quinoxaline (QU, PQ), pyrazine (TP, PQ) and electron-rich group (such as thiophene derivative) are copolymerized, 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 (II) phthalocyanine, zinc phthalocyanine, tris [4- (5-dicyanomethylenemethyl-2-thienyl) phenyl ] amine, 2, 4-bis [4- (N, N-dibenzylamino) -2, 6-dihydroxyphenyl ] squaraine, benzo [ B ] anthracene and pentacene, B8, B10, and the like. Preferably, the donor material is selected from one or more of PBDB-T, PM6, PM7, PBT1-C-2Cl, ES1, SZ2, PTQ10, PTQ11, PB 2F. The electron acceptor material is selected from side chain polymers as described by the general formula (I).
The photoactive layer may be formed by the following method: the photoactive material, such as an electron donor and/or electron acceptor, is dissolved in an organic solvent, and then the resulting solution is coated by methods such as spin coating, dip coating, screen printing, gravure printing, spray coating, doctor blade, slot coating, and ink jet printing, but is not limited thereto.
The anode buffer layer material may be selected from PEDOT of poly (styrenesulfonic acid): PSS (poly (3, 4-ethylenedioxythiophene)), molybdenum oxide (MoOx), vanadium oxide (V) 2 O 5 ) Nickel oxide (NiO), tungsten oxide (WO x， Preferably, x is selected from 2 or 3), etc., but is not limited thereto.
The cathode buffer layer material can be electron-withdrawing metal oxide or polymer, and the metal oxide can be metal complex containing 8-hydroxyquinoline and Alq 3 Metal complex containing Liq, liF, ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs 2 CO 3 ) Etc., the polymer may be PFN-Br or PFN or PDINN or PNDIT-F3N-Br, etc., but is not limited thereto.
The invention also relates to the use of the organic solar cell according to the invention in various devices including, but not limited to, automotive and Building Integrated Photovoltaics (BIPV), electronic price tags, indoor photovoltaics, internet of things, smart agriculture, and the like.
The invention will be described in connection with the preferred embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims summarize the scope of the invention and those skilled in the art who have the benefit of this disclosure will recognize certain changes that may be made to the embodiments of the invention and that are intended to be covered by the spirit and scope of the appended claims.
Synthesis example 1: synthesis of side chain Polymer (7)
Synthesis of Compound 7-1:
the compound 3, 6-dibromo-4, 5-dinitro-o-phenylenediamine (17.8 g,50 mmol) was accurately weighed and added into a 500mL three-necked flask, 200mL glacial acetic acid was added, then an aqueous solution of sodium nitrite (4.14 g dissolved in 80mL deionized water) was slowly added dropwise to the reaction system, and the reaction was carried out at room temperature for 1 hour. Suction filtration is carried out, and filter cakes are leached by deionized water for a plurality of times. About 10.2g of crude compound 7-1 was obtained. Yield: 56%.
Synthesis of Compound 7-2:
compound 7-1 (7.34 g,20.0 mmol) and potassium carbonate (5.53 g,40.0 mmol) were dissolved in 180mL of a mixed solvent of N, N-dimethylformamide dehydrated over magnesium sulfate and 5mL of dimethyl sulfoxide under nitrogen, the reaction mixture was reacted at 85℃for 1 hour, and 10-bromo-1-decene (5.26 g,24.0 mmol) was further added under nitrogen, and the reaction mixture was heated to 90℃for 8 hours. After cooling, the reaction solution was poured into cold water, and the product was extracted with water and dichloromethane, and repeated 3 times. Purification by silica gel column chromatography gave compound 7-2 in about 6.6g, 65% yield. MS:505.71.
Synthesis of Compound 7-3:
7-2 (2.5 g,5 mmol) and tributyl (6-undecylthiophene [3,2-b ] thiophen-2-yl) stannane (6.42 g,11 mmol) were weighed into a 100mL round bottom flask and bis (triphenylphosphine) palladium dichloride (0.16 g,0.22 mmol) was added to the system under argon. The mixture was refluxed at 80℃for 20 hours. Cooling to the solid temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain the compound 7-3 with the yield of about 2.6g and 56%. MS:932.46.
synthesis of Compound 7-4:
in a 100mL round bottom flask, compound 7-3 (2.33 g,2.5 mmol), triethyl phosphite (15 mL) and o-dichlorobenzene (5 mL) were charged. The mixture was reacted at 180℃for 15 hours under argon protection. Cooling to room temperature, distilling under reduced pressure to remove solvent, and separating and purifying by silica gel column chromatography to obtain compound 7-4 with yield of about 1.23g and 57%. MS:868.54.
Synthesis of Compound 7-5:
in a 250mL flask, compound 7-4 (0.87 g,1 mmol), potassium hydroxide (0.4 g,7.13 mmol), bromoisooctane (0.58 g,3 mmol) and dimethyl sulfoxide (30 mL) were added, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with methylene chloride, and the solvent was dried by spin-drying, and the compound 7-5 was isolated and purified by silica gel column chromatography to give compound 7-5 about 0.51g in 47% yield. MS:1092.54.
Synthesis of Compounds 7-6:
in a 100mL 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℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. The temperature was raised to 90℃and stirred overnight, cooled to room temperature and extracted with dichloromethane, the solvent was removed by spin-on, and the resulting product was purified by column chromatography on silica gel to give compound 7-6 in a yield of about 0.39g and 74%. MS:1148.58.
Synthesis of Compounds 7-7:
in a 250mL round bottom flask, compound 7-6 (0.35 g,0.3 mmol) and 5, 6-difluoro-3- (dicyanomethylene) indidone (0.69 g,3.0 mmol) were dissolved in 135mL chloroform, 3mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and suction filtered to obtain a crude product, and the crude product was separated and purified by silica gel column chromatography to obtain compound 7-7 about 0.33g in 71% yield. MALDI-TOF MS 1572.86.
Synthesis of side chain polymer (7):
0.1572g of Compound 7-7 and 0.020mmol of Azobisisobutyronitrile (AIBN) were charged into a 25mL Schlenk flask under an argon atmosphere, 10mL of tetrahydrofuran was added into the flask, the temperature was raised to 50℃and the mixture was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved in methylene chloride, settled in methanol, dried again in vacuo to give 0.091g of polymer (7). Wherein: mn=14.1k, pdi=1.73.
Synthesis example 2: synthesis of side chain Polymer (10)
Synthesis of Compound 10-1:
in a 100mL round bottom flask, compound 7-6 (0.115 g,0.10 mmol) and 2- (2-bromo-4-oxo-4, 5-dihydro-6H-cyclopenta-nitrile [ b ] thiophen-6-ylidene) malononitrile (0.279 g,1.00 mmol) were dissolved in 45mL chloroform, 1mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and suction filtered to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 10-1 about 0.10g, MALDI-TOF MS:1671.59.
Synthesis of side chain Polymer (10):
0.1g of the compound 10-1 and 0.020mmol of azobisisobutyronitrile AIBN were charged into a 25mL Schlenk flask under argon atmosphere, 10mL of tetrahydrofuran THF was added into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved with methylene chloride, settled in methanol, dried again in vacuo to give 0.049g of polymer (10). Wherein: mn=12.6k, pdi=1.85.
Synthesis example 3: synthesis of side chain Polymer (14)
Synthesis of Compound 14-2:
in a 250mL 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, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with dichloromethane, and the solvent was dried by spin-drying, and then separated and purified by silica gel column chromatography to give Compound 14-2 about 0.6g in 50% yield. MS:1205.46.
Synthesis of Compound 14-3:
in a 100mL 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℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. The temperature was raised to 90℃and stirred overnight, cooled to room temperature and extracted with dichloromethane, the solvent was removed by spin-on, and the product was purified by column chromatography on silica gel to give compound 14-3 in a yield of about 0.45g and 78%. MALDI-TOF MS 1261.37. Synthesis of Compound 14-4:
in a 250mL round bottom flask, compound 14-3 (0.38 g,0.3 mmol) and 5, 6-dichloro-3- (dicyanomethylene) indidone (0.79 g,3.0 mmol) were dissolved in 135mL chloroform, 3mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and suction filtered to obtain a crude product, and the crude product was separated and purified by silica gel column chromatography to obtain compound 14-4 about 0.4g in 77% yield. MALDI-TOF MS 1751.29.
Synthesis of side chain Polymer (14):
0.1g of Compound 14-4 and 0.020mmol of Azobisisobutyronitrile (AIBN) were charged into a 25mL Schlenk flask under an argon atmosphere, 10mL of tetrahydrofuran was added into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved in methylene chloride, settled in methanol, and dried again in vacuo to give 0.058g of side chain polymer (14). Wherein: mn=17.5k, pdi=1.91.
Synthesis example 4: synthesis of side chain Polymer (17)
Synthesis of Compound 17-1:
in a 250mL round bottom flask, compound 7-2 (10.06 g,20 mmol) and (thieno [3,2-B ] thiophen-2-yl) tributylstannane (18.89 g,44 mmol) were weighed into 100mL tetrahydrofuran and ditriphenylphosphine palladium dichloride (0.62 g,0.88 mmol) was added to the system under argon. The mixture was refluxed at 80℃for 20 hours. Cooling to a real temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain compound 17-1 about 7.6g, yield 61%, MS:623.58.
synthesis of Compound 17-2:
in a 250mL 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℃for 15 hours under argon protection. Cooling to room temperature, distilling under reduced pressure to remove solvent, separating and purifying by silica gel column chromatography to obtain compound 17-2 about 3.73g, and yield 67%. MS:559.90.
synthesis of Compound 17-3:
in a 250mL flask, compound 17-2 (2.8 g,5 mmol), potassium hydroxide (2 g,35.64 mmol), bromoisooctane (2.90 g,15 mmol) and dimethyl sulfoxide (120 mL) were added, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with methylene chloride, and the solvent was dried by spin-drying, and then separated and purified by silica gel column chromatography to give compound 17-3 of about 2.19g in a yield of 56%. MS:784.45.
Synthesis of Compound 17-4:
in a 100mL three-necked flask, 17-3 (0.36 g,0.46 mmol) and anhydrous N, N-dimethylformamide (20 mL) were added, the temperature was lowered to 0℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. The temperature was raised to 90℃and stirred overnight, cooled to room temperature and extracted with dichloromethane, then the organic solvent was dried by spin-drying, and purified by column chromatography on silica gel to give compound 17-4 in an amount of about 0.30g and 78% yield. MS:840.14.
synthesis of Compound 17-5:
in a 250mL round bottom flask, compound 17-4 (0.251 g,0.30 mmol) and thiophen indenone (0.60 g,3.0 mmol) were dissolved in 45mL chloroform, 1mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and suction filtration was performed to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 17-5 about 0.20g in 55% yield. MALDI-TOF MS:1204.42.
synthesis of side chain Polymer (17):
in a 25mL Schlenk flask, 0.1g of the compound 17-5 and 0.020mmol of azobisisobutyronitrile AIBN were charged under argon atmosphere, 10mL of tetrahydrofuran THF was charged into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved with methylene chloride, settled in methanol, dried again in vacuo to give 0.051g of side chain polymer (17). Wherein: mn=14.4k, pdi=2.07.
Synthesis example 5: synthesis of side chain Polymer (25)
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Synthesis of Compound 25-1:
accurately weighing 3-bromothieno [3,2-b ]]Thiophene (3.28 g,15 mmol), tributyl (4-hexylphenyl) stannane (7.44 g,16.5 mmol), pd (PPh 3 ) 2 Cl 2 (1.05 g,1.5 mmol) was put into a 250mL three-necked flask, 100mL of anhydrous toluene was added, nitrogen was replaced three times, the temperature was raised to 110 ℃, the reaction was carried out for 20 hours, after the raw materials were completely reacted, the reaction was cooled to room temperature, diluted with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, distilled off under reduced pressure to remove the excess solvent, and purified by silica gel column chromatography to obtain 3.6g of compound 25-1, yield: 80%, MS:300.20.
synthesis of Compound 25-2:
accurately weighing compound 25-1 (3.0 g,10 mmol) in 100mL dry anhydrous tetrahydrofuran, stirring thoroughly, after three nitrogen substitutions, the mixture was cooled to-70℃and LDA (2M, 5mL,10 mmol) was slowly added dropwise. The mixture was stirred at-70℃for 2 hours, then Me was added 3 SnCl (1.0M, 10mL,10 mmol) was stirred for 1 hour with heat preservation. Then naturally warmed to room temperature and stirred overnight. After complete reaction of the starting materials, the resulting mixture was poured into water and extracted with DCM. Final concentration and drying gave compound 25-2 about 3.93g. Yield: 85%. MS:463.14.
Synthesis of Compound 25-3:
in a 250mL round bottom flask, compound 7-2 (1.82 g,3.6 mmol) and compound 25-2 (3.7 g,8 mmol) were weighed into 30mL tetrahydrofuran and bis (triphenylphosphine) palladium dichloride (0.05 g,0.072 mmol) was added to the system under argon. The mixture was refluxed at 80℃for 20 hours. Cooling to a real temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain 25-3 about 1.9g of a compound with a yield: 56%. MS:944.23. synthesis of Compound 25-4:
in a 250mL 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℃for 15 hours under argon protection. Cooling to room temperature, distilling under reduced pressure to remove solvent, separating and purifying by silica gel column chromatography to obtain compound 25-4 about 1.0g, yield: 57%, MS:880.45.
synthesis of Compound 25-5:
in a 250mL flask, compound 25-4 (0.88 g,1.0 mmol), potassium hydroxide (0.39 g,7 mmol), bromoisooctane (0.58 g,3 mmol) and dimethyl sulfoxide (30 mL) were added, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with methylene chloride, separated, and then the solvent was dried by spin-drying, and purification was performed by silica gel column chromatography to obtain Compound 25-5 about 0.86g. Yield: 78%, MS:1104.70.
Synthesis of Compound 25-6:
in a 100mL 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℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. Heating to 90 ℃ and stirring overnight, cooling to room temperature, extracting with dichloromethane, separating liquid, spin-drying organic solvent, and separating and purifying by silica gel column chromatography to obtain compound 25-6 about 0.422g, yield: 79%, MS:1160.48.
synthesis of Compound 25-7:
in a 250mL round bottom flask, compound 25-6 (0.116 g,0.10 mmol) and 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile (0.230 g,1.00 mmol) were dissolved in 45mL chloroform, 1mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and then suction filtration gave a crude product, which was purified by silica gel column chromatography to give compound 25-7 about 0.10g, yield: 64%, MALDI-TOF MS:1585.53.
synthesis of side chain Polymer (25):
0.1g of 25-7 and 0.020mmol of azobisisobutyronitrile AIBN were charged into a 25mL Schlenk flask under argon atmosphere, 10mL of tetrahydrofuran was added into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved in methylene chloride, settled in methanol, dried again in vacuo to give 0.063g of polymer (25). Wherein: mn=15.9k, pdi=1.60.
Synthesis example 6: synthesis of side chain Polymer (28)
Synthesis of Compound 28-1:
in a 250mL round bottom flask, compound 7-2 (10.06 g,20 mmol) and tributyl (6-undecylselenophen [3,2-b ] thiophen-2-yl) stannane (27.72 g,44 mmol) were weighed into 100mL tetrahydrofuran and bis (triphenylphosphine) palladium dichloride (0.62 g,0.88 mmol) was added to the system under argon. The mixture was refluxed at 80℃for 20 hours. Cooling to a solid temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain 28-1 about 10.54g of the compound. Yield: 51%, MS:1026.22.
Synthesis of Compound 28-2:
in a 250mL round bottom flask, compound 28-1 (10.26 g,10 mmol), triethyl phosphite (50 mL) and o-dichlorobenzene (20 mL) were added. The mixture was reacted at 180℃for 15 hours under argon. Cooling to room temperature, distilling under reduced pressure to remove solvent, and separating and purifying by silica gel column chromatography to obtain compound 28-2 about 5.0g. Yield: 52%, MS:962.32.
Synthesis of Compound 28-3:
in a 250mL flask, compound 28-2 (4.81 g,5 mmol), potassium hydroxide (2 g,35.64 mmol), bromoisooctane (2.90 g,15 mmol) and dimethyl sulfoxide (120 mL) were added, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with dichloromethane, separated, then the solvent was dried by spin-drying, and purification was performed by silica gel column chromatography to obtain compound 28-3 about 4.3g. Yield: 73% MALDI-TOF MS 1186.58.
Synthesis of Compound 28-4:
in a 100mL three-necked flask, 28-3 (0.546 g,0.46 mmol) and anhydrous N, N-dimethylformamide (20 mL) were added, the temperature was lowered to 0℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. Heating to 90 ℃ and stirring overnight, cooling to room temperature, extracting with dichloromethane, separating liquid, spin-drying organic solvent, and separating and purifying by silica gel column chromatography to obtain 28-4 about 0.42g of compound with yield: 74%, MALDI-TOF MS:1242.55.
Synthesis of Compound 28-5:
in a 250mL 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 45mL chloroform, 1mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and then suction filtered to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 28-5 about 0.11g. Yield: 64% MALDI-TOF MS 1732.55.
Synthesis of side chain Polymer (28):
under argon atmosphere, 0.1g of 28-5 and 0.020mmol of azobisisobutyronitrile were added into a 25mL Schlenk flask, 10mL of tetrahydrofuran was added into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo, dissolved in methylene chloride, precipitated in methanol, dried again in vacuo to give 0.067g of side chain polymer (28). Wherein: mn=22.5k, pdi=1.55.
Synthesis example 7: synthesis of side chain Polymer (34)
Synthesis of Compound 34-1:
in a 250ml 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 into 100ml tetrahydrofuran and ditriphenylphosphine palladium dichloride (0.62 g,0.88 mmol) was added to the system under argon. The mixture was refluxed at 80℃for 20 hours. Cooling to a solid temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain 34-1 about 10.54g of a compound. Yield: 72%, MS:735.01.
Synthesis of Compound 34-2:
in a 250mL round bottom flask, compound 34-1 (7.35 g,10 mmol), triethyl phosphite (50 mL) and o-dichlorobenzene (20 mL) were added. The mixture was reacted at 180℃for 15 hours under argon. Cooling to room temperature, distilling under reduced pressure to remove solvent, and separating and purifying by silica gel column chromatography to obtain compound 34-2 about 5.0g, yield: 74%, MS:671.99.
Synthesis of Compound 34-3:
in a 250mL flask, compound 34-2 (3.36 g,5 mmol), potassium hydroxide (2 g,35.64 mmol), bromoisooctane (2.90 g,15 mmol) and dimethyl sulfoxide (120 mL) were added, the mixture was reacted at 80℃for 16 hours under the protection of argon, cooled to room temperature, extracted with dichloromethane, and the solvent was dried by spin-drying, and purified by silica gel column chromatography to give compound 34-3 about 3.7g, yield: 83%, MS:896.15.
Synthesis of Compound 34-4:
in a 100mL three-necked flask, compound 34-3 (0.82 g,0.92 mmol) and anhydrous N, N-dimethylformamide (20 mL) were added, the temperature was lowered to 0℃and phosphorus oxychloride (1 mL) was added thereto, followed by stirring for 2 hours. The mixture was stirred overnight at 90℃and cooled to room temperature, and then extracted with dichloromethane, the solvent was dried by spin-drying, and the mixture was purified by silica gel column chromatography to give about 0.58g of compound 34-4. Yield: 66%, MS:952.12.
Synthesis of Compound 34-5:
in a 250mL round bottom flask, compound 34-4 (0.19 g,0.20 mmol) and 5, 6-difluoro-3- (dicyanomethylene) indidone (0.46 g,2.00 mmol) were dissolved in 45mL chloroform, 1mL pyridine was added, the mixture was refluxed under argon for 12 hours, cooled to room temperature, poured into 200mL anhydrous methanol, and suction filtered to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain compound 34-5 about 0.18g. Yield: 67% MALDI-TOF MS 1376.35.
Synthesis of side chain Polymer (34):
0.1g of compound 34-5 and 0.020mmol of azobisisobutyronitrile AIBN were charged into a 25mL Schlenk flask under argon atmosphere, 10mL of tetrahydrofuran was added into the flask, the temperature was raised to 50℃and the reaction was stirred under argon for 48 hours, then cooled to room temperature, the reaction solution was poured into acetone, the precipitated solid was filtered, dried in vacuo and then dissolved in methylene chloride, settled in methanol, and dried again in vacuo to give 0.061g of side chain polymer (34). Wherein: mn=15.1k, pdi=1.78.
OPV device example preparation:
the process of preparing an OPV device comprising the above side chain polymer is described in detail below by means of specific examples.
Device example 1 the preparation steps are as follows:
1) Cleaning an ITO substrate:
the ITO conductive glass is cleaned by a detergent, washed by deionized water, acetone and isopropanol for 15 minutes, and then dried by nitrogen and treated in a plasma cleaner for 5 minutes, so as to further clean the surface and improve the wettability.
2) Preparation of anode buffer layer
PEDOT: PSS (clevelos) TM pVP Al 4083) is uniformly spin-coated on ITO at a spin speed of 3000-4000rpm/min and dried at 150deg.C for 15min to obtain an anode modification layer with a thickness of 20 nm.
3) Photoactive layer preparation
Uniformly spin-coating a photoactive layer material (the concentration of the mixture of the donor material and the acceptor material in chloroform is 15.4 mg/mL) on an anode buffer layer at a rotation speed of 1800-3000rpm/min in a glove box (inert gas atmosphere), so as 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 side chain polymers (7); the mass ratio of donor material to acceptor material was 1:1.2.
4) Cathode buffer layer preparation
After thermal annealing for 10min on a hot bench at 100 ℃, uniformly spin-coating a cathode buffer layer material PDINN (PDINN is dissolved in methanol to prepare a solution with the concentration of 1 mg/mL) on an active layer, wherein the spin-coating speed is 2000-4000rpm/min, and the cathode buffer layer with the thickness of 5nm is obtained;
5) Cathode layer preparation
In high vacuum (1X 10) -6 Millibar) Ag was evaporated onto the cathode buffer layer to form a cathode layer with a thickness of 100 nm.
6) Packaging
The device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
Device examples 2-7 were prepared as in device example 1, except that the photoactive layer acceptor materials were selected differently and the specific device structures are shown in table 1.
TABLE 1 organic solar cell device structure
Device embodiment Anode Anode buffer layer Photoactive layer materials Cathode buffer layer Cathode electrode
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
Performance test is carried out on the prepared organic solar cell device, a cell current-voltage curve is tested under the irradiation of standard light of a solar simulator (SS-F5-3A) AM1.5G, and photoelectric conversion efficiency is calculated as shown in Table 2:
TABLE 2
Device embodiment Photoactive layer materials Photoelectric conversion efficiency (%)
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
As can be seen from the data in table 2, the side chain polymer according to the present invention exhibits excellent photoelectric conversion performance when applied as an acceptor material in an organic solar cell device.
The above examples further illustrate the content of the present application but should not be construed as limiting the present application. Modifications and substitutions to methods, procedures, or conditions of the present application without departing from the spirit and substance of the present application are intended to be within the scope of the present application. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.

Claims (10)

1. A side chain polymer characterized by: the side chain polymer has a structure shown in a general formula (I):
wherein:
l is independently selected from the group consisting of, for each occurrence, a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, a straight chain alkoxy group having 1 to 20 carbon atoms, a branched chain alkoxy group having 3 to 20 carbon atoms, a straight chain alkylthio group having 1 to 20 carbon atoms, a branched alkylthio group having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
Ar 1 、Ar 2 each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
m is independently selected from O or C (CN) for each occurrence 2 ；
Ar 3 、Ar 4 Each occurrence is independently selected from unsubstituted or substituted * Substituted aromatic groups having 6-20 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R 1 、R 2 independently selected for each occurrence from the group consisting of straight chain alkyl groups having 1 to 20 carbon atoms, branched chain alkyl groups having 3 to 20 carbon atoms, straight chain alkoxy groups having 1 to 20 carbon atoms, branched chain alkoxy groups having 3 to 20 carbon atoms, straight chain alkylthio groups having 1 to 20 carbon atoms, branched chain alkylthio groups having 3 to 20 carbon atoms, unsubstituted or substituted with R * Substituted aromatic groups having 6-10 carbon atoms, or unsubstituted or substituted by R * Substituted heteroaromatic groups having 5 to 20 ring atoms;
R * independently for each occurrence-D, halogen, cyano, nitro, straight chain alkyl having 1 to 20 carbon atoms, branched or cyclic alkyl having 3 to 20 carbon atoms, straight chain alkoxy having 1 to 20 carbon atoms, branched or cyclic alkoxy having 3 to 20 carbon atoms, straight chain alkylthio having 1 to 20 carbon atoms, branched or cyclic alkylthio having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or a combination thereof;
n is the number of repeating units and n is an integer of 2 or more.
2. The side chain polymer of claim 1, wherein: ar (Ar) 1 、Ar 2 Each occurrence is independently selected from any one of the following groups:
wherein:
y is independently selected from O, S, or Se for each occurrence;
R 3 independently selected from the group consisting of-H, -D, a straight chain alkyl group having 1-20 carbon atoms, a branched chain alkyl group having 3-20 carbon atoms, a straight chain alkoxy group having 1-20 carbon atoms, a branched chain alkoxy group having 3-20 carbon atoms, a straight chain alkylthio group having 1-20 carbon atoms, a branched alkylthio group having 3-20 carbon atoms, an aromatic group having 6-20 carbon atoms, and a heteroaromatic group having 5-20 ring atoms, or a combination thereof;
* Represents a fused ring site selected from the group consisting of C atoms;
# represents the ligation site.
3. The side chain polymer of claim 2, wherein: ar (Ar) 1 、Ar 2 Each occurrence is independently selected from any one of the following groups:
4. the side chain polymer of claim 2, wherein: the side chain polymer is selected from structures shown in a general formula (II) or (III):
5. the side chain polymer according to any one of claims 1 to 4, wherein: ar (Ar) 3 、Ar 4 Each occurrence is independently selected from any one of the following groups:
wherein,
x is independently selected from N or CR for each occurrence 4 ；
Each occurrence of W is independently selected from O, S, se;
R 4 independently at each occurrence, a group selected from the group consisting of-H, -D, halogen, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, and combinations thereof;
* Represents a fused ring site selected from the group consisting of C atoms.
6. The side chain polymer of claim 1, wherein: in the general formula (I)Each occurrence is independently selected from any one of the following groups:
wherein: # represents the ligation site.
7. The side chain polymer according to any one of claims 1 to 4, wherein: l is independently selected from linear alkyl groups having 1 to 16 carbon atoms for each occurrence.
8. The side chain polymer of claim 1, wherein: the side chain polymer is selected from the following structural formulas:
wherein: in the above structural formula- (CH) 2 ) m -represents a linear alkyl group having m carbon atoms, m being an integer from 0 to 15.
9. A mixture characterized by: the mixture comprising a side chain polymer according to any one of claims 1 to 8, and at least one further 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 a side chain polymer according to any one of claims 1 to 8 or a mixture according to claim 9.
CN202311677674.0A 2023-12-08 2023-12-08 Side chain polymer and application thereof in organic electronic device Pending CN117659243A (en)

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