CN115386069B - Copolymer, active layer, and organic photovoltaic element - Google Patents
Copolymer, active layer, and organic photovoltaic element Download PDFInfo
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- CN115386069B CN115386069B CN202211197788.0A CN202211197788A CN115386069B CN 115386069 B CN115386069 B CN 115386069B CN 202211197788 A CN202211197788 A CN 202211197788A CN 115386069 B CN115386069 B CN 115386069B
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- active layer
- copolymer
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- organic photovoltaic
- alkyl
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 62
- 238000013086 organic photovoltaic Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 48
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
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- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 4
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- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- -1 PC60BM and PC70 BM) Chemical class 0.000 description 3
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/10—Definition of the polymer structure
- C08G2261/19—Definition of the polymer structure partially conjugated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
A copolymer as an electron acceptor material, an active layer, and an organic photovoltaic device including the copolymer. The copolymer has wide absorption wavelength distribution and high absorption degree in ultraviolet-visible light region, so that the copolymer can be used as an electron acceptor material for improving photocurrent density, and has excellent photoelectric conversion property.
Description
Technical Field
The present invention relates to a copolymer (copolymer) capable of being used as an electron acceptor material, an active layer and an organic photovoltaic device comprising the copolymer, and more particularly, to a random copolymer (random copolymer) and an active layer and an organic photovoltaic device comprising the random copolymer.
Background
With the evolution of the age, the consumption of energy resources such as coal, petroleum, natural gas and nuclear energy is increasing, and the energy crisis also relatively emerging, so that the solar power generation is developed. Solar power generation is a renewable environment-friendly power generation mode and can reduce environmental pollution. The first generation of solar cells was based on silicon-based (silicon-based) solar cells, which have high photoelectric conversion rates. The second generation solar cell is a thin-film cadmium telluride (CdTe) solar cell, but the toxicity of raw materials and the manufacturing process of the solar cell have great pollution to the environment. Accordingly, the third generation organic solar cells have grown with the implications that include dye sensitized cells (dye-sensitized solar cell, DSSC), nanocrystalline cells or organic photovoltaic elements (organic photovoltaic, OPV). Compared with inorganic materials which need to be manufactured by vacuum Cheng Dumo, the organic photovoltaic element can be manufactured by dip coating, spin coating, slit coating, screen printing, ink-jet printing and the like, so that the economic benefits of low cost and mass production are easier to realize. In the process of manufacturing the new generation of organic photovoltaic devices, electron acceptor materials and electron donor materials (polymers) are used as materials of the active layer (light absorption layer). The new generation of organic photovoltaic elements has several advantages: (1) the weight is light, and the manufacturing cost is low; (2) has flexibility; (3) the designability of the device structure is strong; (4) is suitable for liquid phase process, and can be applied in large area.
Although organic photovoltaic devices have many advantages, the current development on electron acceptor materials is mostly based on fullerene derivatives (such as PC60BM and PC70 BM), however fullerene derivatives themselves have the following disadvantages: easy dimerization under illumination, easy crystallization when heating, weak absorption in visible light region, less easy structure modification and purification, high price and the like. Therefore, non-fullerene electron acceptor materials have been actively developed in recent years in various fields for higher performance. As far as known, compared with non-fullerene electron acceptor materials in the form of small organic molecules, polymer electron acceptor materials generally have good mechanical properties, film forming property and thermal stability, so that polymer electron acceptor materials are used as active layers of organic photovoltaic devices to improve energy conversion efficiency (PCE) of the organic photovoltaic devices, which is an important research direction of recent scientists. For example, chinese patent publication No. CN113174032a (document one) and CN113024780a (document two).
In the fabrication of the active layer of the organic photovoltaic device, there are also issues such as the kind of solvent capable of dissolving the electron acceptor material in the polymer form, the solubility, and whether precipitation occurs after standing, and the influence of the formed active layer solution on the film forming property and PCE in the formation of the active layer. However, the literature does not address the issues mentioned above, nor does it disclose the type of solvent used for the active layer. In addition, the choice of the solvent type is preferably a non-chlorine (meaning chlorine-free) solvent based on environmental issues, and even if a non-chlorine solvent is used, it is preferable in view of solubility and whether or not the active layer solution generates a precipitate after standing, in particular, an active layer solution having no precipitate. Although it is mentioned in the second document that a non-chlorine solvent such as toluene can be used as the active layer solvent, chloroform containing chlorine is still used as the solvent in the example, and PCE is only 12.6% at the maximum. In fact, when the solvent of the active layer of document two is replaced with a non-chlorine solvent such as xylene, it can be found from the experimental results that the precipitate of the polymer type electron acceptor material in the active layer solution adheres to the wall surface of the container (this will be described later in the comparative example), so that when the solvent of the active layer is replaced with a non-chlorine solvent such as xylene, the precipitate may cause poor film forming property or defect formation at the time of forming the active layer, and further the PCE is lower than 12.6%.
One of the factors that arises in the second problem is that the polymer type electron acceptor material of the second document is a homopolymer (homo polymer), and the solubility thereof is low due to the good crystallinity of the homopolymer, which results in that a chlorine-containing solvent, such as chloroform, which is not environment-friendly, is required to be used to dissolve the homopolymer to have high solubility, whereas when a non-chlorine solvent, such as xylene, is used, although it is stated that the homopolymer can be dissolved, the above-mentioned precipitate easily appears, and thus the film forming property of the active layer is poor or defects are formed.
Therefore, developing a structure that can use a relatively environmentally friendly chlorine-free solvent (e.g., toluene, xylene) dissolved polymer as an active layer material such that the active layer solution does not have generation of precipitates, and an active layer having good electron transport properties of fullerene derivatives, and an organic photovoltaic element having a high PCE, e.g., higher than 16%, has been the object of the current research.
Disclosure of Invention
In view of the problems of the conventional organic photovoltaic devices, the present invention provides a copolymer capable of being used as an electron acceptor material, which can be matched with an electron donor material to be used as an active layer of the organic photovoltaic device. In particular, the present invention provides a random copolymer comprising at least two repeating units in a random arrangement in the main chain of the random copolymer, the two repeating units being different from each other, and thus having reduced crystallinity, so that the random copolymer can be dissolved using a relatively environmentally friendly solvent (e.g., toluene, xylene) having no chlorine. In addition, the active layer also has good electron transport properties of the fullerene derivative. Surprisingly, the copolymer of the present invention has a broad absorption wavelength distribution and a high absorbance in the uv-visible region, so that the absorption in the visible region can be improved, the photocurrent density can be increased, and further the organic photovoltaic device can have excellent photoelectric conversion characteristics and have good energy conversion efficiency (PCE).
Accordingly, a first object of the present invention is to provide a copolymer. The copolymer referred to in the present invention should be understood as any of random copolymer (random copolymer) or block copolymer (block copolymer), except where a random copolymer is specifically indicated. Preferably, the copolymers referred to herein are random copolymers.
Thus, the copolymer of the present invention comprises a structure represented by the following formula (I):
[ chemical formula (I)]
Wherein,
is a first repeating unit structure;
is a second repeating unit structure;
the first repeating unit structure is different from the second repeating unit structure;
a and b are both real numbers of molar fractions, and 0< a <1,0< b <1, and the sum of a and b is 1;
π 1 pi 2 Each independently is an aromatic or heteroaromatic ring group, pi 1 Pi 2 May be the same or different from each other;
SMA 2 a group of FUSED RING (FUSED RING) structure or a group of NON FUSED RING (NON FUSED RING) structure;
SMA 1 is that
C 1 And C 2 Each independently is
C 1 And C 2 Can be phase with each otherIdentical or different;
x is O, S, se, -NR 5 -or
R 1 And R is R 2 Each independently is C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl, R 1 And R is R 2 May be the same or different from each other;
R 3 and R is R 4 Each independently is unsubstituted or R 0 Substituted C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl or C 1 ～C 30 Alkoxy heteroaryl, R 3 And R is R 4 May be the same or different from each other;
R 0 is C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl or C 1 ～C 30 An alkoxyheteroaryl group;
R 5 is C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group;
R 6 and R is R 7 Each independently H, F, cl, R 8 、-CN、-OR 9 、-SR 10 、-C(＝O)OR 11 Aryl or heteroaryl, R 6 And R is R 7 May be the same or different from each other;
R 8 to R 11 Respectively unsubstituted or at least one R 12 Substituted C 4 ～C 30 Linear, branched or cyclic alkyl, unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkenyl, or unsubstituted or with at least one R 12 Substituted C 4 ～C 30 Alkynyl, R 12 Is halogen or-CN;
EG is as follows
Z 1 To Z 3 Each independently H, F, cl, br, R 8 、-CN、-OR 9 、-SR 10 -OR C (=o) OR 11 ，Z 1 To Z 3 May be the same or different from each other.
Specifically, the term "alkylaryl", "alkylheteroaryl", "alkoxyaryl" and "alkoxyheteroaryl" as used herein refers to "alkyl-substituted aryl", "alkyl-substituted heteroaryl", "alkoxy-substituted aryl" and "alkoxy-substituted heteroaryl", respectively. In addition, the preceding carbon number refers to the carbon number of the alkyl group, e.g. C 1 ～C 30 Alkylaryl is referred to as C 1 ～C 30 Alkyl-substituted aryl, C 1 ～C 30 Alkyl heteroaryl is referred to as C 1 ～C 30 Alkyl-substituted heteroaryl, C 1 ～C 30 Alkoxy aryl refers to C 1 ～C 30 Alkoxy substituted aryl, C 1 ～C 30 Alkoxy heteroaryl is referred to as C 1 ～C 30 Alkoxy substituted heteroaryl. The term "small molecule group" refers to a Residue (Residue) of a compound that is not a polymer or an Oligomer. In addition, the present invention describes "Z 1 To Z 3 "means" Z 1 、Z 2 Z is as follows 3 The "" R "", the 8 To R 11 "means" R 8 、R 9 、R 10 R is R 11 The rest of the analogy is not repeated. Further, it is known from the structure of the EG group that the EG group is an electron withdrawing group.
Preferably, SMA 2 Is a group of this condensed ring structure.
Preferably, the group of the condensed ring structure is a five-membered condensed ring derivative group, a seven-membered condensed ring derivative group or a nine-membered condensed ring derivative group.
Preferably, the five-membered condensed ring derivative group is
The seven-membered condensed ring derivative group is
The nine-membered condensed ring derivative group is
U is NQ 23 、C(Q 24 ) 2 Or Si (Q) 25 ) 2 ，Q 1 To Q 22 Each independently H, C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl, Q 23 To Q 25 Each independently H, C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group; q (Q) 1 To Q 6 May be the same or different from each other, Q 7 To Q 12 May be the same or different from each other, Q 13 To Q 16 May be the same or different from each other, and/or Q 17 To Q 22 May be the same or different from each other.
Preferably, the group of the non-condensed ring structure is R 13 Is 2-ethylhexyl (2-ethylhexyl), R 14 Is 2-hexyldecyl (2-hexydecyl).
Specifically, based on the above examples of the group related to the condensed ring structure and the group not condensed ring structure, the group of the condensed ring structure is the group shown in SMA 2 In the structure of (a) a plurality of carbocycles and/or a plurality of heterocycles on the main chain of each electron withdrawing group (EG group) connected at the left end and the right end are connected in a shared ring edge manner, namely SMA 2 All the main chains of (a) are all condensed ring structures connected by condensed rings; in contrast, the non-condensed ring structure is defined as a structure in SMA 2 At least one single bond is present in the main chain connecting the left and right ends of the other electron withdrawing groups (EG groups) to connect a plurality of other carbocycles and/or a plurality of other heterocycles, i.e. SMA 2 Is a non-fully condensed ring structure in which not all condensed rings are connected to each other.
Preferably pi 1 Pi 2 Each independently is V is S, O or Se, R 17 To R 18 Definition and R as previously described 6 Is defined identically and R 17 And R is R 18 May be the same or different from each other, and n is an integer of 0 to 12.
It is therefore a second object of the present invention to provide an active layer comprising the aforementioned copolymer.
Preferably, the active layer comprises an electron donor material and an electron acceptor material, the electron acceptor material comprising the copolymer.
Preferably, the electron acceptor material further comprises a fullerene derivative, i.e. the electron acceptor material comprises the copolymer and the fullerene derivative, the fullerene derivative is PC 60 BM or PC 70 BM。
Accordingly, a third object of the present invention is to provide an organic photovoltaic device comprising the aforementioned copolymer and/or the active layer.
Preferably, the organic photovoltaic device comprises a substrate, a first electrode laminated on the substrate, an electron transport layer laminated on the first electrode, an active layer laminated on the electron transport layer, a hole transport layer laminated on the active layer, and a second electrode laminated on the hole transport layer, wherein the active layer comprises the copolymer.
Preferably, the organic photovoltaic device comprises a substrate, a first electrode laminated on the substrate, a hole transport layer laminated on the first electrode, an active layer laminated on the hole transport layer, an electron transport layer laminated on the active layer, and a second electrode laminated on the electron transport layer, wherein the active layer comprises the copolymer.
The invention has the following effects: since the copolymer of the present invention as an electron acceptor material contains a strong electron withdrawing group [ SMA ] in the main chain 1 ]Another strong electron withdrawing group [ SMA ] 2 ]By means of different chemical structures, the absorption wavelength distribution in the ultraviolet-visible region is increased and the conjugated group [ pi ] is transmitted]To adjust the energy level and solubility. Especially when the copolymer is a random copolymer and/or SMA 2 In the case of the polyvalent fused ring derivative group, since crystallinity and/or polarity of the copolymer are reduced, the polyvalent fused ring derivative group can be dissolved in a relatively environmentally friendly solvent (e.g., toluene or xylene) containing no chlorine. The copolymer of the invention can be properly added into an active layer to improve the energy level matching property between an electron donor material and an electron acceptor material. Therefore, when the copolymer is used as an electron acceptor material, the photocurrent density is increased by utilizing the absorption wavelength of a wide ultraviolet-visible light region and high absorbance, so that the energy conversion efficiency of the organic photovoltaic element is improved.
Drawings
Other features and effects of the present invention will be apparent from the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a spectrum illustrating the UV-visible absorption spectra of copolymers 1-3 and polymers 1-2 in solution;
FIG. 2 is a spectrum illustrating the UV-visible absorption spectra of copolymers 1-3 and polymers 1-2 in solid state film formation;
FIG. 3 is a photographic view of the solubility of polymers 1-2 and copolymers in xylene;
FIG. 4 is a schematic cross-sectional view illustrating a first structure of the organic photovoltaic device of the present invention;
FIG. 5 is a schematic cross-sectional view illustrating a second structure of the organic photovoltaic device of the present invention; and
Fig. 6 is a graph illustrating the voltage-current densities of the organic photovoltaic devices of comparative examples 1 to 3 and application examples 1 to 3, respectively.
[ symbolic description ]
70: substrate board
80: first electrode
90: organic semiconductor layer
91: electron transport layer
92: active layer
93: hole transport layer
100: second electrode
Detailed Description
< preparation of copolymers 1 to 3>.
Preparation example 1: copolymer 1 was prepared.
Preparation of compound 3:
compound 1 (5 g,6.7 mmol) was added to dimethylformamide (DMF, 40 mL), followed by addition of potassium carbonate (5.5 g,40 mmol) and compound 2 (11 g,27 mmol), and then heated to 80 ℃ for 3 hours. Then, heptane and water were added at a reduced temperature to extract, and the organic layer was dried over anhydrous magnesium sulfate and concentrated to remove the solvent. Finally, after precipitating the solid with heptane and isopropanol, compound 3 (5.8 g, yield: 67%) was obtained as a brown solid.
Preparation of Compound 4:
compound 3 (5.5 g,4.2 mmol) was dissolved in 1, 2-dichloroethane (55 mL) and anhydrous dimethylformamide (19 mL,252 mmol) was added thereto, and phosphorus oxychloride (12 mL,126 mmol) was slowly added dropwise under ice-bath. Then, the temperature was raised to reflux and stirred for 2 hours. After the reaction was completed, extraction was performed by adding methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated and drained with a rotary concentrator. Finally, purification by column chromatography on silica gel (dichloromethane: n-heptane=2:1 as the eluent) and drying in vacuo gave compound 4 (3.8 g, yield: 67%) as an orange liquid.
Preparation of Compound 6:
after chloroform (38 mL) was added to compound 4 (3.8 g,0.28 mmol) and compound 5 (2.1 g,8.5 mmol), pyridine (0.3 mL) was slowly added dropwise and reacted under nitrogen for 3 hours. After the reaction is finished, cooling and concentrating and pumping by a rotary concentrator. Then, a solid was precipitated with methanol, purified by column chromatography on silica gel (chloroform as a punching liquid) and dried under vacuum to obtain a dark purple solid, namely, compound 6 (4.9 g, yield: 93%).
Preparation of compound 8:
after chloroform (15 mL) was added to compound 7 (1.5 g,1.56 mmol) and compound 5 (1.27 g,4.67 mmol), pyridine (py, 0.1 mL) was slowly added dropwise and reacted under nitrogen for 3 hours. After the reaction is finished, cooling and concentrating and pumping by a rotary concentrator. Then, a solid was precipitated with methanol, purified by column chromatography on silica gel (chloroform as a punching liquid) and dried under vacuum to obtain a dark purple solid, namely compound 8 (2.1 g, yield: 90%).
Preparation of copolymer 1:
compound 6 (186 mmol), compound 8 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) are reacted under nitrogen 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd ] 2 (dba) 3 ](10.6 mmol) was charged into a 50mL reaction flask. Then, 12mL of anhydrous chlorobenzene (PhCl) was added, and the mixture was stirred at 130 ℃ for 3 hours, and after cooling the reaction to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to Soxhlet extraction with methanol, acetone and chloroform in this order. Finally, the chloroform raffinate was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to obtain copolymer 1.
Preparation example 2: copolymer 2 was prepared.
Preparation of compound 10:
after chloroform (20 mL) was added to compound 9 (2 g,1.85 mmol) and compound 5 (1.51 g,5.56 mmol), pyridine (0.2 mL) was slowly added dropwise and reacted under nitrogen for 3 hours. After the reaction is finished, cooling and concentrating and pumping by a rotary concentrator. Then, a solid was separated out with methanol, purified by column chromatography on silica gel (chloroform as a punching liquid) and dried in vacuo to obtain a dark purple solid, namely compound 8 (2.6 g, yield: 88%).
Preparation of copolymer 2:
compound 6 (1.86 mmol), compound 10 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) under nitrogen 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd ] 2 (dba) 3 ](10.6 mmol) was charged into a 50mL reaction flask. Then21mL of anhydrous chlorobenzene (PhCl) was added and stirred at 130℃for 3 hours, after which the reaction was cooled to room temperature, the contents of the flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to Soxhlet extraction with methanol, acetone and chloroform in this order. Finally, the chloroform raffinate was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to obtain copolymer 2.
Preparation example 3: copolymer 3 was prepared.
Preparation of compound 12:
after chloroform (20 mL) was added to compound 11 (2 g,1.36 mmol) and compound 5 (1.12 g,4.1 mmol), pyridine (0.2 mL) was slowly added dropwise and reacted under nitrogen for 3 hours. After the reaction is finished, cooling and concentrating and pumping by a rotary concentrator. Next, a solid was precipitated with methanol, purified by column chromatography on silica gel (chloroform as a punching liquid) and dried under vacuum to obtain a dark purple solid, namely compound 12 (2.4 g, yield: 90%).
Preparation of copolymer 3:
compound 6 (1.86 mmol), compound 12 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) under nitrogen 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd ] 2 (dba) 3 ](10.6 mmol) was charged into a 50mL reaction flask. Then, 21mL of anhydrous chlorobenzene (PhCl) was added, and the mixture was stirred at 130℃for 3 hours, and after cooling the reaction to room temperature, the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to Soxhlet extraction with methanol, acetone and chloroform in this order. Finally, the chloroform raffinate was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to obtain copolymer 3.
< providing polymers 1 and 2> used in the comparative examples described below.
Polymer 1 comprises repeating units as shown below, polymer 1 being a homopolymer:
polymer 2 comprises repeating units as shown below, polymer 2 being a homopolymer:
< ultraviolet-visible (UV-Vis) absorption spectrum >.
In FIG. 1, the ultraviolet-visible light absorption spectra of the copolymers 1 to 3 and the polymers 1 to 2 were measured by an instrument after they were dissolved in chloroform, respectively; FIG. 2 shows the ultraviolet-visible light absorption spectra measured by an instrument after the copolymers 1 to 3 and the polymers 1 to 2 were dissolved in chloroform, coated on a transparent glass slide and dried to form a solid film.
Referring to the spectral diagrams of FIGS. 1 and 2, copolymers 1-3 have a broad absorption wavelength distribution in the UV-visible region; in addition, the copolymers 1 to 3 have higher absorptivity in the ultraviolet-visible region than the polymers 1 to 2, and thus the copolymers 1 to 3 can be used as electron acceptor materials having a wide absorption wavelength distribution.
< solubility in chlorine-free solvents >.
FIG. 3 shows the results of placing 10mg of each of polymers 1 to 2 and copolymer 3 in a glass vessel, adding 1ml of xylene as a chlorine-free solvent, heating to 100℃and stirring for 3 hours, and finally returning to room temperature. Clearly, the glass containers on the left and in the middle of each of polymers 1 and 2 had precipitates, indicating that polymers 1 and 2 were insoluble in xylene or low in solubility; in contrast, the right glass vessel containing copolymer 3 did not have a precipitate, indicating that copolymer 3 was xylene soluble and highly soluble.
< organic photoelectric element Structure >
Organic photovoltaic devices of the present invention include, but are not limited to, organic light-emitting diodes (organic light-emitting diodes), organic thin film transistors (organic thin film transistor), organic photovoltaic devices (OPVs), and organic photodetectors ((organic photodetectors, OPD), the present invention being exemplified by organic photovoltaic devices (OPVs).
Fig. 4 is a cross-sectional view of a first structure of an organic photovoltaic element used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic semiconductor layer 90. The organic semiconductor layer 90 includes an electron transport layer 91 stacked above the first electrode 80, an active layer 92 stacked above the electron transport layer 91, and a hole transport layer 93 stacked above the active layer 92. Thus, the second electrode 100 is laminated on the hole transport layer 93.
Fig. 5 is a cross-sectional view of a second structure of an organic photovoltaic device used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic semiconductor layer 90. The organic semiconductor layer 90 includes a hole transport layer 93 stacked over the first electrode 80, an active layer 92 stacked over the hole transport layer 93, and an electron transport layer 91 stacked over the active layer 92. Thus, the second electrode 100 is laminated on the electron transport layer 91.
For convenience of description and understanding, the following is an embodiment using the structure of the organic photovoltaic device of fig. 4 as an application example.
Comparative examples 1 to 3 and application examples 1 to 3.
Organic photovoltaic elements (OPV) were prepared.
Organic photovoltaic devices of comparative examples 1 to 3 and application examples 1 to 3 were prepared according to the active layer materials (electron donor material and electron acceptor material) of the organic photovoltaic devices listed in table 1 below, and in the methods for preparing organic photovoltaic devices described later.
TABLE 1
The electron donor materials used in comparative examples 1 to 3 and application examples 1 to 3 were polymers 4 containing repeating units shown below, and the polymers 4 were homopolymers:
the electron acceptor materials used in comparative examples 1 to 3 and application examples 1 to 3 include compound 14 and compound 15:
the following is a method of making an organic photovoltaic element.
Before the organic photovoltaic element is manufactured, the patterned ITO glass substrate (12 omega/≡) is sequentially cleaned in an ultrasonic vibration groove for 10 minutes by using a cleaning agent, deionized water, acetone and isopropanol. After the ITO glass substrate is cleaned by ultrasonic vibration, surface treatment is carried out for 30 minutes in an ultraviolet ozone (UV-ozone) cleaner. The glass substrate is the substrate 70, the ito is the first electrode 80, and the anode is the structure of fig. 3.
Zinc acetate [ Zn (OAc) 2 ]The solution was spin-coated on an ITO glass substrate and baked at 170 ℃ for 30 minutes to form a ZnO layer (zinc oxide layer), which is the aforementioned electron transport layer 91.
Polymer 4 shown in comparative example 1 in table 1 was used as an electron donor material, and mixed with a non-fullerene electron acceptor material (compound 14) and a fullerene electron acceptor material (fullerene derivative, compound 15) at a weight ratio of 1:1.2:0.2, and then prepared into an active layer solution using o-xylene as a solvent. In comparison with comparative example 1, comparative examples 2 and 3 were each further added with polymers 1 and 2, polymer 4: compound 14: compound 15: the weight ratio of the polymer 1 or the polymer 2 is 1:1.2:0.2:0.1.
the copolymer 4 shown in application examples 1 to 3 in Table 1 was used as an electron donor material, and mixed with a non-fullerene electron acceptor material (compound 14), a copolymer 1 or 2 or 3, and a fullerene electron acceptor material (compound 15) in a weight ratio of 1:1.1:0.1:0.2, and then prepared into an active layer solution using o-xylene as a solvent.
Next, the active layer solution was spin-coated on the ZnO layer (electron transport layer 91) and baked at 120 ℃ for 10 minutes under nitrogen to form the active layer 92 on the ZnO layer (electron transport layer 91). Then, the mixture is sent into a vacuum cavity to deposit molybdenum trioxide (MoO) 3 ) A metal oxide (about 10 nm) is formed on the active layer 92 to form the hole transport layer 93. Next, ag metal (about 100 nm) is deposited as the aforementioned second electrode 100 by heating, i.e., the cathode in the structure of fig. 4.
< Electrical analysis of organic photovoltaic element >
The measurement area of the organic photovoltaic element was defined as 0.04cm via the metal mask 2 . Keithley 2400 as the power supply was programmed with Lab-View at an illuminance of 100mW/cm 2 The electrical properties of the device were measured under irradiation of AM1.5G simulated sunlight (SAN-EI XES-40S 3), and recorded by computer program, and voltage-current curves obtained for the organic photovoltaic devices of comparative examples 1 to 3 and application examples 1 to 3 are shown in FIG. 6, respectively.
< analysis of energy conversion efficiency (PCE) of organic photovoltaic element >
TABLE 2
In table 2, voc represents an open voltage (open voltage), jsc represents a short-circuit current (short-circuit current), FF represents a fill factor (fill factor), and PCE represents energy conversion efficiency (energy conversion efficiency). The open circuit voltage and the short circuit current are the intercept of the voltage-current density curve on the X-axis and the Y-axis respectively, and when the two values are increased, the efficiency of the organic photovoltaic element is improved better. In addition, the fill factor is a value obtained by dividing the area that can be plotted in the curve by the product of the short-circuit current and the open-circuit voltage. When three values of open circuit voltage, short circuit current, and fill factor are divided by the irradiated light, energy conversion efficiency is obtained, and the energy conversion efficiency is preferably higher. From the results of table 2, it can be found that the energy conversion efficiency pce=15.7% of comparative example 1, the PCEs of comparative examples 2 and 3 were only 10.6% and 10.7%, respectively, whereas the organic photovoltaic cells of application examples 1 to 3 all exceeded 16% of energy conversion efficiency. Therefore, the copolymer of the invention can be added into the electron acceptor material to amplify the visible light absorption distribution of the active layer and improve the absorption degree, thereby increasing the photocurrent density, and simultaneously, the energy level can be effectively regulated to ensure that the voltage is slightly increased. In addition, in application examples 1 to 3, the energy conversion efficiency pce=16.4% of the organic photovoltaic element prepared by adding the copolymer 1 and the copolymer 3 to the electron acceptor material was the optimum value.
Therefore, it is apparent from the above results that the copolymer of the present invention has broader visible light absorption characteristics and high absorptivity, and thus the proper addition of the copolymer of the present invention to the active layer formulation can increase the photocurrent density and improve the matching of energy levels among the copolymer donor material, the non-fullerene electron acceptor material and the fullerene electron acceptor material. The voltage slightly increases and increases the current density to effectively increase the energy conversion efficiency (PCE) of the organic photovoltaic cell.
However, the foregoing is only illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (9)
1. A copolymer comprising a repeating unit represented by the following formula (I):
[ chemical formula (I)]
Wherein,
is a first repeating unit structure;
is a second repeating unit structure;
the first repeating unit structure is different from the second repeating unit structure;
a and b are both real numbers of molar fractions, and 0< a <1,0< b <1, and the sum of a and b is 1;
π 1 pi 2 Each independently is an aromatic or heteroaromatic ring group;
SMA 2 is a group of a condensed ring structure, which is referred to as SMA 2 In the structure of (a), a plurality of carbocycles and/or a plurality of heterocycles on the main chain of each electron withdrawing group connected with the left end and the right end are connected in a shared ring edge way; wherein the group of the condensed ring structure is a five-membered condensed ring derivative group, a seven-membered condensed ring derivative group or a nine-membered condensed ring derivative group; wherein the five-membered condensed ring derivative group isThe seven-membered condensed ring derivative group is +.> The nine-membered condensed ring derivative group isU is NQ 23 、C(Q 24 ) 2 Or Si (Q) 25 ) 2 ，Q 1 To Q 22 Each independently H, C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl, Q 23 To Q 25 Each independently H, C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group;
SMA 1 is that
C 1 And C 2 Each independently is
X is O, S, se, -NR 5 -or
R 1 And R is R 2 Each independently is C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl;
R 3 and R is R 4 Each independently is unsubstituted or R 0 Substituted C 1 ～C 30 Alkyl, C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl or C 1 ～C 30 An alkoxyheteroaryl group;
R 0 is C 1 ～C 30 Alkoxy, C 1 ～C 30 Alkylaryl, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl or C 1 ～C 30 An alkoxyheteroaryl group;
R 5 is C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group;
R 6 and R is R 7 Each independently H, F, cl, R 8 、-CN、-OR 9 、-SR 10 、-C(＝O)OR 11 An aryl or heteroaryl group;
R 8 to R 11 Respectively unsubstituted or at least one R 12 Substituted C 4 ～C 30 Linear, branched or cyclic alkyl, unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkenyl, or unsubstituted or with at least one R 12 Substituted C 4 ～C 30 Alkynyl, R 12 Is halogen or-CN;
EG is as followsOr (b)
Z 1 To Z 3 Each independently H, F, cl, br, R 8 、-CN、-OR 9 、-SR 10 -OR C (=o) OR 11 。
2. The copolymer of claim 1, wherein pi 1 Pi 2 Each independently is
V is S, O or Se, R 17 To R 18 Definition and R as previously described 6 And n is an integer of 0 to 12.
3. An active layer comprising the copolymer of claim 1.
4. The active layer of claim 3, wherein the active layer comprises an electron donor material and an electron acceptor material, the electron acceptor material comprising the copolymer.
5. The active layer of claim 4, wherein the electron acceptor material further comprises a fullerene derivative.
6. The active layer of claim 5, wherein the electron acceptor material further comprises a fullerene derivative, the fullerene derivative being PC 60 BM or PC 70 BM。
7. An organic photovoltaic element comprising the copolymer of claim 1.
8. The organic photovoltaic device of claim 7, wherein the organic photovoltaic device comprises a substrate, a first electrode layered over the substrate, an electron transport layer layered over the first electrode, an active layer layered over the electron transport layer, a hole transport layer layered over the active layer, and a second electrode layered over the hole transport layer, and the active layer comprises the copolymer.
9. The organic photovoltaic device of claim 7, wherein the organic photovoltaic device comprises a substrate, a first electrode layered over the substrate, a hole transport layer layered over the first electrode, an active layer layered over the hole transport layer, an electron transport layer layered over the active layer, and a second electrode layered over the electron transport layer, and the active layer comprises the copolymer.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862518A (en) * | 2019-10-15 | 2020-03-06 | 华南理工大学 | Multi-component copolymer based on multi-component condensed ring structure and application of multi-component copolymer in organic photoelectric device |
| CN111499840A (en) * | 2020-04-30 | 2020-08-07 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN112225882A (en) * | 2020-09-11 | 2021-01-15 | 华南理工大学 | N-type polymer containing non-condensed ring acceptor unit and preparation method and application thereof |
| CN112521404A (en) * | 2020-11-18 | 2021-03-19 | 位速科技股份有限公司 | Seven-membered fused ring compound, electron acceptor material mixture, preparation method of electron acceptor material mixture and organic photovoltaic cell |
| CN113061235A (en) * | 2021-03-22 | 2021-07-02 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN114044885A (en) * | 2021-10-12 | 2022-02-15 | 中国科学院大学 | Polymer electron acceptor material containing non-covalent fused ring acceptor unit and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862518A (en) * | 2019-10-15 | 2020-03-06 | 华南理工大学 | Multi-component copolymer based on multi-component condensed ring structure and application of multi-component copolymer in organic photoelectric device |
| CN111499840A (en) * | 2020-04-30 | 2020-08-07 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN112225882A (en) * | 2020-09-11 | 2021-01-15 | 华南理工大学 | N-type polymer containing non-condensed ring acceptor unit and preparation method and application thereof |
| CN112521404A (en) * | 2020-11-18 | 2021-03-19 | 位速科技股份有限公司 | Seven-membered fused ring compound, electron acceptor material mixture, preparation method of electron acceptor material mixture and organic photovoltaic cell |
| CN113061235A (en) * | 2021-03-22 | 2021-07-02 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN114044885A (en) * | 2021-10-12 | 2022-02-15 | 中国科学院大学 | Polymer electron acceptor material containing non-covalent fused ring acceptor unit and application thereof |
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