A polymer and its application in organic electronic devices

Abstract

In order to improve the device performance of organic electronic devices, especially the device performance of organic solar cells, the present application provides a polymer, the structure of which is shown in formula (I). When the polymer is used as a photoactive layer donor material in an organic electronic device, the device has a higher open circuit voltage, thereby improving the device efficiency. At the same time, the polymer protected by the present invention is simple to synthesize and can be industrialized.

Description

Technical Field

[0001] The present invention relates to the field of organic electronic device materials, and in particular to a polymer and its application in organic electronic devices, in particular in organic photovoltaic devices (OPV). Background Art

[0002] Solar energy is the world's largest renewable clean energy with environmentally friendly characteristics. Photovoltaic technology based on solar power generation has become an important part of human renewable energy technology and an effective way to solve the energy supply shortage in China and even the world. In recent years, the country has placed the promotion of sustainable development of energy ecology and civilization in a prominent strategic position, and actively promoting the revolution in the production and consumption of primary energy has become a core strategic task for the development of renewable energy society. Organic solar energy technology has the characteristics of low cost, green and non-toxic, high efficiency, flexibility, color and translucency, and can be prepared by large-area printing using low-temperature solution method. It is an ideal photoelectric conversion technology that can be applied to wearable electronic devices, Internet of Things, electronic price tags, building photovoltaic integration, new energy vehicles and other scenarios, and has broad market prospects.

[0003] Organic solar cells generally consist of five parts: anode, anode buffer layer, active layer, cathode buffer layer and cathode. The active layer generally contains donor materials and acceptor materials. Its working principle is: when sunlight passes through the transparent substrate and electrode and enters the active layer, the donor and acceptor materials absorb photons with energy greater than their band gap energy, and the electrons are excited to transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), and corresponding holes are generated at the HOMO. Due to the small relative dielectric constant of organic materials, the electrons and holes at this time exist in the bound exciton state. Afterwards, the excitons diffuse to the donor-acceptor interface, and driven by the energy level difference, the excitons dissociate to achieve charge separation. Subsequently, under the action of the built-in electric field, the free holes and electrons are transmitted along the continuous channels of the donor and acceptor materials to the anode and cathode respectively, and are collected by the electrodes and output to the external circuit to form current. From the above, it can be seen that the selection of active layer materials is crucial to the efficiency of organic solar cell devices.

[0004] Commonly used polymer donors such as PM6 and D18 and their derivatives reported in the literature have advantages such as optical absorption and energy level matching with high-efficiency non-fullerene acceptor materials, high hole mobility, etc., but their structure is complex and the synthesis route is lengthy, often requiring 20-30 steps, so the total yield is extremely low, the repeatability is poor and the price is expensive, making it impossible to achieve industrial production of these materials. Although CN10894827A discloses a polymer donor material with simple synthesis, the corresponding solar device photoelectric conversion efficiency is only 10.18% at most, and the device efficiency needs to be further improved. Therefore, how to design a photoactive layer donor material with simple synthesis and high device conversion efficiency is the key technical problem that we must first solve. Summary of the invention

[0005] Based on this, the purpose of the present invention is to provide a simple and easy-to-synthesize polymer, which is used as a donor material in an organic solar cell to improve the photoelectric conversion efficiency of the device.

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

[0007] A polymer having a structure as shown in general formula (I):

[0008]

[0009] in:

[0010] x, y are molar percentages; 0.5≤x<1; 0 <y≤0.5;x+y=1;

[0011] n represents the unit repetition number, and n is selected from an integer from 1 to 10000;

[0012] R1-R8 are independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched or cyclic alkyl having 3 to 20 C atoms, branched or cyclic alkoxy having 3 to 20 C atoms, branched or cyclic alkylthio having 3 to 20 C atoms, silyl, keto having 1 to 20 C atoms, alkoxycarbonyl having 2 to 20 C atoms, aryloxycarbonyl having 7 to 20 C atoms, cyano The invention also includes but is not limited to aryl, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amine, -Cl, -Br, -F, -I, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 50 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or a combination of these groups.

[0013] The present application also provides a mixture, comprising the above polymer and at least one organic functional material.

[0014] The present application also provides an application of the polymer or mixture as described above in an organic electronic device.

[0015] The present application also provides an organic electronic device, comprising at least one functional layer, wherein the functional layer comprises the above polymer or the above mixture.

[0016] Beneficial effects:

[0017] The polymer protected in this application is A certain proportion of Thus, the HOMO energy level of the polymer is reduced; when the polymer is used as a donor material in an OPV device, the device has a higher open circuit voltage and the device efficiency is improved. At the same time, the polymer protected by the present invention is simple to synthesize and can be industrialized. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1This is a schematic diagram of the structure of an organic solar cell device provided in an embodiment of the present application. In the figure, 101 is a substrate, 102 is an anode, 103 is an anode buffer layer, 104 is an active layer, 105 is a cathode buffer layer, and 106 is a cathode. DETAILED DESCRIPTION

[0020] The present application provides an organic compound, a mixture and its application in an organic electronic device. To make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0021] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0022] In the present invention, organic photovoltaic device and organic solar cell have the same meaning and can be interchangeable.

[0023] In the present invention, aromatic group, aromatic series and aromatic ring system have the same meaning and can be interchanged.

[0024] In the present invention, heteroaromatic group, heteroaromatic series and heteroaromatic ring system have the same meaning and can be interchanged.

[0025] In the present invention, "heteroatom" refers to non-carbon atoms, and may be N atom, O atom, S atom or the like.

[0026] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0027] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0028] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that the defined group may be substituted by one or more substituents R, wherein R is selected from but not limited to: deuterium atom, cyano, isocyano, nitro or halogen, alkyl containing 1-20 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted by substituents acceptable in the art; it is understandable that R' and R" in -NR'R" are independently selected from but not limited to: H, deuterium, Preferably, R is selected from but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1-10 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted by substituents acceptable in the art.

[0029] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0030] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aromatic group having 6 to 40 ring atoms" refers to an aromatic group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aromatic group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aromatic group having 6 to 14 ring atoms, and the aromatic group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and derivatives thereof. It is understandable that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g. <10% non-H atoms, such as C, N or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aromatic groups.

[0031] "Heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a heteroaryl having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted, and suitable examples include but are not limited to: thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, Triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophenyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothiophenyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0032] In the present invention, "alkyl" may refer to a linear, branched and / or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 15, 1 to 10 or 1 to 6. Phrases containing this term, such as "C 1-9"Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl 2-Hexyldecyl, 2-octyldecyl, 2-undecyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, 2-undecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-tridecyl, 2-tetradecyl, 2-pentadecyl, 2-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, 2-heptadecyl, 2-octylhexadecyl, 2-octadecyl, 2-octadecyl, 2-nonadecyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, 2-heneicosyl, 2-heneicosyl, 2-heconicosyl, 2-docosyl, 2-tricosyl, 2-tetracosyl, 2-pentacosyl, 2-hexacosyl, 2-heptacosyl, 2-octacosyl, 2-nonacosyl, 2-triacontyl, etc.

[0033] "Amine" refers to an amine derivative having the structural features of the formula -N(X)2, wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, etc. Non-limiting types of amines include -NH2, -N(alkyl), -NH(alkyl), -N(cycloalkyl), -NH(cycloalkyl), -N(heterocyclyl), -NH(heterocyclyl), -N(aryl), -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclyl), -N(cycloalkyl)(heterocyclyl), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0034] In the present invention, unless otherwise defined, a hydroxyl group refers to -OH, a carboxyl group refers to -COOH, a carbonyl group refers to -C(=O)-, an amino group refers to -NH2, a formyl group refers to -C(=O)H, a haloformyl group refers to -C(=O)z (wherein z represents a halogen), a carbamoyl group refers to -C(=O)NH2, an isocyanate group refers to -NCO, and an isothiocyanate group refers to -NCS.

[0035] The term "alkoxy" refers to a group having a structure of "-O-alkyl", i.e., an alkyl group as defined above is connected to other groups via an oxygen atom. Phrases containing the term, suitable examples include, but are not limited to, methoxy (-O-CH or -OMe), ethoxy (-O-CHCH or -OEt) and tert-butoxy (-OC(CH) or -OtBu).

[0036] The term "alkylthio" refers to a group having a structure of "-S-alkyl", i.e., an alkyl group as defined above is connected to other groups via a sulfur atom. Phrases containing the term, suitable examples include, but are not limited to, methylthio (-S-CH or -SMe), ethylthio (-S-CHCH or -SEt) and tert-butylthio (-SC(CH) or -StBu).

[0037] In the present invention, "*" connected to a single bond indicates a connection or fusion site;

[0038] In the present invention, when a linking site is not specified in a group, it means that any linking site in the group can be used as a linking site;

[0039] In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. The six Rs on the benzene ring may be the same as or different from each other.

[0040] As used in the present invention, "combinations thereof", "any combination thereof", "any combination thereof", "combination" and the like refer to all suitable combinations of any two, any three, any four or more of the listed groups.

[0041] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0042] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0043] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0044] The technical solution of this application is as follows:

[0045] A polymer having a structure as shown in general formula (I):

[0046]

[0047] in:

[0048] x, y are molar percentages; 0.5≤x<1; 0 <y≤0.5;x+y=1;

[0049] n represents the unit repetition number, and n is selected from an integer from 1 to 10000;

[0050] R1-R8 are independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched or cyclic alkyl having 3 to 20 C atoms, branched or cyclic alkoxy having 3 to 20 C atoms, branched or cyclic alkylthio having 3 to 20 C atoms, silyl, keto having 1 to 20 C atoms, alkoxycarbonyl having 2 to 20 C atoms, aryloxycarbonyl having 7 to 20 C atoms, cyano The invention also includes but is not limited to aryl, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amine, -Cl, -Br, -F, -I, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 50 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or a combination of these groups.

[0051] In one embodiment, R1-R8 are independently selected from: -H, -D, a straight-chain alkyl group having 1 to 18 C atoms, a straight-chain alkoxy group having 1 to 18 C atoms, a straight-chain alkylthio group having 1 to 18 C atoms, a branched-chain alkyl group having 3 to 18 C atoms, a branched-chain alkoxy group having 3 to 18 C atoms, a branched-chain alkylthio group having 3 to 18 C atoms, a cyano group, an isocyano group, an isohydroxy group, a nitro group, -Cl, -Br, -F, -I, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 5 to 10 ring atoms, or a combination of these groups.

[0052] In one embodiment, 0.6≤x<1; <y≤0.4;x+y=1;

[0053] In one embodiment, 0.7≤x<1; <y≤0.3;x+y=1;

[0054] In one embodiment, 0.8≤x<1; <y≤0.2;x+y=1;

[0055] In one embodiment, 0.9≤x<1; <y≤0.1;x+y=1;

[0056] In one embodiment, 0.7≤x≤0.9; 0.1≤y≤0.3; x+y=1.

[0057] In one embodiment, x=0.8, y=0.2.

[0058] In one embodiment, n is selected from an integer of 5-1000; in one embodiment, n is selected from an integer of 5-300; in one embodiment, n is selected from an integer of 15-100; in one embodiment, n is selected from an integer of 20-50.

[0059] In one embodiment, R1-R4 are independently selected from: -H, -D, a straight-chain alkyl group having 1 to 11 C atoms, a straight-chain alkoxy group having 1 to 11 C atoms, a straight-chain alkylthio group having 1 to 11 C atoms, a branched-chain alkyl group having 3 to 11 C atoms, a branched-chain alkoxy group having 3 to 11 C atoms, a branched-chain alkylthio group having 3 to 11 C atoms, or a combination of these groups.

[0060] In one embodiment, R1 and / or R2 are selected from -H, -D, a linear alkyl group having 1 to 11 C atoms, a branched alkyl group having 3 to 11 C atoms, or a combination of these groups.

[0061] In one embodiment, R1 and / or R2 are selected from -H, -D, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, a linear or branched CH 13 , straight chain or branched C8H 17 , or straight or branched chain C 11 H 23 ; One or more H atoms in the above alkyl groups are unsubstituted or substituted by D.

[0062] In one embodiment, R3 and / or R4 are selected from -H, -D, a linear alkyl group having 1 to 11 C atoms, a branched alkyl group having 3 to 11 C atoms, or a combination of these groups.

[0063] In one embodiment, R3 and / or R4 are selected from -H, -D, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, a linear or branched CH 13 , straight chain or branched C8H 17 , or straight or branched chain C 11 H 23 ; One or more H atoms in the above alkyl groups are unsubstituted or substituted by D.

[0064] In one embodiment, R5-R8 are independently selected from: -H, -D, a straight-chain alkyl group having 1 to 18 C atoms, a straight-chain alkoxy group having 1 to 18 C atoms, a straight-chain alkylthio group having 1 to 18 C atoms, a branched-chain alkyl group having 3 to 18 C atoms, a branched-chain alkoxy group having 3 to 18 C atoms, a branched-chain alkylthio group having 3 to 18 C atoms, a cyano group, an isocyano group, an isohydroxy group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a furanyl group, a thienyl group, or a combination of these groups.

[0065] In one embodiment, R5 and / or R6 are selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furanyl group substituted by R*; each occurrence of said R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0066] In one embodiment, R7 and / or R8 are selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furanyl group substituted by R*; each occurrence of said R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0067] In one embodiment, R5 and R6 are selected from the same structure, preferably, R5 and R6 are both selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furyl group substituted by R*; each occurrence of R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0068] In one embodiment, R5 and R6 are selected from different structures; preferably, one of R5 and R6 is selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furyl group substituted by R*; each occurrence of said R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms; the other is selected from -H, -D, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0069] In one embodiment, R7 and R8 are selected from the same structure, preferably, R7 and R8 are both selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furyl group substituted by R*; each occurrence of R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0070] In one embodiment, R7 and R8 are selected from different structures; preferably, one of R7 and R8 is selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furyl group substituted by R*; each occurrence of said R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms; the other is selected from -H, -D, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

[0071] In one embodiment, the polymer according to the present invention is selected from the structure represented by general formula (II):

[0072]

[0073] Wherein: R1, R3, R5-R8, x, y, and n have the same meanings as above.

[0074] Furthermore, the polymer according to the present invention is selected from the structure represented by general formula (III-1) or (III-2):

[0075]

[0076]

[0077] wherein: R9 each occurrence is independently selected from a straight chain alkoxy group having 6 to 16 C atoms or a branched chain alkoxy group having 6 to 16 C atoms.

[0078] In one embodiment, each occurrence of R9 is independently selected from a linear or branched C6H 13 , straight chain or branched C8H 17 , straight chain or branched chain C 11 H 23 , straight chain or branched chain C 12 H 25 , or straight or branched chain C 16 H33 .

[0079] According to a polymer of the present invention, the polymer is selected from the following structural formula, but is not limited thereto:

[0080]

[0081]

[0082] Wherein: The above chemical formula can be further substituted.

[0083] In the above chemical formulas (1) to (26), when x=0.9, y=0.1; when x=0.8, y=0.2; when x=0.7, y=0.3; when x=0.6, y=0.4; when x=0.5, y=0.5.

[0084] In a preferred embodiment, the present invention relates to a method for synthesizing a polymer, wherein a raw material containing an active group is used for the reaction. Suitable reactions for forming CC connections are well known to those skilled in the art and are described in the literature, particularly suitable and preferred coupling reaction methods are SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0085] In a preferred embodiment, the glass transition temperature (Tg) of the polymer is ≥100°C, preferably ≥120°C, more preferably ≥140°C, even more preferably ≥160°C, and most preferably ≥180°C.

[0086] In a preferred embodiment, the molecular weight distribution (PDI) of the polymer is preferably in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1 to 1.5.

[0087] In a preferred embodiment, the molecular weight of the polymer is Mw≥10000 g / mol; further, Mw≥20000 g / mol; further, Mw≥300000 g / mol; further, Mw≥400000 g / mol.

[0088] The polymer provided by the present invention can be used as an active layer material in organic electronic devices; preferably, the polymer provided by the present invention can be used as an active layer donor material in organic solar devices.

[0089] The present invention also relates to a mixture, comprising at least one of the above-mentioned polymers and at least another organic functional material, wherein the at least another organic functional material can be selected from anode buffer layer materials, cathode buffer layer materials, active layer donor materials, or active layer acceptor materials. The weight ratio of the at least another organic functional material to the another acceptor material is from 1:99 to 99:1. In one embodiment, the photoactive layer comprises a donor material and an acceptor material, and the weight ratio of the donor material / acceptor material is 1 / 1.2.

[0090] In one embodiment, the photoactive layer comprises a donor material and two acceptor materials; preferably, one acceptor material is selected from non-fullerene acceptor materials, and the other acceptor material is selected from fullerene acceptor materials; further, the weight ratio of donor material: non-fullerene acceptor material: fullerene acceptor material = 1:1.2:0.1.

[0091] The present application further relates to an electron donor material, which is selected from the polymers or mixtures as described above.

[0092] The present application further relates to an application of the polymer or mixture as described above in an organic electronic device. The organic electronic device can be selected from, but not limited to, an organic solar cell (OPV), an organic light emitting diode (OLED), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and OPV is particularly preferred.

[0093] The present application also relates to an organic electronic device, comprising at least one functional layer, wherein the functional layer comprises the above polymer or the above mixture. Preferably, the functional layer is selected from an anode buffer layer, an active layer or a cathode buffer layer.

[0094] In one embodiment, the organic electronic device comprises at least a first electrode, a second electrode and one or more functional layers between the first electrode and the second electrode. Preferably, the one or more functional layers are selected from active layers; more preferably, the one or more functional layers are selected from anode buffer layers, active layers and cathode buffer layers.

[0095] In one embodiment, the organic electronic device is selected from an organic solar cell. Preferably, the donor material of the organic solar cell comprises the above polymer or the above mixture.

[0096] Furthermore, the organic solar cell further comprises a substrate. Specifically, the substrate may be disposed below the first electrode.

[0097] 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.

[0098] In one embodiment, as a substrate, a substrate having excellent transparency, surface smoothness, ease of handling and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto, and a substrate commonly used for organic solar cells may also be used.

[0099] At least one of the anode electrode and the cathode electrode is made of a transparent or translucent material. The electrode material may include metals such as silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni) and palladium (Pd), magnesium (Mg), vanadium (V), chromium (Cr), zinc (Zn) or their alloys, etc.; materials with a multilayer structure such as Al / Li, Al / BaF2 and Al / BaF2 / Ba, Al / Yb, etc.; conductive nanomaterials such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as PEDOT:PSS (poly (3,4-ethylenedioxythiophene)) of poly (styrene sulfonic acid), polypyrrole and polyaniline, etc., but are not limited thereto.

[0100] The active layer includes an electron donor material and an electron acceptor material. In the present specification, the active layer material may mean an electron donor material and an electron acceptor material.

[0101] Specifically, the electron acceptor material may be a fullerene derivative or a non-fullerene derivative. Fullerene molecules include hollow spheres, ellipsoids or tubes. The fullerene acceptor may be a spherical C20 or C2n molecule, where n is an integer in the range of, for example, 12 to 100. In some examples, the fullerene acceptor is C60 or C70 or a derivative thereof, such as PC 61 BM, PC 71 The non-fullerene acceptor material may be selected from Y6, ITIC, EH-IDTBR, TTPBT-IC, IEICO-4F, HEICO-4F or the following structures, but is not limited thereto.

[0102]

[0103]

[0104] The photoactive layer may be formed by dissolving a photoactive material, such as an electron donor and / or an electron acceptor, in an organic solvent, and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spray coating, doctor blade, slit coating, and inkjet printing, but the method is not limited thereto.

[0105] The anode buffer layer can be selected from materials with higher work functions, such as PEDOT:PSS (poly(3,4-ethylenedioxythiophene)), molybdenum oxide (MoOm), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO m ), etc. Preferably, m is selected from 2 or 3, but not limited thereto.

[0106] The cathode buffer layer material can be a low work function material, such as a metal complex containing 8-hydroxyquinoline, LiQ, LiF, titanium oxide (TiOm), zinc oxide (ZnO), cesium carbonate (Cs2CO3), and polymers such as PFN-Br or PFN, but is not limited thereto.

[0107] The present invention also relates to the application of the organic solar cell according to the present invention in various devices, including, but not limited to, automobiles and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0108] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific embodiments

[0110] Here, the specific synthesis method of the polymer and the organic electronic device of the present invention are exemplified, but the present invention is not limited to the following embodiments.

[0111] Compound preparation

[0112] Example 1: Synthesis of polymer P1

[0113]

[0114] Synthesis of compound (1-1):

[0115] In a 250 ml double-necked flask, compound A (3.3 g, 1 mmol) and glyoxylic acid (1.67 mL, 1.5 mmol) were weighed and dissolved in 100 ml of acetic acid. After nitrogen was pumped in three times, the mixture was heated to 40 ° C for 10 minutes, then stirred at room temperature for 3 hours, filtered and dried to obtain a white solid. The obtained white solid (3.2 g, 0.86 mmol), potassium tert-butyrate (0.96 g, 1 mmol) and 1-bromo-2-hexyldecane (2.63 g, 0.86 mmol) were dissolved in methanol, and the above mixture was refluxed for 12 hours and then cooled to room temperature. The mixture was poured into a saturated NH4Cl solution, extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and then the excess solvent was distilled off under reduced pressure. The silica gel sample was mixed with the column chromatography, and the eluent was PE:DCM = 10:1 (volume ratio), and about 5.3 g of colorless oily liquid compound (1-1) was obtained, with a yield of 88.6%.

[0116] Synthesis of polymer P1

[0117] In a 100 ml thick-walled pressure-resistant tube, accurately weigh compound (1-1) (47.8 mg, 0.8 mmol), compound (1-2) (11.3 mg, 0.2 mmol) and intermediate (1-3) (41 mg, 1 mmol) and dissolve in 40 ml of anhydrous toluene. Stir at room temperature for 15 minutes under argon protection, then add tetrakistriphenylphosphine palladium (0.07 g, 0.06 mmol) to the system and stir at room temperature for half an hour. Then heat to 80 ° C and reflux for 48 hours. Cool to room temperature, pour the reaction solution into methanol to precipitate solid, filter with suction, add the filter cake to a Soxhlet extractor, extract with n-hexane, methanol and chloroform for 24 hours respectively, then add the chloroform extract dropwise to methanol to precipitate solid, filter with suction and dry to obtain polymer P1 with a yield of 52%, Mw of 29.3K and PDI of 1.45.

[0118] Example 2: Synthesis of polymer P2

[0119]

[0120] The synthesis of polymer P2 refers to the synthesis of polymer P1, except that the molar amount of compound (1-1) is adjusted to 0.9 mmol, and the molar amount of compound (1-2) is adjusted to 0.1 mmol, to obtain polymer P2 with a yield of 50.55%, Mw of 30.2K, and PDI of 1.76.

[0121] Example 3: Synthesis of polymer P3

[0122]

[0123] The synthesis of polymer P3 refers to the synthesis of polymer P1, except that the molar amount of compound (1-1) is adjusted to 0.7 mmol, and the molar amount of compound (1-2) is adjusted to 0.3 mmol, to obtain polymer P3 with a yield of 51.2%, Mw of 29.8K, and PDI of 1.63.

[0124] Example 4: Synthesis of polymer P4

[0125]

[0126] The synthesis of polymer P4 refers to the synthesis of polymer P1, except that the molar amount of compound (1-1) is adjusted to 0.6 mmol, and the molar amount of compound (1-2) is adjusted to 0.4 mmol, to obtain polymer P4 with a yield of 53.6%, Mw of 32.1K, and PDI of 1.88.

[0127] Example 5: Synthesis of polymer P5

[0128]

[0129] The synthesis of polymer P5 refers to the synthesis of polymer P1, except that the molar amount of compound (1-1) is adjusted to 0.5 mmol, and the molar amount of compound (1-2) is adjusted to 0.5 mmol, to obtain polymer P5 with a yield of 58%, Mw of 29.6k, and PDI of 1.96.

[0130] Example 6: Synthesis of polymer P6

[0131]

[0132] In a 100 ml thick-walled pressure-resistant tube, accurately weigh compound (4-1) (61.2 mg, 0.8 mmol), compound (4-2) (14.7 mg, 0.2 mmol) and intermediate (3-5) (49.3 mg, 1 mmol) and dissolve in 40 ml of anhydrous toluene. Stir at room temperature for 15 minutes under argon protection, then add tetrakistriphenylphosphine palladium (0.07 g, 0.06 mmol) to the system and stir at room temperature for half an hour. Then heat to 80 ° C and reflux for 48 hours. Cool to room temperature, pour the reaction solution into methanol to precipitate solid, filter with suction, add the filter cake to a Soxhlet extractor, extract with n-hexane, methanol and chloroform for 24 hours respectively, then add the chloroform extract dropwise to methanol to precipitate solid, filter with suction and dry to obtain polymer P6 with a yield of 52%, Mw of 26.3K and PDI of 1.58.

[0133] Example 7: Synthesis of polymer P7

[0134]

[0135] The synthesis of polymer P7 refers to the synthesis of polymer P6, with the difference that the molar amount of compound (4-1) is adjusted to 0.9 mmol, and the molar amount of compound (4-2) is adjusted to 0.1 mmol, to obtain polymer P7 with a yield of 58%, Mw of 27.6k, and PDI of 1.96.

[0136] Example 8: Synthesis of polymer P8

[0137]

[0138] The synthesis of polymer P8 refers to the synthesis of polymer P6, with the difference that the molar amount of compound (4-1) is adjusted to 0.7 mmol, and the molar amount of compound (4-2) is adjusted to 0.3 mmol, to obtain polymer P8 with a yield of 58.9%, Mw of 26.6k, and PDI of 1.86.

[0139] Device preparation

[0140] The following is a detailed description of the preparation process of the OPV device containing the S-heterocyclic organic compound through a specific device example. The OPV device structure is as follows: Indium Tin Oxide ITO / PEDOT:PSS (20nm) / Active Layer (100nm) / PFN-Br (5nm) / Ag (100nm)

[0141] The steps for preparing device 1 are as follows:

[0142] 1) ITO substrate cleaning:

[0143] The ITO conductive glass layer is cleaned with detergent, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes. After being blown dry with nitrogen or dried in an oven, it is treated in a plasma cleaner for 5 minutes (to improve the electrode work function and surface wettability).

[0144] 2) Anode buffer layer preparation

[0145] PEDOT:PSS was evenly spin-coated on ITO in air at a spin-coating speed of 3000-4000 rpm, and dried at 150° C. for 15 min to obtain an anode modification layer with a thickness of 20 nm.

[0146] 3) Preparation of photoactive layer

[0147] In a glove box (inert gas atmosphere), the photoactive layer material is evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of 100 nm; wherein the donor material in the photoactive layer material is selected from polymer P1; the acceptor material is selected from compound Y6 and compound A; the mass ratio of polymer P1:compound Y6:compound A is 1:1.2:0.1.

[0148] 4) Preparation of cathode buffer layer

[0149] After thermal annealing on a hot plate at 100° C. for 10 minutes, the cathode buffer layer material PFN-Br was evenly spin-coated on the active layer at a spin-coating speed of 1800-4000 rpm to obtain a cathode buffer layer with a thickness of 5 nm.

[0150] 5) Cathode layer preparation

[0151] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of 100 nm.

[0152] 6) Packaging

[0153] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0154] Y6 Compound A

[0155] The structures of Comparative Examples 1-4 are as follows:

[0156]

[0157] Synthesis step reference: The synthesis of polymer Ref 1 refers to the synthesis step of polymer P1; the synthesis of polymer Ref 2 refers to the synthesis step of polymer P6.

[0158] Device 2: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P2.

[0159] Device 3: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P3.

[0160] Device 4: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P4.

[0161] Device 5: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P5.

[0162] Device 6: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P6.

[0163] Device 7: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P7.

[0164] Device 8: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer P8.

[0165] Comparative device 1: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer Ref 1.

[0166] Comparative device 2: The preparation method is the same as that of device 1, except that the donor material in the photoactive layer is polymer Ref 2.

[0167] The prepared organic solar cell device was subjected to performance testing. Under the irradiation of AM1.5G standard light of a solar simulator (SS-F5-3A), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated. The results are shown in Table 1:

[0168] Table 1

[0169]

[0170]

[0171] It can be seen from the characterization data of the above device embodiments that when a certain proportion of When the unit is 1:1, the device efficiency is the best when the molar ratio of x to y is 0.8:0.2. The reasons are as follows: ① The doping of chlorine atoms reduces the HOMO of the polymer, thereby improving the open circuit of the device. The higher the open circuit voltage of the device, the more conducive it is to improving the device efficiency; ② The doping of chlorine atoms will also deepen the LUMO of the polymer, but the LUMO value of the polymer donor needs to match the LUMO value of the acceptor material to ensure that the excitons are effectively separated at the donor-acceptor interface; ③ Compared with fluorine atoms, chlorine atoms have a large and loose outermost electron cloud, which can improve the intermolecular π-π stacking and orbital overlap, which is beneficial to improve the charge transfer efficiency; therefore, when the molar ratio of x to y is 0.8:0.2, the polymer donor material has relatively better HOMO and LUMO, and better molecular morphology, thereby ensuring that the device has a good photoelectric conversion efficiency.

[0172] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0173] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A polymer, characterized in that: Having a structure as shown in general formula (I): in: x, y are molar percentages; 0.6≤x<1; 0 <y≤0.4;x+y=1; n represents the unit repetition number, and n is selected from an integer from 1 to 10000; R1-R4 are independently selected from: -H, -D, a straight-chain alkyl group having 1 to 11 C atoms, a straight-chain alkoxy group having 1 to 11 C atoms, a straight-chain alkylthio group having 1 to 11 C atoms, a branched-chain alkyl group having 3 to 11 C atoms, a branched-chain alkoxy group having 3 to 11 C atoms, a branched-chain alkylthio group having 3 to 11 C atoms, or a combination of these groups; R5-R8 are independently selected from: -H, -D, a straight-chain alkyl group having 1 to 18 C atoms, a straight-chain alkoxy group having 1 to 18 C atoms, a straight-chain alkylthio group having 1 to 18 C atoms, a branched-chain alkyl group having 3 to 18 C atoms, a branched-chain alkoxy group having 3 to 18 C atoms, a branched-chain alkylthio group having 3 to 18 C atoms, a phenyl group, a furyl group, a thienyl group, or a combination of these groups.

2. The polymer according to claim 1, characterized in that: 0.7≤x<1;0 <y≤0.3;x+y=1。 3. The polymer according to claim 1, characterized in that: x=0.8, y=0.

2.

4. The polymer according to claim 1, characterized in that: R1-R4 are independently selected from: -H, -D, a straight chain alkyl group having 1 to 11 C atoms, a branched chain alkyl group having 3 to 11 C atoms, or a combination of these groups.

5. The polymer according to claim 1, characterized in that: R5 and / or R6 are selected from a linear alkoxy group having 6 to 18 C atoms, a branched alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furanyl group substituted by R*; each occurrence of said R* is independently selected from a linear alkoxy group having 6 to 18 C atoms, a branched alkoxy group having 6 to 18 C atoms, a linear alkyl group having 1 to 18 C atoms, or a branched alkyl group having 3 to 18 C atoms; R7 and / or R8 are selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a phenyl group substituted by R*, a thienyl group substituted by R*, a furyl group substituted by R*; each occurrence of said R* is independently selected from a straight-chain alkoxy group having 6 to 18 C atoms, a branched-chain alkoxy group having 6 to 18 C atoms, a straight-chain alkyl group having 1 to 18 C atoms, or a branched-chain alkyl group having 3 to 18 C atoms.

6. The polymer according to any one of claims 1 to 5, characterized in that: The polymer is selected from the structure shown in general formula (III-1) or (III-2): Wherein: R9 is independently selected from a linear or branched C6H 13 , straight chain or branched C8H 17 , straight chain or branched chain C 11 H 23 , straight chain or branched chain C 12 H 25 , or straight or branched chain C 16 H 33 .

7. The polymer according to claim 1, characterized in that: The polymer is selected from any one of the structures of chemical formula (1) to chemical formula (26):

8. A mixture, characterized in that: The mixture comprises the polymer according to any one of claims 1 to 7, and at least another organic functional material, wherein the at least another organic functional material is selected from anode buffer layer materials, cathode buffer layer materials, active layer donor materials or active layer acceptor materials.

9. An electron donor material, characterized in that: The electron donor material is selected from the polymer according to any one of claims 1 to 7 or the mixture according to claim 8.

10. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer material is selected from the polymer according to any one of claims 1 to 7 or the mixture according to claim 8.

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