Multi-copolymer photoelectric material as well as preparation method and application thereof

Abstract

The invention discloses a multipolymer photoelectric material as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: mixing a thiophene unit and a quinoxaline unit with electron-rich units Ar1 and Ar3 and / or electron-deficient units Ar2 and Ar4, adding a catalyst for reaction, and adopting a purification method combining polar solvent gradient regulation and normal-temperature step-by-step extraction to obtain the multipolymer photoelectric material. By introducing other identical or different electron-rich units and electron-deficient units on the main chain of the polymer, the absorption range of the obtained multipolymer can be adjusted within the wavelength of 300-1000nm, so that good complementation can be realized in sunlight absorption when the multipolymer is matched with fullerene receptors, narrow-band gap fused ring receptors, non-fused ring receptors and the like. By adjusting the content of the quinoxaline unit, the thiophene unit and other raw materials, the highest energy conversion efficiency exceeding 20% can be obtained, the application range is wider, and the stability is higher.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a multi-component copolymer optoelectronic material, its preparation method, and its application. Background Technology

[0002] A solar cell is a device that directly converts solar energy into electrical energy through the photovoltaic effect. It is an effective way to utilize solar energy. Currently, commercially available solar cells are mainly inorganic crystalline silicon solar cells. Compared with silicon-based solar cells, organic solar cells based on polymer photovoltaic materials have the following advantages: ① They are solution-processable, allowing for processing using large-area printing, inkjet printing, and other methods; ② They are lightweight, suitable for portable and personalized applications; ③ They can be processed into flexible and semi-transparent devices with a wider range of applications; ④ They are inexpensive, with lower production and processing costs than inorganic crystalline silicon solar cells. Since organic conjugated polymers have demonstrated great application potential in the field of organic photovoltaics, they have received widespread attention from all sectors of society.

[0003] PTQ series polymers have been widely used in organic solar cells due to their high efficiency and simple structure. PTQ-based polymers typically possess deep highest occupied molecular orbital (HOMO) levels, and thanks to their excellent charge transport properties, they usually exhibit high open-circuit voltage, high fill factor, and good matching with narrow bandgap non-fullerene acceptors. However, existing binary polymers PTQ10 and PTQ11 cannot achieve broad tuning of the energy levels, absorption, morphology, and bandgap of the conjugated polymer, and are not suitable for all organic solar cell devices. Therefore, further optimization of the polymer's physicochemical properties is of great significance.

[0004] The purity of polymeric optoelectronic materials directly affects the performance and stability of the optoelectronic materials in batteries. The purification of polymeric optoelectronic materials typically employs the Soxhlet extractor method. In this method, a suitable solvent (such as methanol or hexane) is added to a round-bottom flask and heated to boiling. The boiling solvent vapor rises through a connecting tube to a condenser, where it is condensed into liquid and dripped into the extraction tube, contacting the sample to be extracted. When the liquid level in the extraction tube exceeds the siphon tube, the solvent flows back into the round-bottom flask, forming a siphon, and the extraction continues. This method plays a crucial role in controlling the molecular weight and polydispersity index of polymers. However, this method requires a heat source, is time-consuming, costly, consumes large amounts of solvent, exhibits significant batch-to-batch variability, cannot purify temperature-sensitive polymers, and cannot be industrialized for large-scale production (the quality of a single purification of polymeric optoelectronic materials is limited by the size of the Soxhlet extractor). Another method for purifying polymeric optoelectronic materials is column chromatography, which operates on the principle of "adsorption-desorption dynamic equilibrium," achieving separation through the differences in the interactions between different components and the stationary and mobile phases. While this method achieves good separation results, it suffers from complex packing material selection, low separation efficiency, and a tendency to cause sample adsorption loss and cross-contamination. Furthermore, it requires larger solvent volumes and involves cumbersome procedures, making it unsuitable for large-scale production. Therefore, developing simpler, more efficient, reproducible purification methods applicable to polymer materials is a crucial step in promoting the practical application of polymer optoelectronic materials. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a multi-component copolymer optoelectronic material, its preparation method and application, so as to solve the technical problem of low adjustability of existing conjugated polymers in terms of energy level, absorption, morphology and band gap.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: to provide a multi-component copolymer optoelectronic material, the general structural formula of which is: , Where x, y, z and m take values ​​in the range of 0≤x<1, 0≤y<1, 0≤z<1, 0≤m<1, and the sum of x, y, z and m is equal to 1, n is an integer from 2 to 1000, x, y and z are not simultaneously equal to 0, x, y and m are not simultaneously equal to 0, x, z and m are not simultaneously equal to 0, and y, z and m are not simultaneously equal to 0. R1-R6 are hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, alkylamine, hydroxyl, acyl, acyloxy, acylthio, ester, amino, amide, alkenyl, alkynyl, carboxyl, cyano, sulfonic acid, or nitro; alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, or alkylamine are straight-chain or branched alkyl groups with 1-30 carbon atoms; Ar1 and Ar3 are electron-rich units, selected from any of the following groups: A1. A substituted or unsubstituted three-membered, four-membered, five-membered, six-membered, seven-membered, eight-membered, nine-membered, or ten-membered ring system, wherein the system contains 0-4 heteroatoms independently selected from oxygen, nitrogen, sulfur, selenium, or silicon; or In A2 and A1, the groups are directly connected to each other or form fused rings through bridging atoms, and the number of groups is at least one. Ar2 and Ar4 are electron-deficient units, selected from any of the following groups: B1. A substituted or unsubstituted three-membered ring system, four-membered ring system, five-membered ring system, six-membered ring system, seven-membered ring system, eight-membered ring system, nine-membered ring system, or ten-membered ring system, wherein the system contains 0-4 heteroatoms independently selected from oxygen, nitrogen, sulfur, selenium, or silicon; or In B2 and B1, the groups are directly connected to each other or form fused rings through bridging atoms, and the number of groups is at least one.

[0007] Introducing two alternating electron-rich and electron-deficient units into the main chain of a conjugated polymer molecule to modulate its absorption, energy levels, morphology, and band gap to obtain the desired product is significant. The main chain of ternary copolymer solar cells typically includes two electron-rich units and one electron-deficient unit, or one electron-rich unit and two electron-deficient units. Multi-component copolymers, on the other hand, add other electron-rich or electron-deficient units to the ternary copolymer structure. The alternating sequence of molecules in the main chain usually leads to significant changes in the absorption, morphology, and properties of the conjugated polymer, improving the original polymer aggregation state and thus achieving optimal photoelectric performance.

[0008] Based on the above technical solution, the present invention can be further improved as follows: Furthermore, the structural formula of the multi-component copolymer optoelectronic material is as follows: .

[0009] Furthermore, Ar1 and Ar3 are groups containing the structures of furan, thiophene, selenophene, tetrahydrofuran, tetrahydrothiophene, tetrahydroselenophene, benzene, cyclohexene, cyclohexadiene, cyclopentene, cyclopentadiene, cycloheptene, cycloheptadiene, cyclohepttriene, cyclooctene, cyclooctadiene, cyclooctatetraene, cyclooctane, cycloheptane, cyclohexane, or cyclopentane.

[0010] Furthermore, the structural formulas for Ar1 and Ar3 are as follows: , Where X is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, or silicon atom; R7-R 10 The atoms are hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, alkylamine, hydroxyl, acyl, acyloxy, acylthio, ester, amino, amide, alkenyl, alkynyl, carboxyl, carbonyl, cyano, sulfonic acid, or nitro; the alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, or alkylamine are straight-chain or branched alkyl groups with 1-30 carbon atoms.

[0011] Furthermore, Ar2 and Ar4 contain pyrazine, quinoxaline, benzoquinoxaline, thienopyrazine, triazole, benzotriazole, naphthotriazole, thienotriazole, thiadiazole, benzothiadiazole, naphthothiadiazole, thienothiadiazole, selenide, benzoselenide, naphthoselenide, thienoselenide, oxadiazole, benzooxadiazole, naphthooxadiazole, thienooxadiazole, pyridine, thienopyridine, pyrimidine, benzopyrimidine, and thiophene. Groups with the structure of pyrimidine, pyrazine, pyridazine, benzopyridazine, quinoline, isoquinoline, benzoisoquinoline, imidazole, benzimidazole, oxazole, benzoxazole, thiazole, benzothiazole, thienothiazole, purine, pyrazole, benzopyrazole, isothiazole, benzoisothiazole, pteridine, benzopteridine, maleic anhydride, γ-butyrolactone, caprolactam, azircycloheptane-2,7-dione, cytosine, uracil, thymine, adenine, or guanine.

[0012] Furthermore, the structural formulas for Ar2 and Ar4 are as follows: , Where X is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, or silicon atom; R7-R 11The atoms are hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, alkylamine, hydroxyl, acyl, acyloxy, acylthio, ester, amino, amide, alkenyl, alkynyl, carboxyl, carbonyl, cyano, sulfonic acid, or nitro; the alkyl, alkoxy, alkylthio, silyl, fluoroalkyl, alkyl chloride, aralkyl, heterocyclic aralkyl, alicyclic, or alkylamine are straight-chain or branched alkyl groups with 1-30 carbon atoms.

[0013] Furthermore, when the electron-rich units Ar1 and Ar3 are borate groups, borate ester groups, zinc halide groups, magnesium halide groups, or trialkyltin groups, the electron-deficient units Ar2 and Ar4 are Cl, Br, or I; when the electron-rich units Ar1 and Ar3 are Cl, Br, or I, the electron-deficient units Ar2 and Ar4 are borate groups, borate ester groups, zinc halide groups, magnesium halide groups, or trialkyltin groups.

[0014] The present invention also discloses a method for preparing the above-mentioned multi-component copolymer optoelectronic material, comprising the following steps: mixing thiophene units and quinoxaline units with electron-rich units Ar1 and Ar3 and / or electron-deficient units Ar2 and Ar4 in organic solvent A, adding a catalyst, reacting at 10-160℃ for 0.5-50 h, purifying, and obtaining the multi-component copolymer optoelectronic material; the ratio of the sum of the molar amounts of the catalyst, thiophene units, Ar1 and Ar3 to the sum of the molar amounts of quinoxaline units, Ar2 and Ar4 is 0.01%-10%:1:0.5-2; the molar ratio of thiophene units, Ar1 and Ar3 is 0-2:0-1:0-1, and the molar amounts of thiophene units, Ar1 and Ar3 are not simultaneously 0; the molar ratio of quinoxaline units, Ar2 and Ar4 is 0-2:0-1:0-1, and the molar amounts of quinoxaline units, Ar2 and Ar4 are not simultaneously 0.

[0015] Based on the above technical solution, the present invention can be further improved as follows: Furthermore, organic solvent A is at least one of tetrahydrofuran, toluene, chlorobenzene, and N,N-dimethylformamide.

[0016] Furthermore, the catalyst is tetra(triphenylphosphine)palladium, [1,2-bis(diphenylphosphine)ethane]nickel dichloride, tris(dibenzylideneacetone)palladium, palladium chloride, palladium acetate, palladium nitrate, palladium oxide, or palladium hydride.

[0017] Furthermore, when the thiophene unit, electron-rich units Ar1 and Ar3 are borate or borate ester groups, a multi-component copolymer optoelectronic material is prepared using the Suzuki reaction. The organic solvent A is at least one of tetrahydrofuran, toluene, and chlorobenzene, the catalyst is tetra(triphenylphosphine)palladium, and the reaction temperature is 20-160℃. The reaction equation is as follows: ,or .

[0018] Furthermore, when the thiophene unit, electron-rich units Ar1, and Ar3 are zinc halide groups, a multi-component copolymer optoelectronic material is prepared using the Rieke reaction. The organic solvent A is tetrahydrofuran, the catalyst is [1,2-bis(diphenylphosphino)ethane]nickel dichloride, and the reaction temperature is 10-100℃. The reaction equation is as follows: .

[0019] Furthermore, when the thiophene unit, electron-rich units Ar1, and Ar3 are magnesium halide groups, a multi-component copolymer optoelectronic material is prepared using the McCullough reaction. The organic solvent A is at least one of tetrahydrofuran, toluene, and chlorobenzene, the catalyst is tetra(triphenylphosphine)palladium, and the reaction temperature is 10-160℃. The reaction equation is as follows: .

[0020] Furthermore, when the thiophene unit, electron-rich units Ar1 and Ar3 are trialkyltin groups, and the quinoxaline unit, electron-deficient units Ar2 and Ar4 are aromatic dihalides, or when the thiophene unit, electron-rich units Ar1 and Ar3 are aromatic dihalides, and the quinoxaline unit, electron-deficient units Ar2 and Ar4 are trialkyltin groups, a multi-component copolymer optoelectronic material is prepared using the Stille reaction. The organic solvent A is at least one of tetrahydrofuran, toluene, chlorobenzene, and N,N-dimethylformamide; the catalyst is tetra(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium chloride, palladium acetate, palladium nitrate, palladium oxide, or palladium hydride; the trialkyltin group is a bis(trimethyltin) aromatic hydrocarbon; the aromatic dihalide is an aromatic dibromide; and the reaction temperature is 10-160℃. The reaction equation is as follows: .

[0021] The present invention also discloses a purification method for the above-mentioned multi-component copolymer optoelectronic materials, comprising the following steps: S1. After the reaction is complete, add 1-100000 wt% organic solvent B to the reactants, stir at room temperature for 0.1-24 h, and separate the solid and liquid phases to obtain the solid product phase. S2. Repeat step S1 1-20 times; S3. Place the product obtained in S2 in a vacuum and dry it at 50-70°C to constant weight.

[0022] Based on the above technical solution, the present invention can be further improved as follows: Furthermore, the mass fraction of organic solvent B is 100-5000 times that of the reactants.

[0023] Furthermore, organic solvent B is at least one selected from methanol, ethanol, isopropanol, petroleum ether, diethyl ether, propyl ether, n-hexane, cyclohexane, acetone, dichloromethane, dichloroethane, toluene, xylene, trimethylbenzene, fluorobenzene, difluorobenzene, chlorobenzene, dichlorobenzene, bromobenzene, dibromobenzene, ethyl acetate, tetrahydrofuran, dimethyltetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, anisole, 2,5-dibromothiophene, and chloroform.

[0024] Furthermore, organic solvent B is at least one of methanol, petroleum ether, n-hexane, cyclohexane, acetone, dichloromethane, chlorobenzene, and chloroform.

[0025] Furthermore, the stirring time is 0.1-10 hours.

[0026] Furthermore, the solid-liquid separation in S1 is as follows: let the substance to be separated stand for 1-1000 min, or centrifuge at 1000-12000 rpm for 1-10 min.

[0027] Furthermore, the solid-liquid separation in S1 is as follows: let the substance to be separated stand for 10-200 min, or centrifuge at 3000-8000 rpm for 1-10 min.

[0028] This invention also discloses the application of the above-mentioned multi-component copolymer photoelectric materials in the preparation of organic solar cell devices.

[0029] Based on the above technical solution, the present invention can be further improved as follows: Furthermore, the organic solar cell device, from bottom to top, consists of: a first electrode, a semiconductor layer, and a second electrode, wherein the semiconductor layer comprises the aforementioned multi-component copolymer photoelectric material.

[0030] Furthermore, the semiconductor layer also includes an n-type organic semiconductor acceptor, the mass ratio of the multi-component copolymer photoelectric material to the n-type organic semiconductor acceptor is 1:0.1-10, and the total concentration of the multi-component copolymer photoelectric material and the n-type organic semiconductor acceptor is 0.2-80 mg / mL.

[0031] Furthermore, the n-type organic semiconductor receptor is a fullerene receptor, a non-fullerene small molecule receptor, or a polymer receptor.

[0032] Furthermore, the n-type organic semiconductor receptor is an acceptor–donor–acceptor–donor–acceptor (A-DA'DA) type fused-ring receptor, or a small molecule receptor whose outer chain contains thiophene or benzene. m -TEH or m -PEH. m -TEH and mThe structural formula for -PEH is shown below: ; .

[0033] Furthermore, n-type organic semiconductor acceptors are m -TEH.

[0034] Furthermore, the solvent used when mixing the semiconductor layer is at least one of chloroform, tetrahydrofuran, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, trimethylbenzene, and anisole.

[0035] Furthermore, the mass ratio of the multi-component copolymer optoelectronic material to the n-type organic semiconductor acceptor is 1:0.5-2.

[0036] Furthermore, the total concentration of the multi-component copolymer optoelectronic material and the n-type organic semiconductor acceptor is 15-22 mg / mL.

[0037] Furthermore, the total concentration of the multi-component copolymer optoelectronic material and the n-type organic semiconductor acceptor was 18 mg / mL.

[0038] The beneficial effects of this invention are as follows: 1. This invention, by introducing other identical or different electron-rich and electron-deficient units into the polymer backbone, allows for adjustment of the absorption range of the resulting multi-component copolymer within the wavelength range of 300-1000 nm. Therefore, it achieves good complementarity in sunlight absorption when matching fullerene acceptors, narrow-bandgap fused-ring acceptors, and non-fused-ring acceptors. By adjusting the content of quinoxaline units, thiophene units, and other introduced electron-rich and electron-deficient units, an energy conversion efficiency exceeding 20% ​​can be achieved when matching narrow-bandgap fused-ring molecular acceptors.

[0039] 2. The multi-component copolymer optoelectronic material prepared by this invention contains water- and oxygen-resistant groups, high mechanical strength groups, high chemical stability groups, and high temperature-resistant groups, which can realize large-area coating processing of high-toughness organic photovoltaic modules in air, with a wider range of applications and stronger stability.

[0040] 3. The method of the present invention has mild reaction conditions, low cost, and is easy to realize large-scale commercial application.

[0041] 4. The purification steps of this invention are simple, low-cost, reduce solvent consumption, have mild processing conditions, and short processing time. Magnetic stirring ensures uniform mixing and low cost. The resulting polymer optoelectronic materials have performance comparable to or even superior to polymers obtained by the traditional Soxhlet extractor method. This method helps the large-scale green industrial production of polymer optoelectronic materials. Attached Figure Description

[0042] Figure 1 The absorption spectrum of P6 purified by the method of this invention in thin film state; Figure 2 The UV-Vis absorption spectrum of P20 purified using the method of this invention is shown. Figure 3 The absorption spectrum is that of the blended thin film of multi-component copolymer optoelectronic materials P6 and m-TEH. Figure 4 Current density-open circuit voltage curves of P20 purified by different methods when matched with m-TEH. Detailed Implementation

[0043] The specific embodiments of the present invention are described below to facilitate understanding of the invention by those skilled in the art. Unless otherwise specified, specific conditions are applied according to conventional conditions or the manufacturer's recommendations. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various modifications are obvious as long as they fall within the spirit and scope of the invention as defined and determined by the appended claims. All inventions utilizing the concept of this invention are protected.

[0044] Example 1 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.19 mmol of 2,5-bis(trimethyltinyl)thiophene (M1), 0.01 mmol of 3,3'-difluoro-[2,2'-bithiophene]-5,5'-diyl)bistrimethyltin (M2), 0.20 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyldecyl)oxy)quinoxaline (M3), and 0.01 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 8 mL of toluene and 2 mL of DMF. After mixing thoroughly, the air in the flask was purged with argon gas, and the reaction was terminated at 110 °C in the dark for 24 h. The reaction was then quenched with methanol and purified to obtain a multi-component copolymer optoelectronic material (P1) with a yield of 91%. The molecular weight of P1 was determined to be 28.7 kDa by gel permeation chromatography (GPC).

[0045] Example 2 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.6 mmol of 2,5-bis(trimethyltinyl)thiophene (M1), 0.03 mmol of 5,8-dibromo-6,7-difluoro-2-((2-butyloctyl)oxy)-3-trifluoromethylquinoxaline (M4), 0.57 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyloctyl)oxy)quinoxaline (M5), and 0.025 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 20 mL of toluene and 5 mL of DMF. After mixing thoroughly, the air in the flask was purged with argon gas, and the reaction was terminated at 110 °C in the dark for 12 h. The reaction was then quenched with methanol and purified to obtain a multi-component copolymer optoelectronic material (P3) with a yield of 82%. The molecular weight of P3 was determined to be 33.1 kDa by gel permeation chromatography (GPC).

[0046] Example 3 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.3 mmol of 2,5-bis(trimethyltinyl)thiophene (M1), 0.015 mmol of 1,3-dibromo-5-(2-butyloctyl)-4H-thieno[3,4-C]pyrrole-4,6(5H)-dione (M6), 0.285 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyldecyl)oxy)quinoxaline (M3) and 0.025 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 15 mL of toluene and 3 mL of DMF. After mixing thoroughly, the air in the flask was purged with argon gas, and the reaction was terminated at 110 °C in the dark for 36 h. The reaction was then quenched with methanol and purified to obtain a multi-component copolymer optoelectronic material (P6) with a yield of 84%. The molecular weight of P6 was determined to be 33.7 kDa by gel permeation chromatography (GPC).

[0047] Example 4 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.2 mmol of 3,4-difluoro-2,5-bis(trimethyltin)thiophene (M7), 0.1 mmol of 5,9-dibromo-7-ethyl-2-((2-hexyldecyl)oxy)-6H-pyrrolo[3,4-g]quinoxaline-6,8(7H)-dione (M8), 0.1 mmol of 5,8-dibromo-6,7-dicyano-2-((2-hexyldecyl)oxy)quinoxaline (M9), and 0.03 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 5 mL of toluene and 0.5 mL of DMF. After mixing thoroughly, the air in the flask was purged with argon gas, and the reaction was terminated after 24 h in the dark at 110 °C. The reaction was then quenched with methanol and purified to obtain a multi-component copolymer optoelectronic material (P10) with a yield of 92%. The molecular weight of P10 was determined to be 29.1 kDa by gel permeation chromatography (GPC).

[0048] Example 5 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.2 mmol of 2,5-bis(trimethyltinyl)thiophene (M1), 0.08 mmol of 4,7-dibromo-5,6-difluoro-2-(2-octyldodecyl)benzo[b]thiophene (M10), 0.12 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyldecyl)oxy)quinoxaline (M3) and 0.06 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 8 mL of toluene and 1 mL of DMF. After mixing thoroughly, the air in the flask was purged with argon gas, and the reaction was terminated at 110 °C in the dark for 20 h. The reaction was then quenched with methanol and purified to obtain a multi-component copolymer optoelectronic material (P15) with a yield of 74%. The molecular weight of P15 was determined to be 36.4 kDa by gel permeation chromatography (GPC).

[0049] Example 6 A method for preparing a multi-component copolymer optoelectronic material, the reaction equation of which is as follows: , The specific steps include: adding 0.5 mmol of 2,5-bis(trimethyltinyl)thiophene (M1), 0.125 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyldecyl)oxy)-3-methylquinoxaline (M11), 0.125 mmol of 5,8-dibromo-6,7-difluoro-2-((2-hexyldecyl)oxy)quinoxaline (M3), 0.25 mmol of 5,8-dibromo-6-fluoro-2-((2-hexyldecyl)oxy)quinoxaline (M12) and 0.1 mmol of tetra(triphenylphosphine)palladium to a flask and mixing them. Then, adding 15 mL of toluene and 5 mL of LDMF, mixing thoroughly, and purging the air in the flask with argon gas, and then stopping the reaction at 110 °C in the dark for 30 h. The reaction was then quenched with methanol and purified to obtain the multi-component copolymer optoelectronic material (P19) with a yield of 77%. The molecular weight of P19 was determined to be 41.9 kDa by gel permeation chromatography (GPC).

[0050] Example 7 The preparation method of polymer P20, and the reaction equation are as follows: , The specific steps include: adding 0.1 mmol of (4,8-bis(5-(2-ethylhexyl)-4-fluorothiophene)benzo[1,2-B:4,5-B']dithiophene)bis(trimethyltinyl) (M13), 0.1 mmol of 5,8-bis(5-bromo-4-(2-hexyldecyl)thiophene)dithiophene[3',2':3,4;2'',3'':5,6]benzo[1,2-c][1,2,5]thiadiazole (M15) and 0.0075 mmol of tetra(triphenylphosphine)palladium to a flask, followed by adding 6 mL of toluene and 0.45 mL of DMF. After mixing thoroughly, the air in the flask is purged with argon gas, and the reaction is terminated at 110 °C in the dark for 15 h. After purification, polymer P20 is obtained.

[0051] Example 8 The polymer P6 obtained in Example 3 was purified by the following steps: Step 1: Preliminary dissolution and impurity removal a. Place the crude P6 product obtained in Example 3 into a 250 mL clean glass beaker and add a magnetic stir bar; b. Add 60 mL of acetone and stir continuously at 800 rpm for 20 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to centrifuge tubes and centrifuge at 6000 rpm for 3 min using a high-speed centrifuge to separate the supernatant (containing acetone and soluble byproducts) from the solid product phase (containing P6 and undissolved byproducts). Step 2: Replace the solvent and wash further. a. Place the solid product phase obtained in step 1 into a 250 mL clean glass beaker and add a magnetic stir bar; b. Add 100 mL of n-hexane and stir continuously at 800 rpm for 20 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to centrifuge tubes and centrifuge at 6000 rpm for 3 min using a high-speed centrifuge to separate the supernatant (containing n-hexane and soluble byproducts) from the solid product phase (containing P6 and undissolved byproducts). Step 3: Replace the solvent and wash further. a. Place the solid product phase obtained in step 2 into a 250 mL clean glass beaker and add a magnetic stir bar; b. Add 100 mL of dichloromethane and stir continuously at 800 rpm for 20 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to a centrifuge tube and centrifuge at 6000 rpm for 3 min using a high-speed centrifuge to separate the supernatant (containing dichloromethane and soluble byproducts) from the solid product phase; d. Dry the solid product phase in a vacuum drying oven at 60°C; Step 4: Redissolution and secondary purification 5 mL of chloroform was added to the dried material obtained in step 3, and the mixture was chemically precipitated dropwise in methanol. The methanol was removed by centrifugation at 7000 rpm, and finally, the material was vacuum dried at 40 °C to obtain a multi-component copolymer optoelectronic material (denoted as P6-A) with a yield of 82%. The molecular weight of P6-A was determined to be 32.0 kDa by gel permeation chromatography (GPC).

[0052] Figure 1 The image shows the UV-Vis absorption spectrum of P6-A polymer after it has been processed into a 120 nm thin film. As can be seen from the figure, P6-A polymer has good absorption in the 450 nm-650 nm range, and may achieve excellent energy conversion efficiency when paired with a narrow bandgap electron acceptor.

[0053] Example 9 The polymer P20 obtained in Example 7 was purified by the following steps: Step 1: Preliminary dissolution and impurity removal a. Place the crude P20 product obtained in Example 7 into a 500 mL clean glass beaker and add a magnetic stir bar; b. Add 200 mL of acetone and stir continuously at 1000 rpm for 20 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to centrifuge tubes and centrifuge at 6000 rpm for 3 min using a high-speed centrifuge to separate the supernatant (containing acetone and soluble byproducts) from the solid product phase (containing P20 and undissolved byproducts). Step 2: Replace the solvent and wash further. a. Place the solid product phase obtained in step 1 into a 500 mL clean glass beaker and add a magnetic stir bar at the same time; b. Add 200 mL of petroleum ether and stir continuously at 1000 rpm for 300 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to centrifuge tubes and centrifuge at 8000 rpm for 10 min using a high-speed centrifuge to separate the supernatant (containing petroleum ether and soluble byproducts) from the solid product phase (containing P20 and undissolved byproducts). Step 3: Replace the solvent and wash further. a. Place the solid product phase obtained in step 2 into a 500 mL clean glass beaker and add a magnetic stir bar; b. Add 300 mL of dichloromethane and stir continuously at 1000 rpm for 120 min at room temperature to fully dissolve the byproducts; c. Transfer the mixture to a centrifuge tube and centrifuge at 10,000 rpm for 10 min using a high-speed centrifuge to separate the supernatant (containing dichloromethane and soluble byproducts) from the solid product phase; d. Dry the solid product phase in a vacuum drying oven at 60°C; Step 4: Redissolution and secondary purification 10 mL of chloroform was added to the dried material obtained in step 3, and the mixture was chemically precipitated dropwise in methanol. The methanol was removed by centrifugation at 7000 rpm, and finally, the material was vacuum dried at 40 °C to obtain the multi-component copolymer optoelectronic material (P20) with a yield of 76%. The molecular weight of P20 was determined to be 62.2 kDa by gel permeation chromatography (GPC).

[0054] Figure 2 The UV-Vis absorption spectrum of the P20 polymer obtained after purification in Example 9 was measured after being processed into a 120 nm thick film. As can be seen from the figure, the three polymers have good absorption in the 500 nm-650 nm range, and may achieve excellent energy conversion efficiency when paired with a narrow bandgap electron acceptor.

[0055] Experimental Example 1 The following experiments were conducted using the multi-component copolymer optoelectronic materials P6, P10, and P19 prepared in Examples 3, 4, and 6 as examples.

[0056] 1. Combine the multi-component copolymer optoelectronic material P6 with... m-TEH was mixed and dissolved in chloroform at a 1:1 mass ratio to a solution concentration of 20 g / L. The solution was then transferred to a nitrogen-filled glove box. The battery device was fabricated on a transparent glass slide in the following sequence: indium tin oxide (ITO) / poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) / active layer film / PDINN / Ag. PEDOT:PSS, the active layer film, and PDINN were spin-coated, while the Ag electrode was prepared by vapor deposition. PEDOT:PSS served as the anode modification layer, and PDINN as the cathode modification layer, resulting in battery device A.

[0057] 2. The multi-component copolymer optoelectronic material polymer P10 and... m -TEH was mixed and dissolved in tetrahydrofuran at a 1:1 mass ratio, with a solution concentration of 18 g / L. The solution was then transferred to a nitrogen-filled glove box. The battery device was fabricated on a transparent glass slide in the following sequence: indium tin oxide (ITO) / poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) / active layer film / PDINN / Ag. PEDOT:PSS, the active layer film, and PDINN were spin-coated, while the Ag electrode was prepared by vapor deposition. PEDOT:PSS served as the anode modification layer, and PDINN as the cathode modification layer, resulting in battery device B.

[0058] 3. The multi-component copolymer optoelectronic material polymer P19 and... m -TEH was mixed and dissolved in toluene at a 1:1 mass ratio, resulting in a solution concentration of 22 g / L. The solution was then transferred to a nitrogen-filled glove box. The battery device was fabricated on a transparent glass slide in the following sequence: indium tin oxide (ITO) / poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) / active layer film / PDINN / Ag. PEDOT:PSS, the active layer film, and PDINN were spin-coated, while the Ag electrode was prepared by vapor deposition. PEDOT:PSS served as the anode modification layer, and PDINN as the cathode modification layer, resulting in battery device C.

[0059] The glove box was equipped with calibrated standard sunlight, namely AM1.5G (100mW / cm²). 2 The AC characteristic curves of the fabricated battery device were tested under simulated sunlight intensity. The formula for calculating the energy conversion efficiency (%) is as follows: ; Where a is the energy conversion efficiency (%), b is the open-circuit voltage (V), and c is the short-circuit current density (mA / cm²). 2 ; d is the fill factor, % P in The power of the incident light is expressed in mW / cm².2 .

[0060] The power of the incident light in the above tests P in 100mW / cm 2 The test data is shown in Table 1.

[0061] Table 1 Photovoltaic performance parameters of organic solar cell devices (AC)

[0062] As can be seen from Table 1, all battery devices AC achieved excellent performance, indicating that P6, P10, and P19 are superior to those in the standard battery. m When the TEH receptors are matched, they can achieve good complementarity in the absorption of sunlight. The different parameters of the three devices can meet the diversified production needs of industrialization.

[0063] Figure 3 For P6 and m The UV-Vis absorption spectrum of a 120nm thin film prepared by mixing TEH at a mass ratio of 1:1.2 is shown in the figure. (P6:) m -TEH hybrid membranes exhibit good absorption in the 450nm-900nm range, which is a prerequisite for achieving good energy conversion efficiency.

[0064] Experiment Example 2 A layer of PEDOT was uniformly coated onto a 10cm x 10cm glass slide containing ITO and a flexible PET substrate using a coating machine on the outside of the glove box. Then, a layer-by-layer coating method was employed, first coating a layer of chloroform solution (300nm) of the multi-component copolymer P19, followed by a layer of... m A chloroform solution of TEH (300 nm) and a layer of PFN-Br in methanol were used, without any annealing treatment. After depositing a 150 nm thick silver electrode, testing was conducted using an ENLITECH SS-X series AM1.5 standard spectral solar simulator. The test was performed under calibrated standard sunlight (AM 1.5G, 100 mW / cm²). -2 The above P19 was measured below: m JV characteristic curves of the 10cm×10cm rigid device (battery device D) of -TEH. Performance data are shown in Table 2.

[0065] Table 2 (Based on P19): m Photovoltaic performance parameters of D and E of -TEH organic solar cell devices

[0066] Battery component description: 1. Battery device D is the original P19 containing a 10cm × 10cm glass substrate: m -TEH devices.

[0067] 2. Battery device E is a flexible device made by replacing the glass substrate in battery device D with a flexible PET substrate.

[0068] As shown in Table 2, battery device D ultimately achieved an energy conversion efficiency of 12.00%, with an open-circuit voltage of 0.843V and a short-circuit current density of 24.21mA / cm². -2 The fill factor is 58.8%. (See page 19 above.) m -TEH's 10cm×10cm flexible device (battery device E) has a power conversion efficiency of 11.25%, with an open-circuit voltage of 0.840V and a short-circuit current density of 23.96mA. -2 The fill factor is 55.9%.

[0069] Experimental Example 3 To verify the storage and thermal stability of a large-area rigid device fabricated in air, battery device D was placed in air, and its storage stability was tested at different temperatures. The results are shown in Table 3.

[0070] Table 3 (Based on P19): m Photovoltaic performance parameters of -TEH organic solar cell device FH

[0071] Battery component description: 1. Battery device F is an aged device of battery device D after being stored in air at room temperature for 3000 hours.

[0072] 2. Battery device G is an aged device of battery device D after being stored in air at 65°C for 1000 hours.

[0073] 3. Battery device H is the device after battery device E has been bent 10,000 times in the air.

[0074] After aging at room temperature for 3000 hours, the performance of battery device F decreased by 20% of its initial efficiency (the measured efficiency was 9.61%). After aging at 65°C for 1000 hours, the performance of battery device G decreased by 20% of its initial efficiency (the measured efficiency was 9.60%). After the flexible battery device E was subjected to 10,000 bends in air, the performance of battery device H decreased by 20% of its initial efficiency (the measured efficiency was 9.00%). This demonstrates that the multi-component copolymer P19 possesses excellent water and oxygen resistance, high mechanical strength, and high stability, enabling large-area air-coating processing and broad application range.

[0075] Experiment Example 4 The polymers P6 and P20 prepared in Examples 3 and 7 were purified using a Soxhlet extractor to verify the effect of the purification method of the present invention on the material properties. The Soxhlet extractor purification method specifically involved: after the reaction was complete, the polymers were sequentially purified in a Soxhlet extractor using 100 mL of methanol, 100 mL of n-hexane, and 100 mL of chloroform; followed by rotary evaporation, chemical precipitation in methanol, centrifugation at 7000 rpm to remove methanol, and finally vacuum drying at 40 °C to obtain the Soxhlet-purified multi-component copolymer optoelectronic materials P6 and P20.

[0076] The multi-component copolymer optoelectronic material P6 / P6-A (Example 8), prepared by two different purification methods, was compared with... m -TEH was mixed and dissolved in chloroform at a mass ratio of 1:1.2, resulting in a solution concentration of 18 g / L. The solution was then transferred to a nitrogen-filled glove box. The battery devices were fabricated on a transparent glass slide in the following sequence: indium tin oxide (ITO) / poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) / active layer film / PDINN / Ag. PEDOT:PSS, the active layer film, and PDINN were spin-coated, while the Ag electrode was prepared by vapor deposition. PEDOT:PSS served as the anode modification layer, and PDINN as the cathode modification layer, resulting in battery devices I and J.

[0077] The glove box was equipped with calibrated standard sunlight, namely AM1.5G (100mW / cm²). 2 The JV characteristic curves of the fabricated battery devices I and J were tested under simulated sunlight intensity. The performance data are shown in Table 4.

[0078] Table 4. Photovoltaic performance parameters of organic solar cell devices I and J based on different polymer purification methods.

[0079] Battery component description: 1. Battery device I is based on P6:m -TEH organic solar cell devices.

[0080] 2. Battery device J is based on P6-A: m -TEH organic solar cell devices.

[0081] As shown in Table 4, battery device I ultimately achieved an energy conversion efficiency of 18.59%, with an open-circuit voltage of 0.905V and a short-circuit current density of 26.95mA / cm². -2 The fill factor was 76.23%. Battery device J ultimately achieved a power conversion efficiency of 19.41%, with an open-circuit voltage of 0.905V and a short-circuit current density of 27.54mA / cm². -2 The fill factor is 77.86%. This invention employs a simple and efficient purification method, and the purified polymer optoelectronic material P6-A-based battery device exhibits superior short-circuit current density and fill factor compared to P6-based battery devices.

[0082] Figure 4 P20 obtained in Example 9 and m The current density-voltage curve during TEH matching shows that: P20 obtained based on the purification method of this invention, when matched with... m -TEH matching results in a higher open-circuit voltage for P20 compared to traditional Soxhlet extraction and purification, thus enabling higher energy conversion efficiency.

[0083] In summary, the polymeric optoelectronic materials obtained by the purification method of this invention have performance comparable to or even superior to polymers obtained by the traditional Soxhlet extractor method. This method is expected to facilitate the large-scale green industrial production of polymeric optoelectronic materials.

Claims

1. A multi-component copolymer optoelectronic material, characterized in that, The general structural formula of the multi-component copolymer optoelectronic material is: ， Where x, y, z and m take values ​​in the range of 0≤x<1, 0≤y<1, 0≤z<1, 0≤m<1, and the sum of x, y, z and m is equal to 1, n is an integer from 2 to 1000, x, y and z are not simultaneously equal to 0, x, y and m are not simultaneously equal to 0, x, z and m are not simultaneously equal to 0, and y, z and m are not simultaneously equal to 0. R1-R6 are hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, alkyl groups, alkoxy groups, alkylthio groups, silyl groups, fluoroalkyl groups, alkyl chlorides, aralkyl groups, heterocyclic aralkyl groups, alicyclic groups, alkylamines, hydroxyl groups, acyl groups, acyloxy groups, acylthio groups, ester groups, amino groups, amide groups, alkenyl groups, alkynyl groups, carboxyl groups, cyano groups, sulfonic acid groups, or nitro groups; wherein the alkyl groups, alkoxy groups, alkylthio groups, silyl groups, fluoroalkyl groups, alkyl chlorides, aralkyl groups, heterocyclic aralkyl groups, alicyclic groups, or alkylamines are straight-chain or branched alkyl groups having 1-30 carbon atoms; Ar1 and Ar3 are electron-rich units, selected from any of the following groups: A1. A substituted or unsubstituted three-membered, four-membered, five-membered, six-membered, seven-membered, eight-membered, nine-membered, or ten-membered ring system, wherein the system contains 0-4 heteroatoms independently selected from oxygen, nitrogen, sulfur, selenium, or silicon; or A2. The fused rings in A1, where the groups are directly connected to each other or constructed through bridging atoms, have at least one group. Ar2 and Ar4 are electron-deficient units, selected from any of the following groups: B1. A substituted or unsubstituted three-membered ring system, four-membered ring system, five-membered ring system, six-membered ring system, seven-membered ring system, eight-membered ring system, nine-membered ring system, or ten-membered ring system, wherein the system contains 0-4 heteroatoms independently selected from oxygen, nitrogen, sulfur, selenium, or silicon; or B2, the fused rings in B1 that are directly connected to each other or constructed through bridging atoms, have at least one group.

2. The multi-component copolymer optoelectronic material according to claim 1, characterized in that, The structural formulas of Ar1 and Ar3 are as follows: ， Where X is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, or silicon atom; R7-R 10 The alkyl group, alkoxy group, alkoxy group, alkylthio group, silyl group, fluoroalkyl group, alkyl chloride group, aralkyl group, heterocyclic aralkyl group, alicyclic group, alkylamine group, hydroxy group, acyl group, acyloxy group, acylthio group, ester group, amino group, amide group, alkenyl group, alkynyl group, carboxyl group, carbonyl group, cyano group, sulfonic acid group, or nitro group; wherein the alkyl group, alkoxy group, alkoxy group, silyl group, fluoroalkyl group, alkyl chloride group, aralkyl group, heterocyclic aralkyl group, alicyclic group, or alkylamine group is a straight-chain or branched alkyl group with 1-30 carbon atoms.

3. The multi-component copolymer optoelectronic material according to claim 1, characterized in that, The structural formulas for Ar2 and Ar4 are as follows: ， Where X is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, or silicon atom; R7-R 11 The alkyl group, alkoxy group, alkoxy group, alkylthio group, silyl group, fluoroalkyl group, alkyl chloride group, aralkyl group, heterocyclic aralkyl group, alicyclic group, alkylamine group, hydroxy group, acyl group, acyloxy group, acylthio group, ester group, amino group, amide group, alkenyl group, alkynyl group, carboxyl group, carbonyl group, cyano group, sulfonic acid group, or nitro group; wherein the alkyl group, alkoxy group, alkoxy group, silyl group, fluoroalkyl group, alkyl chloride group, aralkyl group, heterocyclic aralkyl group, alicyclic group, or alkylamine group is a straight-chain or branched alkyl group with 1-30 carbon atoms.

4. The method for preparing the multi-component copolymer optoelectronic material according to any one of claims 1-3, characterized in that, Includes the following steps: Thiophene units and quinoxaline units, along with electron-rich units Ar1 and Ar3 and / or electron-deficient units Ar2 and Ar4, are mixed in organic solvent A. After adding a catalyst, the mixture is reacted at 10-160℃ for 0.5-50 h to obtain a multi-component copolymer optoelectronic material. The ratio of the sum of the molar amounts of the catalyst, thiophene units, Ar1, and Ar3 to the sum of the molar amounts of quinoxaline units, Ar2, and Ar4 is 0.01%-10%:1:0.5-2. The molar ratio of the thiophene units, Ar1, and Ar3 is 0-2:0-1:0-1, and the molar amounts of the thiophene units, Ar1, and Ar3 are not simultaneously 0. The molar ratio of the quinoxaline units, Ar2, and Ar4 is 0-2:0-1:0-1, and the molar amounts of the quinoxaline units, Ar2, and Ar4 are not simultaneously 0.

5. The method for preparing the multi-component copolymer optoelectronic material according to claim 4, characterized in that, The catalyst is tetra(triphenylphosphine)palladium, [1,2-bis(diphenylphosphine)ethane]nickel dichloride, tris(dibenzylideneacetone)palladium, palladium chloride, palladium acetate, palladium nitrate, palladium oxide, or palladium hydride.

6. A method for purifying the multi-component copolymer optoelectronic material according to any one of claims 1-3, characterized in that, Includes the following steps: S1. After the reaction is complete, add 1-100000 wt% organic solvent B to the reactants, stir at room temperature for 0.1-24 h, and separate the solid and liquid phases to obtain the solid product phase. S2. Repeat step S1 1-20 times; S3. Place the product obtained in S2 in a vacuum and dry it at 50-70°C to constant weight.

7. The application of the multi-component copolymer optoelectronic material according to any one of claims 1-3 in the preparation of organic solar cell devices.

8. The application according to claim 7, characterized in that, The organic solar cell device comprises, from bottom to top: a first electrode, a semiconductor layer, and a second electrode, wherein the semiconductor layer comprises the multi-component copolymer photoelectric material as described in any one of claims 1-4.

9. The application according to claim 8, characterized in that, The semiconductor layer further includes an n-type organic semiconductor acceptor, the mass ratio of the multi-component copolymer photoelectric material to the n-type organic semiconductor acceptor is 1:0.1-10, and the total concentration of the multi-component copolymer photoelectric material and the n-type organic semiconductor acceptor is 0.2-80 mg / mL.

10. The application according to claim 9, characterized in that, The n-type organic semiconductor receptor is a fullerene receptor, a non-fullerene small molecule receptor, or a polymer receptor.

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