An organic solar cell device and a polymer therefor

Abstract

The application discloses an organic solar cell device, which comprises at least a first electrode, a second electrode and a photoactive layer between the first electrode and the second electrode, wherein the photoactive layer comprises a donor material and an acceptor material, and the donor material is a double-polymer donor; since two polymers have the same polymer main chain, the double-polymer donor has good miscibility; meanwhile, through optimization of side chain engineering, the double-polymer donor material is matched with a suitable acceptor material to exhibit higher charge mobility and suitable phase separation size and aggregation morphology, so that the photoelectric conversion efficiency of the organic electronic device is improved.

Description

Technical Field

[0001] This invention relates to the field of organic solar cell materials, and particularly to an organic solar cell device and its polymer. Background Technology

[0002] Solar energy is environmentally friendly, and photovoltaic (PV) technology, based on solar power generation, has become an important component of renewable energy technologies and an effective way to solve energy shortages. Organic solar energy technology is characterized by low cost, being green and non-toxic, highly efficient, flexible, colored and semi-transparent, and capable of large-area printing using low-temperature solution methods. It is currently an ideal photoelectric conversion technology applicable to wearable electronic devices, the Internet of Things, electronic shelf labels, building-integrated photovoltaics, new energy vehicles, and other scenarios, and has broad market prospects.

[0003] Organic solar cells generally consist of five parts: an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode. The active layer typically contains donor and acceptor materials. Its working principle is as follows: When sunlight passes through a transparent substrate and electrodes and enters the active layer, the donor and acceptor materials absorb photons with energy greater than their band gaps. Electrons are excited from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), simultaneously creating corresponding holes at the HOMO. Due to the relatively low permittivity of organic materials, the electrons and holes exist in a bound exciton state. Subsequently, the excitons diffuse to the donor-acceptor interface, where, driven by the energy level difference, they dissociate, achieving charge separation. Then, under the influence of the built-in electric field, the free holes and electrons travel along the continuous channels of the donor and acceptor materials to the anode and cathode, respectively, where they are collected by the electrodes and output to the external circuit to form a current. Therefore, the choice of photoactive layer material is crucial to the efficiency of organic solar cell devices.

[0004] In recent years, the photoelectric conversion efficiency of organic solar cells has rapidly improved due to the vigorous development of Y-series (such as Y6, L8-BO) non-fullerene acceptor materials and wide-bandgap donor materials (such as PM6, PM7). To date, many strategies have been developed to enhance their photovoltaic performance. Given the simple fabrication steps and low production cost of ternary organic solar cell devices, this hybrid strategy has attracted increasing attention. However, current ternary devices mainly focus on combining one donor polymer with two small-molecule acceptor materials, while the development of ternary devices based on dual polymer donors has been relatively slow. This is because the entanglement between the two polymers easily leads to poor phase separation, making it difficult to control the crystallization and morphology of the active layer, thus limiting the improvement of photovoltaic performance. Therefore, developing suitable dual polymer donor systems is of great significance for the further development of organic solar cells. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to provide an organic solar cell device whose photoactive layer comprises a dual polymer donor material, and whose device exhibits good photoelectric conversion efficiency.

[0006] To achieve the objective of this invention, the technical solution is as follows:

[0007] An organic solar cell device, comprising at least a first electrode, a second electrode, and a photoactive layer located between the first and second electrodes, the photoactive layer comprising a donor material and an acceptor material, the donor material comprising at least one polymer 1 as described in formula (I) and at least one polymer 2 as described in formula (II):

[0008]

[0009] in,

[0010] X is selected from O, S, or Se;

[0011] R1, R2, and R3, each time appearing independently, are selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, or groups formed by combinations of these groups;

[0012] Each time R4 appears, it is independently selected from -H (hydrogen), -D (deuterium), straight-chain alkyl with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms;

[0013] Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms;

[0014] n is the number of repeating units and is an integer greater than 1.

[0015] The present invention also provides a polymer selected from the structure shown in formula (II) above.

[0016] Accordingly, the present invention also provides a mixture comprising at least one polymer 1 as described in formula (I) and at least one polymer 2 as described in formula (II).

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

[0018] This invention obtains a dual polymer donor by blending polymer 1 having a structure as shown in general formula (I) and polymer 2 having a structure as shown in general formula (II). Since general formula (I) and general formula (II) have the same polymer backbone, they have good miscibility. At the same time, through the optimization of side chain engineering, the dual polymer donor material can be better matched with a suitable acceptor material to balance the aggregation and crystallization tendency of molecules, thereby forming a more ideal thin film morphology and improving the photoelectric conversion efficiency of organic electronic devices. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of the structure of the organic solar cell in the device embodiment of the present invention;

[0021] In the diagram, 101 is the substrate, 102 is the anode, 103 is the anode buffer layer, 104 is the photoactive layer, 105 is the cathode buffer layer, and 106 is the cathode. Detailed Implementation

[0022] To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following provides a further detailed description of this application. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without inventive effort are within the scope of protection of this invention.

[0023] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0024] In this invention, when the position of the substituent on the group is not fixed, it means that any connectable site in the group can serve as a connection site. For example... Can represent

[0025] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... The six R's on the benzene ring can be the same or different from each other.

[0026] The halogens mentioned in this invention refer to fluorine, chlorine, bromine, and iodine;

[0027] In this invention, organic photovoltaic devices, organic solar cells, and OPV have the same meaning and can be used interchangeably.

[0028] In this invention, the active layer and the photoactive layer have the same meaning and can be used interchangeably.

[0029] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0030] In this invention, "alkyl" can refer to straight-chain, branched, and / or cyclic alkyl groups. The number of carbon atoms in a straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the number of carbon atoms in a branched alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; and the number of carbon atoms in a cyclic alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and -C. 10 H 21 -C 11 H 23 -C 12 H 25 -C 13 H 27 -C 14 H 29 -C 15 H 31 -C 16 H 33 Non-limiting examples of branched alkyl groups include: isopropyl, branched alkyl groups containing 4 carbon atoms, branched alkyl groups containing 5 carbon atoms, branched alkyl groups containing 6 carbon atoms, branched alkyl groups containing 7 carbon atoms, branched alkyl groups containing 8 carbon atoms, branched alkyl groups containing 9 carbon atoms, branched alkyl groups containing 10 carbon atoms, branched alkyl groups containing 11 carbon atoms, branched alkyl groups containing 12 carbon atoms, branched alkyl groups containing 13 carbon atoms, branched alkyl groups containing 14 carbon atoms, and branched alkyl groups containing 15 carbon atoms. Branched alkyl groups containing 16 carbon atoms; non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclic alkyl groups containing 7 carbon atoms, cyclic alkyl groups containing 8 carbon atoms, cyclic alkyl groups containing 9 carbon atoms, cyclic alkyl groups containing 10 carbon atoms, cyclic alkyl groups containing 11 carbon atoms, cyclic alkyl groups containing 12 carbon atoms, cyclic alkyl groups containing 13 carbon atoms, cyclic alkyl groups containing 14 carbon atoms, cyclic alkyl groups containing 15 carbon atoms, and cyclic alkyl groups containing 16 carbon atoms.

[0031] The term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. The straight-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkoxy means that the alkyl group in "-O-alkyl" is selected from cyclic alkyl groups, wherein the number of carbon atoms in the cyclic alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0032] The term "alkoxythio" refers to a group with the structure "-S-alkyl", that is, an alkyl group as defined above that is attached to other groups via a sulfur atom. The straight-chain alkoxythio group indicates that the alkyl group in "-S-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxythio group indicates that the alkyl group in "-S-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkoxythio group indicates that the alkyl group in "-S-alkyl" is selected from cyclic alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0033] In this invention, the phrase "independently selected" means that when one or more groups appear simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different.

[0034] In this invention, the terms "combinations thereof", "any combination thereof", "any combination thereof", "combination", etc., refer to all suitable combinations of any two, three, four or more groups listed.

[0035] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0036] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0037] In describing the structural elements of the present invention, the terms "comprising" or "including" or similar terms used in the present invention mean that the device or material preceding the word covers the device or material listed after the word and its equivalents, but does not exclude other devices or materials.

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

[0039] A first aspect of the present invention provides an organic solar cell device, the organic solar cell device comprising at least a first electrode, a second electrode, and a photoactive layer located between the first electrode and the second electrode, the photoactive layer comprising a donor material and an acceptor material, the donor material comprising at least one polymer 1 as described in formula (I) and at least one polymer 2 as described in formula (II):

[0040]

[0041] in,

[0042] X is selected from O, S, or Se;

[0043] R1, R2, and R3, each time appearing independently, are selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, or groups formed by combinations of these groups;

[0044] Each time R4 appears, it is independently selected from -H (hydrogen), -D (deuterium), straight-chain alkyl with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms;

[0045] Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms;

[0046] n is the number of repeating units and is an integer greater than 1.

[0047] In one embodiment, the polymer 1 is selected from formula (I-1), (I-2), or (I-3):

[0048]

[0049]

[0050] Wherein: R4 is selected independently each time it appears from a straight-chain alkyl group having 1-20 carbon atoms, a branched or cyclic alkyl group having 3-20 carbon atoms.

[0051] In one embodiment, each occurrence of R4 is independently selected from straight-chain alkyl groups having 1-16 carbon atoms, branched or cyclic alkyl groups having 3-16 carbon atoms.

[0052] Specifically, each time R4 appears in equation (I-1), (I-2), or (I-3), it is independently selected from any of the following structures:

[0053] *-C6H 13 *-C8H 17

[0054] Where: * indicates a linking group.

[0055] In one embodiment, the polymer 2 is selected from formula (II-1) or (II-2):

[0056]

[0057] Furthermore, each occurrence of R5 is independently selected from straight-chain alkyl groups having 1-16 carbon atoms or branched alkyl groups having 3-16 carbon atoms.

[0058] Specifically, each time R5 appears, it is independently selected from any of the following structures:

[0059] *-C6H 13 *-C8H 17

[0060]

[0061] In one embodiment, each occurrence of R1 and R2 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, straight-chain alkyl with 1-10 carbon atoms, or branched or cyclic alkyl with 3-10 carbon atoms.

[0062] Furthermore, each occurrence of R1 and R2 is independently selected from -H (hydrogen), -F, -Cl, -Br, and *-C6H. 13 、*-C4H9.

[0063] In one embodiment, each occurrence of R3 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, straight-chain alkyl having 1-16 carbon atoms, straight-chain alkoxy having 1-16 carbon atoms, straight-chain alkylthio having 1-16 carbon atoms, branched alkyl having 3-16 carbon atoms, branched alkoxy having 3-16 carbon atoms, and branched alkylthio having 3-16 carbon atoms.

[0064] Furthermore, each occurrence of R3 is independently selected from branched alkyl groups having 3-16 carbon atoms, branched alkoxy groups having 3-16 carbon atoms, or branched alkylthio groups having 3-16 carbon atoms.

[0065] In a specific embodiment, each occurrence of R3 is independently selected from...

[0066]

[0067] In one embodiment, Each occurrence is independently selected from any of the following groups:

[0068]

[0069] In one embodiment, in formula (I) or formula (II), Each time R1, R2, and R3 appear, the groups selected may be the same or different.

[0070] Furthermore, in equation (I) Each time it appears, the selected functional group is the same.

[0071] Furthermore, in equation (II) Each time it appears, the selected functional group is the same.

[0072] In one specific embodiment, the polymer 1 is selected from, but is not limited to, the following structures:

[0073]

[0074]

[0075] In one specific embodiment, the polymer 2 is selected from, but is not limited to, the following structures:

[0076]

[0077]

[0078]

[0079]

[0080] According to the organic solar cell device of the present invention, preferably, polymer 2 is used as a donor material in the photoactive layer because: the appropriate introduction of carboxylic acid ester substituents can effectively control the energy level and crystallinity of the polymer donor, thereby improving the performance of the photoactive layer film.

[0081] In one embodiment, the mass ratio of the donor materials polymer 1 to polymer 2 is 5:5 to 9:1; further, the mass ratio of polymer 1 to polymer 2 is 7:3 to 9:1; and even further, the mass ratio of polymer 1 to polymer 2 is 8:2 to 9:1.

[0082] In one embodiment, n is selected from an integer from 5 to 1000; further, n is selected from an integer from 5 to 300; even further, n is selected from an integer from 10 to 100; even further, n is selected from an integer from 15 to 100; in the most preferred embodiment, n is selected from an integer from 20 to 50.

[0083] In one embodiment, the organic solar cell device according to the present invention, wherein the acceptor material is selected from non-fullerene acceptor materials.

[0084] Furthermore, the receptor material contains at least one structure as described in formula (III) or formula (IV):

[0085]

[0086]

[0087] Among them: R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each time it appears, it is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, or a group formed by combination of these groups;

[0088] n is the number of repeating units and is an integer greater than 1.

[0089] Preferably, each occurrence of R6 and R7 is independently selected from -H (hydrogen), -D (deuterium), straight-chain alkyl with 1-16 carbon atoms, straight-chain alkoxy with 1-16 carbon atoms, straight-chain alkylthio with 1-16 carbon atoms, branched or cyclic alkyl with 3-16 carbon atoms, branched or cyclic alkoxy with 3-16 carbon atoms, and branched or cyclic alkylthio with 3-16 carbon atoms.

[0090] Preferably, each occurrence of R8 and R9 is independently selected from a straight-chain alkyl group having 1-16 carbon atoms or a branched alkyl group having 3-16 carbon atoms. More preferably, each occurrence of R8 and R9 is independently selected from any of the following structures:

[0091] Preferably, R 10 R 11 R 12 R 13 R 14 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, -CF3, and straight-chain or branched alkyl groups having 1-10 carbon atoms.

[0092] Preferably, R 10 R 11 R 12 R 13 R 14Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, -CF3, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl.

[0093] In one specific embodiment, the receptor material contains at least one of the following structures:

[0094]

[0095]

[0096] Preferably, the photoactive layer material comprises a donor material and an acceptor material, wherein the mass ratio of the donor material to the acceptor material is 0.8:1.8 to 1.8:0.8; in one embodiment, the mass ratio of the donor material to the acceptor material is 1:1 to 1:1.8; further, the mass ratio of the donor material to the acceptor material is 1:1 to 1:1.5; further still, the mass ratio of the donor material to the acceptor material is 1:1 to 1:1.2.

[0097] In this invention, "at least one" or "at least one" means that one, two, three or more of the defined materials or functional layers can be selected.

[0098] According to the organic solar cell device of the present invention, in addition to the first electrode, the second electrode and the photoactive layer, the organic solar cell device also includes an anode buffer layer and a cathode buffer layer.

[0099] It should be noted that, in order to improve the performance of organic electronic devices, the functional layer may further include other functional layers, such as charge injection layer and / or charge blocking layer.

[0100] The organic solar cell device according to the present invention further includes a substrate. Specifically, the substrate may be disposed on one side of the first electrode and on a different side from the functional layer.

[0101] In one embodiment, the first electrode is an anode and the second electrode is a cathode; in another embodiment, the first electrode is a cathode and the second electrode is an anode.

[0102] Furthermore, the anode buffer layer is located between the anode and the photoactive layer; the cathode buffer layer is located between the cathode and the photoactive layer.

[0103] In a preferred embodiment, the organic solar cell device comprises a substrate, an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially; or the organic solar cell device comprises a substrate, a cathode, a cathode buffer layer, a photoactive layer, an anode buffer layer, and an anode stacked sequentially.

[0104] Specifically, the substrate can be a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include, but is not limited to, single-layer or multi-layer films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), and polyimide (PI), and may also use substrates commonly used in organic solar cells.

[0105] The materials used to prepare the electrodes can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle pastes, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO∶Al or SnO2∶Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole, and polyaniline, etc.; or materials with multilayer structures, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al∶Li, Al∶BaF2, and Al∶BaF2∶Ba, etc., but are not limited to these.

[0106] In one embodiment, the active layer can be formed by dissolving a photoactive layer material, such as an electron donor and / or an electron acceptor, in an organic solvent, and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spraying, doctor blade coating, slot coating, and inkjet printing, but not limited thereto.

[0107] Specifically, the photoactive layer donor material and acceptor material are dissolved in an organic solvent to prepare a photoactive layer solution. The organic solvent may be selected from dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetrahydrofuran, acetophenone, acetophenone, tetrahydronaphthalene, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indane, methyl benzoate, ethyl benzoate, mesitylene, or mixtures thereof. In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0108] Furthermore, the organic solvent is selected from chlorobenzene.

[0109] In one embodiment, the concentration of the total amount of donor and acceptor materials in the active layer in the organic solvent is selected from 10-30 mg / mL; further, the concentration of the mixture in the organic solvent is selected from 10-20 mg / mL.

[0110] Furthermore, the photoactive layer solution may also include additives for adjusting viscosity, film-forming properties, and improving adhesion. These additives may be selected from, but are not limited to, at least one of surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, and adhesives. In a preferred embodiment, the additives may include, but are not limited to, 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, 1,4-diiodobenzene (DIB), 1,3-dibromo-5-chlorobenzene (DBCl), 3,5-dichlorobromobenzene (DCBB), 1-chloronaphthalene (1-CN), and 1,3,5-tribromobenzene (TBB).

[0111] The anode buffer layer material can be selected from PEDOT:PSS, molybdenum oxide (MoOx), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WOx, preferably, x is selected from 2 or 3), etc., but is not limited to these.

[0112] The cathode buffer layer material can be an electron-withdrawing metal oxide or polymer. The metal oxide can be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc., and the polymer can be PFN-Br, PFN, PDINN, PNDIT-F3N-Br, PNDIT-F3N, etc., but is not limited to these.

[0113] This invention also relates to the application of organic solar cells according to the invention in various devices, including, but not limited to, building-integrated photovoltaics (BIPV), electronic shelf labels, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0114] A second aspect of the invention also relates to a polymer selected from the structure described in formula (II):

[0115]

[0116] in,

[0117] X is selected from O, S, or Se;

[0118] R1, R2, and R3, each time appearing independently, are selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, or groups formed by combinations of these groups;

[0119] Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms;

[0120] n is the number of repeating units and is an integer greater than 1.

[0121] Furthermore, in a preferred embodiment, the polymer described in formula (II) is selected from the following structures:

[0122]

[0123] More preferably, each occurrence of R3 and R5 is independently selected from straight-chain alkyl groups having 1-16 carbon atoms, branched or cyclic alkyl groups having 3-16 carbon atoms;

[0124] Furthermore, each occurrence of R1 and R2 is independently selected from -H, -F, -Cl, -Br, -I, cyano, or -CF3.

[0125] The reason why the thiophene in the polymer according to formula (II) of this invention is selected from carboxylic acid esters is that carboxylic acid ester substituents can greatly reduce the HOMO energy level, thereby ensuring that the device can obtain a large V0. OC Secondly, the gradual substitution of electron-withdrawing groups can further modulate the energy level and temperature-dependent aggregation behavior of polymer donors, thereby improving the photoelectric properties of the photoactive layer.

[0126] The polymer according to formula (II-1) of the present invention utilizes the non-covalent interaction force (O…S) between the carboxylic acid ester and the benzodithiophene group to make the polymer have better coplanarity, improve molecular crystallinity and promote charge transport.

[0127] The polymer synthesis method provided by this invention can utilize raw materials containing active groups to react and form suitable CC-linked reactions, which are well known to those skilled in the art and described in the literature. Preferred coupling reaction methods include, for example, the SUZUKI method, YAMAMOTO method, STILLE method, NIGESHI method, KUMADA method, HECK method, SONOGASHIRA method, HIYAMA method, FUKUYAMA method, HARTWIG-BUCHWALD method, and ULLMAN method.

[0128] 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.

[0129] In a preferred embodiment, the molecular weight of the polymer is Mw ≥ 10000 g / mol; further, Mw ≥ 20000 g / mol; and even further, Mw ≥ 30000 g / mol.

[0130] In one specific embodiment, the polymer according to formula (II) of the present invention is selected from any of the structures of formulas (2-1)-(2-45), but is not limited thereto.

[0131] The polymer according to Formula (II) provided in the second aspect of the present invention can be used as an active layer material in organic electronic devices; preferably, the polymer according to Formula (II) provided in the second aspect of the present invention can be used as an active layer donor material in organic solar energy devices.

[0132] A third aspect of the invention also provides a mixture comprising at least one polymer 1 as described in general formula (I) and at least one polymer 2 as described in general formula (II).

[0133] In a preferred embodiment, the mixture contains at least one polymer 1 as described in general formula (I-2) and at least one polymer 2 as described in general formula (II-1).

[0134] Further, the mass ratio of donor materials polymer 1 to polymer 2 in the mixture is 5:5 to 9:1; further, the mass ratio of polymer 1 to polymer 2 is 7:3 to 9:1; even further, the mass ratio of polymer 1 to polymer 2 is 8:2 to 9:1.

[0135] Furthermore, the mixture further comprises at least one receptor material selected from non-fullerene receptor materials.

[0136] Furthermore, the mixture contains at least one polymer 1 as described in general formula (I), at least one polymer 2 as described in general formula (II), and at least one structure as described in general formula (III) or general formula (IV), wherein the general formula (I), general formula (II), general formula (III), or general formula (IV) is as described above.

[0137] The mixture according to the third aspect of the present invention can be used as an active layer material in organic solar cell devices.

[0138] The present invention will be described below with reference to polymer preparation examples and device examples. However, the present invention is not limited to the following examples. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0139] Example 1: Synthesis of polymer (2-1)

[0140]

[0141] Synthesis of compound 2-1-3:

[0142] Accurately weigh compound 2-1-1 (4.7 g, 20 mmol), compound 2-1-2 (5.59 g, 22 mmol), potassium acetate (3.92 g, 40 mmol), tris(dibenzylacetone)dipalladium (0.12 g, 0.2 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.19 g, 0.4 mmol) into a 100 mL three-necked flask. Add 50 mL of dioxane, purge with nitrogen three times, and then heat to 105 °C and react for 12 h. Cool to room temperature, and remove excess solvent by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 8:1 (v / v)) to give approximately 4.85 g of compound 2-1-3, yield: 86%. MS: 282.44.

[0143] Synthesis of compound 2-1-5:

[0144] Accurately weigh compound 2-1-3 (4.51 g, 16 mmol), compound 2-1-4 (1.95 g, 8 mmol), potassium carbonate (4.42 g, 32 mmol), and [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.12, 0.16 mmol) into a 250 mL three-necked flask. Add 50 mL of toluene, 20 mL of water, and 10 mL of ethanol. After purging with nitrogen three times, the mixture is heated to 80 °C and reacted for 12 h. Cool to room temperature, add ethyl acetate, and separate the liquid phase. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 10:1 (v / v)) to give approximately 2.65 g of compound 2-1-5, yield: 84%. MS: 394.32.

[0145] Synthesis of compound 2-1-6:

[0146] Accurately weigh compound 2-1-5 (1.97 g, 5 mmol) and 20 mL of N,N-dimethylformamide into a 100 mL three-necked flask. Cool to -10 °C, then slowly add N-bromosuccinimide (N,N-dimethylformamide solution) (1.78 g, 10 mmol) dropwise, maintaining the temperature below -10 °C, and react for 2 h. Allow to rise naturally to room temperature, pour the reaction solution into water, precipitate the solid, filter, and purify the crude product by slurrying with methanol to give approximately 2.21 g of compound 2-1-6, yield: 80%. MS: 552.63.

[0147] Synthesis of polymer (2-1):

[0148] Accurately weigh compound 2-1-6 (0.55 g, 1 mmol) and compound 2-1-7 (0.90 g, 1 mmol) into a 100 mL three-necked flask. Add toluene (15 mL), purge with nitrogen for 5 min, then add tetra(triphenylphosphine)palladium (0.069 g, 0.06 mmol), purge with nitrogen for another 10 min, and stir at 110 °C for 20 h. Cool to room temperature, add methanol to precipitate the solid, filter to obtain the crude product, and purify the crude product by Soxhlet extraction (using hexane, acetone, and chlorobenzene sequentially) and column chromatography to obtain approximately 0.59 g of polymer (2-1), yield: 61%. The Mn content was 21.3 kDa, and the PDI was 2.1.

[0149] Example 2: Synthesis of polymer (2-2)

[0150]

[0151] Synthesis of polymer (2-2):

[0152] Accurately weigh compound 2-1-6 (0.55 g, 1 mmol) and compound 2-2-1 (0.94 g, 1 mmol) into a 100 mL three-necked flask. Add toluene (15 mL), purge with nitrogen for 5 min, then add tetrakis(triphenylphosphine)palladium (0.069 g, 0.06 mmol), purge with nitrogen for another 10 min, and stir at 110 °C for 20 h. Cool to room temperature, add methanol to precipitate the solid, filter to obtain the crude product, and purify the crude product by Soxhlet extraction (using hexane, acetone, and chlorobenzene sequentially) and column chromatography to obtain approximately 0.52 g of polymer 2-2. Yield: 52%. Mn was 22.9 kDa, and PDI was 1.8.

[0153] Example 3: Synthesis of polymer (2-20)

[0154]

[0155] Synthesis of compound 2-20-2:

[0156] Accurately weigh compound 2-20-1 (6.38 g, 20 mmol), compound 2-1-2 (5.59 g, 22 mmol), potassium acetate (3.92 g, 40 mmol), tris(dibenzylacetone)dipalladium (0.12 g, 0.2 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.19 g, 0.4 mmol) into a 250 mL three-necked flask. Add 70 mL of dioxane, purge with nitrogen three times, and then heat to 105 °C and react for 12 h. Cool to room temperature, and remove excess solvent by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 9:1 (v / v)) to give approximately 6 g of compound 2-20-2, yield: 82%. MS: 366.60.

[0157] Synthesis of compound 2-20-3:

[0158] Accurately weigh compound 2-20-2 (5.86 g, 16 mmol), compound 2-1-4 (1.95 g, 8 mmol), potassium carbonate (4.42 g, 32 mmol), and [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.12 g, 0.16 mmol) into a 250 mL three-necked flask. Add 60 mL of toluene, 24 mL of water, and 12 mL of ethanol. After purging with nitrogen three times, the mixture is heated to 80 °C and reacted for 12 h. Cool to room temperature, add ethyl acetate, and separate the liquid phase. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 12:1 (v / v)) to give approximately 3.4 g of compound 2-20-3, yield: 76%. MS: 562.55.

[0159] Synthesis of compound 2-20-4:

[0160] Accurately weigh 2.82 g (5 mmol) of compound 2-20-3 and 30 mL of N,N-dimethylformamide into a 100 mL three-necked flask. Cool to -10 °C, then slowly add 1.78 g (10 mmol) of N-bromosuccinimide (N,N-dimethylformamide solution) dropwise, maintaining the temperature below -10 °C, and react for 2 h. Allow to rise naturally to room temperature, pour the reaction solution into water, precipitate the solid, filter, and purify the crude product by slurrying with methanol to give approximately 2.56 g of compound 2-20-4, yield: 71%. MS: 720.94.

[0161] Synthesis of polymer (2-20):

[0162] Accurately weigh compound 2-20-4 (0.72 g, 1 mmol) and compound 2-2-1 (0.94 g, 1 mmol) into a 100 mL three-necked flask, dissolve in toluene (15 mL), purge with nitrogen for 5 min, add tetrakis(triphenylphosphine)palladium (0.069 g, 0.06 mmol), purge with nitrogen for another 10 min, stir at 110 °C for 20 h, cool to room temperature, add methanol to precipitate the solid, filter to obtain the crude product, and purify the crude product by Soxhlet extraction (using hexane, acetone, chlorobenzene sequentially) and column chromatography to obtain approximately 0.62 g of polymer (2-20). Yield: 53%. Mn: 24.7 kDa, PDI: 1.9.

[0163] Example 4: Synthesis of polymer (2-38)

[0164]

[0165] Synthesis of compound 2-38-2:

[0166] Accurately weigh compound 2-38-1 (4.7 g, 20 mmol), compound 2-1-2 (5.59 g, 22 mmol), potassium acetate (3.92 g, 40 mmol), tris(dibenzylacetone)dipalladium (0.12 g, 0.2 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.19 g, 0.4 mmol) into a 250 mL three-necked flask. Add 70 mL of dioxane, purge with nitrogen three times, and then heat to 105 °C and react for 12 h. Cool to room temperature, and remove excess solvent by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 8:1 (v / v)) to give approximately 4.5 g of compound 2-38-2, yield: 80%. MS: 282.75.

[0167] Synthesis of compound 2-38-3:

[0168] Accurately weigh compound 2-38-2 (4.5 g, 16 mmol), compound 2-1-4 (1.95 g, 8 mmol), potassium carbonate (4.42 g, 32 mmol), and [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.12 g, 0.16 mmol) into a 250 mL three-necked flask. Add 60 mL of toluene, 24 mL of water, and 12 mL of ethanol. After purging with nitrogen three times, the mixture is heated to 80 °C and reacted for 12 h. Cool to room temperature, add ethyl acetate, and separate the liquid phase. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 12:1 (v / v)) to give approximately 2.24 g of compound 2-38-3, yield: 71%. MS: 394.98.

[0169] Synthesis of compound 2-38-4:

[0170] Accurately weigh 1.97 g (5 mmol) of compound 2-38-3 and 20 mL of N,N-dimethylformamide into a 100 mL three-necked flask. Cool to -10 °C, then slowly add 1.78 g (10 mmol) of N-bromosuccinimide (N,N-dimethylformamide solution) dropwise, maintaining the temperature below -10 °C, and react for 2 h. Allow to rise naturally to room temperature, pour the reaction solution into water, precipitate the solid, filter, and purify the crude product by slurrying with methanol to give approximately 2.18 g of compound 2-38-4, yield: 79%. MS: 552.48.

[0171] Synthesis of polymer (2-38):

[0172] Accurately weigh compound 2-38-4 (0.55 g, 1 mmol) and compound 2-2-1 (0.94 g, 1 mmol) into a 100 mL three-necked flask, dissolve in toluene (15 mL), purge with nitrogen for 5 min, add tetrakis(triphenylphosphine)palladium (0.069 g, 0.06 mmol), purge with nitrogen for another 10 min, stir at 110 °C for 20 h, cool to room temperature, add methanol to precipitate the solid, filter to obtain the crude product, and purify the crude product by Soxhlet extraction (using hexane, acetone, chlorobenzene in sequence) and column chromatography to obtain approximately 0.46 g of polymer (2-38), yield: 46%. Mn is 20.1 kDa, PDI is 2.0.

[0173] Example 5: Synthesis of polymers (1-10)

[0174]

[0175] Accurately weigh compound 1-10-1 (0.66 g, 1 mmol) and compound 2-1-7 (0.90 g, 1 mmol) into a 100 mL three-necked flask, dissolve in toluene (15 mL), purge with nitrogen for 5 min, add tetrakis(triphenylphosphine)palladium (0.069 g, 0.06 mmol), purge with nitrogen for another 10 min, stir at 110 °C for 20 h, cool to room temperature, add methanol to precipitate the solid, filter to obtain the crude product, and purify the crude product by Soxhlet extraction (using hexane, acetone, chlorobenzene sequentially) and column chromatography to obtain approximately 0.66 g of polymer (1-10). Yield: 62%. Mn: 21.6 kDa, PDI: 1.7.

[0176] OPV device fabrication and characterization

[0177] The fabrication process of the OPV device comprising the above-described polymer will be described in detail below through specific device embodiments. Figure 1 As shown, the OPV device structure is as follows: Indium Tin Oxide (ITO) / PEDOT:PSS / Active Layer / PDINN / Ag

[0178] The device in Example 1 was prepared through the following steps:

[0179] (1) First, clean the ITO conductive glass with detergent, rinse it clean, and then use deionized water, acetone and isopropanol for ultrasonic cleaning for 15 minutes. Then, blow it dry with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0180] (2) Using PEDOT:PSS (Clevios) on ITO conductive glass TM P VP Al 4083) is an anode buffer layer material for spin-coating an anode buffer layer. The specific operation is as follows: PEDOT:PSS is uniformly spin-coated onto ITO in air at a spin speed of 3000-4000 rpm, and then dried at 150℃ for 15 min to obtain an anode buffer layer with a thickness of 20 nm.

[0181] (3) A photoactive layer is spin-coated on the anode buffer layer, wherein the photoactive layer material includes a donor material and an acceptor material. The donor material is selected from polymers (1-10) and (2-1), and the acceptor material is selected from (3-15). The mass ratio of polymers (1-10): (2-1): (3-15) is 0.8:0.2:1.2. The specific operation steps are as follows: the photoactive layer material is dissolved in chloroform in a glove box (inert gas atmosphere) to prepare a solution (concentration of 16 mg / mL) and uniformly spin-coated on the anode buffer layer. The spin-coating speed is 2500-4000 rpm / min to obtain a photoactive layer with a thickness of 100 nm.

[0182] (4) PDINN is spin-coated onto the photoactive layer as a cathode buffer layer material. The specific operation steps are as follows: after heat annealing on a hot table at 100°C for 10 min, PDINN is uniformly spin-coated onto the active layer. The spin-coating speed is 1800-4000 rpm / min to obtain a cathode buffer layer with a thickness of 5 nm.

[0183] (5) A cathode layer is prepared on the cathode buffer layer using Ag as the cathode material. The specific operation steps are as follows: under high vacuum (1×10⁻⁶), the cathode layer is prepared using Ag as the cathode material. -6 Ag is deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of 100 nm.

[0184] (6) Finally, the device is encapsulated in a nitrogen glove box with UV-cured resin.

[0185] Preparation of Device Examples 2-4 and Comparative Device Example 1

[0186] Device Examples 2-4 and Device Comparative Example 1 are identical to Device Example 1 except for the selection of photoactive layer material and mass ratio. The specific selection of photoactive layer material and mass ratio are shown in Table 1.

[0187] Table 1

[0188] Device Example 1 (1-10)：(2-1)：(3-15) 0.8:0.2:1.2 Device Example 2 (1-10)：(2-2)：(3-15) 0.8:0.2:1.2 Device Example 3 (1-10)：(2-20)：(3-15) 0.8:0.2:1.2 Device Example 4 (1-10)：(2-38)：(3-15) 0.8:0.2:1.2 Device Comparison Example 1 (1-10)：(3-15) 1:1.2

[0189] The performance of the prepared organic solar cell device was tested. Under the illumination of AM1.5G standard light from a solar simulator (SS-F5-3A), the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 2.

[0190] Table 2

[0191] Device Example 1 (1-10)：(2-1)：(3-15) 17.29 Device Example 2 (1-10)：(2-2)：(3-15) 17.50 Device Example 3 (1-10)：(2-20)：(3-15) 16.87 Device Example 4 (1-10)：(2-38)：(3-15) 16.54 Device Comparison Example 1 (1-10)：(3-15) 15.92

[0192] Device Examples 5-9 and Device Comparative Example 2 are identical to Device Example 1 except for the selection of photoactive layer material and ratio. The specific selection and ratio of photoactive layer material are described in Table 3.

[0193] Table 3

[0194] Device Example 5 (1-10)：(2-2)：(3-17) 0.9:0.1:1.2 Device Example 6 (1-10)：(2-2)：(3-17) 0.8:0.2:1.2 Device Example 7 (1-10)：(2-2)：(3-17) 0.7:0.3:1.2 Device Example 8 (1-10)：(2-2)：(3-17) 0.6:0.4:1.2 Device Example 9 (1-10)：(2-2)：(3-17) 0.5:0.5:1.2 Device Comparison Example 2 (1-10)：(3-17) 1:1.2

[0195] The organic solar cell device was tested for performance. Under the standard light of AM1.5G from the solar simulator (SS-F5-3A), the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 4.

[0196] Table 4

[0197]

[0198]

[0199] As can be seen from the comparison between device examples 1-4 and device comparative example 1, and between device examples 5-9 and device comparative example 2, the device performance is significantly improved compared to the monomolecular donor material according to the donor mixture of the present invention. This is because: 1. The dual polymer donors of the present invention have the same polymer backbone, thus exhibiting excellent miscibility; 2. The polymer side chain in general formula (II) is selected from carboxylic acid ester groups. Carboxylic acid ester groups substituted with thiophene are easy to prepare and inexpensive. Furthermore, the carboxylic acid ester group can react with adjacent groups (benzodithiophene or...) The formation of non-covalent bonds between the S atoms on the surface helps to obtain a planar molecular structure and strong aggregation behavior. When used as a third component in the polymer (1) and acceptor system, the photoactive layer exhibits high charge mobility and suitable phase separation size and aggregation morphology, thereby improving the photoelectric conversion efficiency of the device.

[0200] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

Claims

1. An organic solar cell device, the organic solar cell device comprising at least a first electrode, a second electrode, and a photoactive layer located between the first electrode and the second electrode, the photoactive layer comprising a donor material and an acceptor material, characterized in that: The donor material comprises at least one polymer 1 as shown in formula (I) and at least one polymer 2 as shown in formula (II): （I）， (II); in, X is selected from S; R1 is selected from -H; Each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, and cyano groups; Each time R3 appears, it is independently selected from a straight-chain alkyl group having 1-20 carbon atoms, or a branched or cyclic alkyl group having 3-20 carbon atoms; Each time R4 appears, it is independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms; Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms; The receptor material is selected from the structure shown in formula (III) or formula (IV): (III), (IV); in, R6 and R7, each time they appear, are independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms, branched or cyclic alkoxy groups having 3-20 carbon atoms, and branched or cyclic alkylthio groups having 3-20 carbon atoms. Each time R8 and R9 appear, they are independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms. R 10 R 11 R 12 R 13 R 14 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, or -CF3; R 15 Each occurrence is independently selected from -H; n is the number of repeating units and is an integer greater than 1.

2. The organic solar cell device according to claim 1, characterized in that: The polymer 1 is selected from formula (I-1), (I-2), or (I-3): ； Each time R4 appears, it is independently selected from straight-chain alkyl groups having 1-16 carbon atoms, branched or cyclic alkyl groups having 3-16 carbon atoms; And / or, polymer 2 is selected from formula (II-1) or (II-2): ； R5 is selected from straight-chain alkyl groups having 1-16 carbon atoms or branched alkyl groups having 3-16 carbon atoms each time it appears.

3. The organic solar cell device according to claim 2, characterized in that: Each occurrence of R2 is independently selected from -H, -D, -F, and -Cl; Each time R3 appears, it is independently selected from straight-chain alkyl groups having 1-16 carbon atoms or branched alkyl groups having 3-16 carbon atoms.

4. The organic solar cell device according to claim 2, characterized in that: The mass ratio of polymer 1 to polymer 2 is selected from 5:5 to 9:

1.

5. An organic solar cell device according to claim 1, characterized in that: The polymer 1 is selected from any of the following structures: ； And / or, the polymer 2 is selected from any of the following structures: 。 6. The organic solar cell device according to claim 1, characterized in that: The receptor material is selected from any of the following structures: 。 7. A polymer, characterized in that: The polymer is selected from the structure of formula (II): (II); in, X is selected from S; R1 is selected from -H; Each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, and cyano groups; Each occurrence of R3 is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, or branched or cyclic alkyl groups having 3-20 carbon atoms; Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms; n is the number of repeating units and is an integer greater than 1.

8. The polymer according to claim 7, characterized in that: The polymer is selected from the following structures: (II-1)。 9. A mixture, characterized in that: The mixture comprises at least one polymer 1 of formula (I) and at least one polymer 2 of formula (II): （I）， (II); in, X is selected from S; R1 is selected from -H; Each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, and cyano groups; Each occurrence of R3 is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, or branched or cyclic alkyl groups having 3-20 carbon atoms; Each time R4 appears, it is independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms; Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms; n is the number of repeating units and is an integer greater than 1.

10. The mixture according to claim 9, characterized in that: The mixture also contains at least one structure as shown in formula (III) or formula (IV): (III) (IV) in: R6 and R7, each time they appear, are independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched or cyclic alkyl groups having 3-20 carbon atoms, branched or cyclic alkoxy groups having 3-20 carbon atoms, and branched or cyclic alkylthio groups having 3-20 carbon atoms. Each time R8 and R9 appear, they are independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms. R 10 R 11 R 12 R 13 R 14 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, or -CF3; R 15 Each occurrence is independently selected from -H; n is the number of repeating units and n is an integer greater than 1.

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