Organic photovoltaic polymer material and application thereof

Abstract

The invention relates to the field of organic photovoltaic materials, in particular to an organic photovoltaic polymer material and application thereof. The invention provides a polymer structure as shown in a general formula (I), and the solubility of the polymer in a non-halogen solvent is optimized by regulating and controlling a branching site of a connecting unit # imgabs0 # alkyl chain, so that the polymer can be applied to preparation of a large-area organic photovoltaic device and shows excellent photoelectric conversion performance.

Description

Technical Field

[0001] The present invention relates to the field of organic photovoltaic materials, and particularly relates to an organic photovoltaic polymer material and its application. Background Art

[0002] Organic photovoltaic (OPV) cells are a new type of photovoltaic cells that use organic semiconductor materials to convert the absorbed sunlight energy into electrical energy. They have the characteristics of light weight and flexibility. In the past 20 years, with the progress of process levels and the emergence of new active layer materials, the device efficiency of organic photovoltaic cells has been continuously improved, exceeding 20%, showing great application potential.

[0003] The device structure of OPV generally consists of five parts: a transparent substrate (such as glass, plastic, etc.), a transparent electrode (such as indium tin oxide (ITO), etc.), an active layer, a metal electrode (such as Al, Ag, etc.), and an interfacial modification layer between the electrode and the active layer. Among them, the active layer is generally composed of a blend of an electron donor and an electron acceptor. The energy conversion process of OPV cells is as follows. When sunlight passes through the transparent substrate and the electrode and enters the active layer, the donor-acceptor material absorbs photons with energy greater than its bandgap energy. Electrons are excited from the highest occupied molecular orbital (HOMO) and jump to the lowest unoccupied molecular orbital (LUMO), and at the same time, corresponding holes are generated at the HOMO. Due to the relatively small relative dielectric constant of organic materials, the electrons and holes at this time exist in the form of bound excitons. Then, the excitons diffuse to the donor-acceptor interface, and under the drive of the energy level difference, the excitons dissociate to achieve charge separation. Subsequently, under the action of the built-in electric field, the free holes and electrons respectively transport along the continuous channels of the donor and acceptor materials to reach the anode and cathode, and are collected by the electrodes and output to the external circuit to form a current.

[0004] According to the principle of OPV technology, the properties of the photoactive layer play a decisive role in the performance of organic photovoltaic devices. Therefore, the development of new polymer donor materials plays an important role in promoting the technological development of OPV. Benzodithiophene (BDT) has a large planar conjugated structure, which is conducive to achieving π-π stacking, improving the mobility, and various substituents can be modified on the central benzene ring of BDT to regulate the molecular properties. Since 2008, when the Yang Yang research group copolymerized BDT with different structural units to regulate the energy level and absorption, a batch of polymer donor materials have been constructed. Since then, the polymer donor materials based on BDT have developed rapidly, promoted the continuous breakthrough of the device efficiency in the OPV field, and become the most important type of polymer electron donor containing fused-ring thiophene structures at present. Currently, the polymer donor materials based on BDT units include but are not limited to: two-dimensional conjugated polymer PBQx-F formed by introducing thiophene on the upper and lower sides of benzodithiophene reported by the Hou Jianhui research group, polymer D18 developed by the Ding Liming research group, etc. However, currently most of the highly efficient polymer donor materials face the problem of poor solubility in non-halogen solvents, resulting in poor efficiency when preparing large-area organic photovoltaic devices. Therefore, the development of highly efficient polymer donor materials suitable for the preparation of large-area devices is of crucial significance for the industrial development of OPV. Summary of the Invention

[0005] In order to improve the problem that the existing polymer donor materials have poor solubility in non-halogen solvents, resulting in poor performance when preparing large-area organic photovoltaic devices, the purpose of the present invention is to provide a new type of organic photovoltaic polymer material, which improves the solubility of the polymer by modifying the alkyl chain, thereby realizing the preparation in large-area organic photovoltaic devices and showing excellent optoelectronic properties.

[0006] The present invention provides an organic photovoltaic polymer material, which comprises a structure shown in the general formula (I):

[0007]

[0008] Wherein:

[0009] Each occurrence of R1 and R2 is independently selected from a straight-chain alkyl or branched-chain alkyl having 1-10 C atoms that is unsubstituted or substituted by R # ;

[0010] Each occurrence of R3 and R4 is independently selected from -H, -D, -F, -Cl, -CF3, -CN, a straight-chain alkyl or branched-chain alkyl having 1-10 carbon atoms that is unsubstituted or substituted by R # ;

[0011] Each occurrence of R5 is independently selected from a straight-chain alkyl or branched-chain alkyl having 1-10 C atoms that is unsubstituted or substituted by R #A straight-chain or branched alkyl group having 1 to 20 carbon atoms and being substituted;

[0012] R # Each occurrence is independently selected from -D, -F, -Cl, or a cycloalkyl group having 3 to 10 carbon atoms;

[0013] Each occurrence of Y is independently selected from O, S, or Se;

[0014] Each occurrence of m is independently selected from 1, 2, or 3;

[0015] Each occurrence of R6 is independently selected from -H, -D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, -F, -Cl, an aromatic group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by combining the above groups;

[0016] n represents the number of repeating units and is selected from natural numbers greater than or equal to 2.

[0017] The present invention further relates to a mixture, which comprises the organic photovoltaic polymer material as described above.

[0018] The present invention further relates to a composition, which comprises the organic photovoltaic polymer material or mixture as described above and at least one organic solvent. Preferably, the organic solvent is selected from non-halogen organic solvents.

[0019] The present invention further relates to an organic photovoltaic device, which comprises a cathode, an anode, and a photoactive layer located between the cathode and the anode, and the photoactive layer comprises the organic photovoltaic polymer material or mixture as described above, or is prepared from the above composition.

[0020] Advantages of the present invention:

[0021] An organic photovoltaic polymer provided by the present invention optimizes the solubility of the polymer in non-halogen solvents by regulating the branching sites of the linking unit alkyl chains (reason: by regulating the branching position, a larger intramolecular steric hindrance is generated in the alkane chain, thereby increasing the solubility of the molecule), enabling it to be applied to the preparation of large-area organic photovoltaic devices and showing excellent optoelectronic conversion performance. Description of the drawings

[0022] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0023] Figure 1 is a schematic structural diagram of a large-area OPV device module of the present application.

[0024] Figure 2 is a partial structural cross-sectional view of a large-area OPV device module of the present application.

[0025] Wherein: 10 - substrate, 101 - first electrode layer, 102 - anode buffer layer, 103 - photoactive layer, 104 - cathode buffer layer, 105 - cathode layer, 20 - upper cover layer, 30 - adhesive layer

[0026] Figure 3 is a GPC spectrum of the polymer (P11) described in Example 4 of polymer synthesis. Specific Embodiments

[0027] The following embodiments are provided to better further understand the present invention. They are not limited to the best embodiments, and do not limit the content and protection scope of the present invention. Any product that is the same as or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features falls within the protection scope of the present invention.

[0028] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0029] In the present invention, organic photovoltaic device, organic photovoltaic cell, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0030] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0031] In the present invention, when the same group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. The six Rs on the benzene ring may be the same as or different from each other.

[0032] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0033] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of quinoline is 10, the number of ring atoms of a thienyl group is 5, the number of ring atoms of thienothiophene is 8, and the number of ring atoms of pyrazine is 6.

[0034] In the present invention, an "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group. In other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated through carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated through carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated through carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as the aromatic groups of the present application. Preferably, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl and their derivatives.

[0035] In the present invention, a "heteroaromatic group" is a heteroaromatic ring or its derivative containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, the heteroaromatic group can be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated through carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic fused-ring. Preferably, it is selected from heteroaromatic groups having 5-30 ring atoms; further preferably, it is selected from heteroaromatic groups having 5-10 ring atoms. The heteroaromatic groups include but are not limited to: thienyl, furyl, selenophenyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, benzothienyl, benzofuryl and their derivatives.

[0036] In the present invention, a "linear alkyl group having 1-10 carbon atoms" is selected from methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), n-pentyl (-C5H 11 ), n-hexyl (-C6H 13 ), n-heptyl (-C7H 15 ), n-octyl (-C8H 17 ), n-nonyl (-C9H 19 ), n-decyl (-C 10 H 21 ).

[0037] In the present invention, a "branched alkyl group having 3-10 carbon atoms" is selected from isopropyl, sec-butyl, tert-butyl, a branched alkyl group having 5 carbon atoms, a branched alkyl group having 6 carbon atoms, a branched alkyl group having 7 carbon atoms, a branched alkyl group having 8 carbon atoms, a branched alkyl group having 9 carbon atoms, a branched alkyl group having 10 carbon atoms.

[0038] In the present invention, the "cycloalkyl group having 3 to 10 carbon atoms" is selected from cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, adamantyl, etc., but is not limited thereto.

[0039] In the present invention, when the connection site is not specified in the group, it means that any optional connection site in the group can be used as the connection site.

[0040] In the present invention, the phrase "independently selected from" for one or more groups means that when one or more groups appear simultaneously and at multiple positions in the compound, they are all independently selected and can be the same or different.

[0041] In the process of describing the structural elements of the present invention, words such as "comprising" or "including" used in the present invention mean that the devices or materials appearing before this word cover the devices or materials listed after this word and their equivalents, without excluding other devices or materials.

[0042] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by terms such as "upper", "lower", "between layers", etc. is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the organic solar cell device is usually placed during use, or the orientation or positional relationship commonly understood by those skilled in the art. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present invention.

[0043] In the present invention, "their combinations", "any of their combinations", "any combination mode thereof", "combination", etc. include all suitable combination modes of any two, any three, or any three or more groups among the listed groups.

[0044] In the present invention, words such as "further", "even further", "especially", etc. are used for descriptive purposes and indicate differences in content, but should not be construed as a limitation to the protection scope of the present invention.

[0045] In the present invention, "optionally", "optional", "option", mean that it can be either present or absent, that is, it refers to any one of the two alternative options of "present" or "absent". If "optional" appears multiple times in a technical solution, without special instructions and without contradictions or mutual constraints, each "optional" is independent.

[0046] In the present invention, for the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open-ended technical solution containing the listed features.

[0047] The first aspect of the present invention relates to an organic photovoltaic polymer material, comprising a structure represented by the general formula (I):

[0048]

[0049] Wherein:

[0050] Each occurrence of R1 and R2 is independently selected from unsubstituted or R-substituted linear or branched alkyl groups having 1 to 10 carbon atoms; #

[0051] Each occurrence of R3 and R4 is independently selected from -H, -D, -F, -Cl, -CF3, -CN, unsubstituted or R-substituted linear or branched alkyl groups having 1 to 10 carbon atoms; #

[0052] Each occurrence of R5 is independently selected from unsubstituted or R-substituted linear or branched alkyl groups having 1 to 20 carbon atoms; #

[0053] R # Each occurrence is independently selected from -D, -F, -Cl, or cycloalkyl groups having 3 to 10 carbon atoms;

[0054] Each occurrence of Y is independently selected from O, S, or Se;

[0055] Each occurrence of m is independently selected from 1, 2, or 3;

[0056] Each occurrence of R6 is independently selected from -H, -D, linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, -F, -Cl, aromatic groups having 6 to 10 carbon atoms, heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combining the above groups;

[0057] n represents the number of repeating units and is selected from natural numbers greater than or equal to 2.

[0058] Furthermore, the organic photovoltaic polymer material comprises structures represented by general formula (II-1), (II-2), or (II-3):

[0059]

[0060] In one embodiment, Y is selected from S.

[0061] In another embodiment, Y is selected from Se.

[0062] In one embodiment, each occurrence of R1 is independently selected from unsubstituted or R-substituted linear alkyl groups having 2 to 6 carbon atoms. #

[0063] Furthermore, R1 is selected from -C2H5, -C4H9, or -C6H​​​​13 。

[0064] In one embodiment, each occurrence of R2 is independently selected from an unsubstituted or R # -substituted straight-chain alkyl having 4 to 8 carbon atoms.

[0065] Further, R2 is selected from -C4H9 or -C6H 13 or -C8H 17 。

[0066] In a specific embodiment, R1 is selected from -C2H5 and R2 is selected from -C4H9.

[0067] In a specific embodiment, R1 is selected from -C4H9 and R2 is selected from -C6H 13 。

[0068] In a specific embodiment, R1 is selected from -C6H 13 , and R2 is selected from -C8H 17 。

[0069] In one embodiment, each occurrence of R3 is independently selected from -H, -D, -CH3, -CD3, -C2H5, -C4H9, -C6H 13 , -F, -Cl, -CF3 or -CN.

[0070] In one embodiment, each occurrence of R4 is independently selected from -H, -D, -CH3, -CD3, -C2H5, -C4H9, -C6H 13 , -F, -Cl, -CF3 or -CN.

[0071] In an alternative embodiment, R4 is selected from -H, -D, -CH3, -CD3, -F or -Cl; and R3 is selected from -H.

[0072] In one embodiment, each occurrence of R5 is independently selected from an unsubstituted or -D-substituted straight-chain or branched-chain alkyl having 1 to 20 carbon atoms.

[0073] Further, each occurrence of R5 is independently selected from an unsubstituted or -D-substituted branched-chain alkyl having 8 to 20 carbon atoms.

[0074] In a specific embodiment, each occurrence of R5 is independently selected from

[0075] In one embodiment, R6 is selected from -H, methyl, ethyl or methoxy.

[0076] In a specific embodiment, the organic photovoltaic polymer material according to the present invention includes the following structure, but is not limited thereto:

[0077]

[0078]

[0079] In one embodiment, for the polymer according to the present invention, the number-average molecular weight (Mn) of the polymer is selected from the range of 10,000 to 1,000,000. Further, the number-average molecular weight (Mn) of the polymer is selected from the range of 10,000 to 100,000. Further, the number-average molecular weight (Mn) of the polymer is selected from the range of 20,000 to 60,000.

[0080] In one embodiment, for the polymer according to the present invention, the value range of the molecular weight distribution (PDI) of the polymer is preferably 1 to 10; more preferably 1 to 6; more preferably 1 to 4.

[0081] The second aspect of the present invention relates to a mixture comprising the organic photovoltaic polymer material as described in the first aspect.

[0082] Further, for the mixture according to the present invention, it further comprises another organic functional material, and the another organic functional material is selected from a photoactive layer donor material or a photoactive layer acceptor material.

[0083] Preferably, the another organic functional material is selected from a photoactive layer acceptor material.

[0084] Specifically, the photoactive layer acceptor can be selected from one or more of the following: ITIC configuration-based acceptor materials, including but not limited to: ITIC, ITIC-4F, ITIC-4Cl, ITCC, ITCC-Cl, etc.; Y-type acceptor materials, including but not limited to: Y6, L8-BO, BTP-eC9, N3, N4, Y6-O, BTP-H2, PY-IT, etc.; fullerene acceptor materials, including but not limited to: PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerenes, etc.

[0085] The third aspect of the present invention relates to a composition, which comprises the organic photovoltaic polymer material as described in the first aspect or the mixture as described in the second aspect, and at least one organic solvent.

[0086] The organic solvent is preferably selected from: tetralin, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decalin, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, chloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, hexamethylphosphoramide, or a mixture of two or more thereof.

[0087] In an alternative embodiment, the organic solvent is preferably a halogen-free solvent. Further, the organic solvent is selected from: 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, 2,4-dimethylanisole, 1-methylnaphthalene, or a mixture of two or more thereof.

[0088] In a specific embodiment, the organic solvent is selected from toluene, o-xylene or p-xylene.

[0089] The fourth aspect of the present invention relates to an organic photovoltaic device, which comprises a cathode, an anode, and a photoactive layer located between the cathode and the anode. The photoactive layer material comprises the organic photovoltaic polymer material as described in the first aspect, or the mixture as described in the second aspect, or is prepared from the composition as described in the third aspect.

[0090] Further, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material, and the photoactive layer donor material comprises the organic photovoltaic polymer material as described in the first aspect.

[0091] The receptor material can be selected from one or more of the following, but is not limited to: ITIC configuration-based receptor materials, including but not limited to: ITIC, ITIC-4F, ITIC-4Cl, ITCC, ITCC-Cl, etc.; Y-type receptor materials, including but not limited to: Y6, L8-BO, BTP-eC9, N3, N4, Y6-O, BTP-H2, PY-IT, etc.; fullerene receptor materials, including but not limited to: PC61BM (methyl [6,6]-phenyl C61 butyrate), PC71BM (methyl [6,6]-phenyl C71 butyrate), indene-containing fullerenes, etc. For details, please refer to Chem. Rev. 2022, 122, 18, 14180–14274.

[0092] The preparation method of the photoactive layer material solution is as follows: The photoactive layer donor material and the receptor material are dissolved in an organic solvent according to a certain mass ratio, and stirred evenly to obtain a fully dissolved photoactive layer solution. The further definition of the organic solvent is as described above.

[0093] The above solution is used to prepare the photoactive layer by a printing or coating method. The printing or coating method can be, but is not limited to, inkjet printing, gravure printing, spraying, letterpress printing, screen printing, dip coating, spin coating, knife coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, slot die coating, etc. Preferred are slot coating, spin coating and inkjet printing.

[0094] The mass ratio of the photoactive layer donor material to the receptor material in the organic solvent is preferably: 1:0.8 to 1:1.5; further, the mass ratio of the photoactive layer donor material to the receptor material in the organic solvent is preferably: 1:1 to 1:1.5; the mass ratio of the photoactive layer donor material to the receptor material in the organic solvent is preferably: 1:1 to 1:1.2.

[0095] The concentration of the photoactive layer donor material in the organic solvent is preferably 3 to 15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4 to 10 mg / mL.

[0096] Furthermore, the photoactive layer material solution can further include additives for adjusting viscosity, film-forming performance, adhesion improvement, etc. The additives can be selected from, 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), 1,3,5-tribromobenzene (TBB), etc., but are not limited thereto.

[0097] At least one of the anode and the cathode is transparent or semi-transparent to facilitate the incidence of light. 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, etc.; conductive nanomaterials such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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 a multilayer structure such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al∶Li, Al∶BaF2, and Al∶BaF2∶Ba, etc., but not limited thereto.

[0098] In one embodiment, the organic photovoltaic device is stacked with an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode in sequence from bottom to top, and the photoactive layer contains the organic photovoltaic polymer material as described above.

[0099] Preferably, the cathode buffer layer material can be selected from metal complexes with low work functions, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited thereto.

[0100] The anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium pentoxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, etc., but not limited thereto.

[0101] It should be noted that in order to improve the performance of the organic photovoltaic cell device, the organic photovoltaic cell may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0102] Furthermore, the organic photovoltaic cell also includes a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the photoactive layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the photoactive layer.

[0103] In one embodiment, as the substrate, a substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness can be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include a film in a single-layer or multi-layer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), polyimide (PI), parylene, etc., but is not limited thereto. Substrates commonly used in organic photovoltaic cells can also be used.

[0104] The organic photovoltaic cell according to the present invention is mainly used in the fields of indoor photovoltaics, wearable devices, intelligent Internet of Things, smart home, smart agriculture, building photovoltaics, new energy vehicles, etc.

[0105] Polymer synthesis examples

[0106] The following examples facilitate a better understanding of the disclosure of the present invention and are not intended to limit it in any way. Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are all prior art and can be obtained from commercial sources unless otherwise specified.

[0107] Synthesis of monomer M-1:

[0108]

[0109] Synthesis of compound 1-3:

[0110] Accurately weigh compound 1-1 (4.0 g, 10.0 mmol) and compound 1-2 (22.2 g, 40.0 mmol) and dissolve them in anhydrous toluene (40 mL) in sequence. Replace nitrogen three times, then add tetrakis(triphenylphosphine)palladium (0.23 g, 0.2 mmol), replace nitrogen three times, and react at 110 °C for 2 h. Stop heating after confirming the reaction is complete. After the reaction is cooled to room temperature, pour the reaction solution into an aqueous potassium fluoride solution for quenching and extract with ethyl acetate. Dry the combined organic phases with anhydrous MgSO4, rotary evaporate under reduced pressure to remove the excess solvent, and perform silica gel column chromatography with the eluent of PE:DCM = 1:1 (volume ratio) to obtain about 4.33 g of compound 1-3, with a yield of 56.1%. MS: 771.92.

[0111] Synthesis of compound M-1:

[0112] Accurately weigh compound 1-3 (2.0 g, 2.59 mmol) and dissolve it in chloroform (20 mL). At -5 °C, add NBS (922 mg, 5.18 mmol) dissolved in chloroform (20 mL) dropwise to the reaction solution, and stir while maintaining the temperature and avoiding light for 2 h. After the reaction is completed, pour the reaction solution into an aqueous sodium sulfite solution for quenching and extract with dichloromethane. Dry the combined organic phases over anhydrous MgSO4, distill off the excess solvent under reduced pressure, and perform silica gel column chromatography with the eluent being PE:DCM = 1:3 (volume ratio) to obtain approximately 1.5 g of compound M-1, with a yield of 62.2%. MS: 928.75.

[0113] Synthesis of monomer M-2:

[0114]

[0115] Synthesis of compound 2-2:

[0116] Accurately weigh compound 2-1 (16.6 g, 60 mmol), magnesium (1.73 g, 72 mmol), and one iodine granule and dissolve them in ultra-dry THF (20 mL). Replace nitrogen three times and react under reflux for 2 h. In another 100 mL reaction flask equipped with a dropping funnel, accurately weigh and add 3-bromothiophene (8.15 g, 50 mmol), 1,3-bis(diphenylphosphinopropane)nickel dichloride (271 mg, 0.5 mmol), and THF (20 mL). Carefully transfer the above-prepared Grignard reagent to a separatory funnel and slowly drip it into the reaction system. After dropping, heat up to reflux and react for 12 hours. After the reaction is completed, cool to room temperature, quench the reaction with dilute hydrochloric acid (2 M) and extract with ethyl acetate (40 mL × 2). Combine the organic phases and wash with saturated NaCl solution (50 mL). Dry the organic phases over anhydrous MgSO4, remove the organic solvent under reduced pressure, and perform silica gel column chromatography with the eluent being PE to obtain approximately 9.56 g of compound 2-2, with a yield of 68.1%. MS: 280.74.

[0117] Synthesis of compound 2-3:

[0118] Accurately weigh compound 2-2 (9.0 g, 32 mmol) and dissolve it in ultradry THF (90 mL). Replace nitrogen three times. Dropwise add n-BuLi (2.5 M, 25.2 mL, 63.6 mmol) at -70 °C. After stirring for 2 hours, at -70 °C, dropwise add tributyltin chloride (22.7 g, 69.6 mmol), keep the temperature and stir for 1 h, and then naturally return to room temperature and stir overnight. After the reaction is completed, pour the reaction solution into an aqueous potassium fluoride solution to quench the reaction and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, rotary evaporate under reduced pressure to remove the excess solvent, and obtain about 17.1 g of compound 2-3 with a yield of 93.7%. MS: 570.18.

[0119] Synthesis of compound 2-4:

[0120] Accurately weigh compound 1-1 (1.12 g, 2.8 mmol) and compound 2-3 (5.6 g, 9.8 mmol) and dissolve them successively in anhydrous toluene (11 mL). Replace nitrogen three times, then add tetrakis(triphenylphosphine)palladium (64 mg, 0.056 mmol), replace nitrogen three times, and react at 110 °C for 2 h. Stop heating after confirming the reaction is completed. After the reaction is cooled to room temperature, pour the reaction solution into an aqueous potassium fluoride solution to quench the reaction and extract with ethyl acetate. Dry the combined organic phases with anhydrous MgSO4, rotary evaporate under reduced pressure to remove the excess solvent, and perform silica gel column chromatography with the eluent PE:DCM = 5:1 (volume ratio) to obtain about 1.44 g of compound 2-4 with a yield of 64.4%. MS: 799.63.

[0121] Synthesis of compound M-2:

[0122] Accurately weigh compound 2-4 (1.2 g, 1.48 mmol) and dissolve it in chloroform (12 mL). At -5 °C, dropwise add NBS (527 mg, 2.96 mmol) dissolved in chloroform (12 mL) to the reaction solution, keep the temperature and stir in the dark for 2 h. After the reaction is completed, pour the reaction solution into an aqueous sodium sulfite solution to quench the reaction and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, distill under reduced pressure to remove the excess solvent, and perform silica gel column chromatography with the eluent PE:DCM = 1:2 (volume ratio) to obtain about 982 mg of compound M-2 with a yield of 69.3%. MS: 957.31.

[0123] Synthesis of monomer M-3

[0124]

[0125] Synthesis of compound 3-2:

[0126] Accurately weigh Compound 3-1 (2.0 g, 4.7 mmol) and Compound 2-3 (6.84 g, 12 mmol), dissolve them successively in anhydrous toluene (20 mL), displace nitrogen three times, then add tetrakis(triphenylphosphine)palladium (810 mg, 0.7 mmol), displace nitrogen three times, and refer to the synthesis of Compound 2-4 for subsequent synthesis steps to obtain about 2.31 g of Compound 3-2 with a yield of 59.4%. MS: 827.57.

[0127] Synthesis of Compound M-3:

[0128] Accurately weigh Compound 3-2 (1.5 g, 1.8 mmol) and dissolve it in chloroform (15 mL). At -5 °C, add NBS (0.65 g, 3.6 mmol) dissolved in chloroform (15 mL) dropwise to the reaction solution, keep warm and stir in the dark for 2 h. After the reaction is completed, pour the reaction solution into an aqueous sodium sulfite solution to quench the reaction and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, distill off the excess solvent under reduced pressure, perform silica gel mixing column chromatography, and the eluent is PE:DCM = 1:1 (volume ratio) to obtain about 1.23 g of Compound M-3 with a yield of 69.3%. MS: 985.70.

[0129] Synthesis of Monomer M-4

[0130]

[0131] Synthesis of Compound 4-2:

[0132] Accurately weigh Compound 4-1 (14.1 g, 60 mmol), magnesium (1.73 g, 72 mmol), and one iodine granule, dissolve them in ultra-dry THF (20 mL), displace nitrogen three times, and react under reflux for 2 h. In another 100 mL reaction flask equipped with a dropping funnel, accurately weigh and add 3-bromothiophene (8.15 g, 50 mmol), 1,3-bis(diphenylphosphino)propane dichloride (271 mg, 0.5 mmol), and THF (20 mL). Carefully transfer the above-prepared Grignard reagent to a separating funnel and slowly drop it into the reaction system. After dropping, heat up to reflux and react for 12 hours. After the reaction is completed, cool to room temperature, quench the reaction with dilute hydrochloric acid (2 M) and extract with ethyl acetate (40 mL × 2). Combine the organic phases and wash with saturated NaCl solution (50 mL). Dry the organic phases with anhydrous MgSO4, remove the organic solvent under reduced pressure, perform silica gel mixing column chromatography, and the eluent is PE to obtain about 8.89 g of Compound 4-2 with a yield of 74.3%. MS: 239.16.

[0133] Synthesis of Compound 4-3:

[0134] Accurately weigh compound 4-2 (8.0 g, 33.5 mmol) and dissolve it in ultradry THF (80 mL). Replace nitrogen three times. Dropwise add n-BuLi (2.5 M, 26.8 mL, 67 mmol) at -70 °C. After stirring for 2 hours, at -70 °C, dropwise add trimethyltin chloride (23.9 g, 73.7 mmol), keep the temperature and stir for 1 h, then naturally restore to room temperature and stir overnight. After the reaction is completed, pour the reaction solution into an aqueous potassium fluoride solution to quench and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, and remove the excess solvent by distillation under reduced pressure to obtain about 15.4 g of compound 4-3, with a yield of 87.2%. MS: 527.34.

[0135] Synthesis of compound 4-4:

[0136] Accurately weigh compound 4-3 (9.2 g, 17.5 mmol) and compound 1-1 (2.0 g, 5.0 mmol) and dissolve them successively in anhydrous toluene (20 mL). Replace nitrogen three times, then add tetrakis(triphenylphosphine)palladium (115 mg, 0.1 mmol) and replace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 2.40 g of compound 4-4, with a yield of 67.1%. MS: 714.83.

[0137] Synthesis of compound M-4:

[0138] Accurately weigh compound 4-4 (2.0 g, 2.8 mmol) and dissolve it in chloroform (20 mL). At -5 °C, dropwise add NBS (0.99 g, 5.6 mmol) dissolved in chloroform (20 mL) to the reaction solution, keep the temperature and stir in the dark for 2 h. After the reaction is completed, pour the reaction solution into an aqueous sodium sulfite solution to quench and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, remove the excess solvent by distillation under reduced pressure, and perform silica gel column chromatography with the eluent PE:DCM = 1:1 (volume ratio) to obtain about 1.49 g of compound M-4, with a yield of 61.0%. MS: 872.69.

[0139] Synthesis of monomer M-5

[0140]

[0141] Synthesis of compound 5-2:

[0142] Accurately weigh compound 5-1 (35.0 g, 120 mmol), magnesium (3.46 g, 144 mmol), and iodine (1 pellet), dissolve them in ultradry THF (40 mL), displace nitrogen three times, and react under reflux for 2 h. In another 250 mL reaction flask equipped with a dropping funnel, accurately weigh and add 3-bromothiophene (16.3 g, 100 mmol), 1,3-bis(diphenylphosphinopropane)nickel dichloride (542 mg, 1.0 mmol), and THF (40 mL). Carefully transfer the Grignard reagent prepared above to a separating funnel and slowly drip it into the reaction system. After dripping, heat up to reflux and react for 12 hours. After the reaction is completed, cool to room temperature, quench the reaction with dilute hydrochloric acid (2 M), and extract with ethyl acetate (80 mL × 2). Combine the organic phases, wash with saturated NaCl solution (100 mL). Dry the organic phase with anhydrous MgSO4, remove the organic solvent under reduced pressure, stir the sample on silica gel column chromatography, and use PE as the eluent to obtain about 21.6 g of compound 5-2, with a yield of 73.3%. MS: 294.65.

[0143] Synthesis of compound 5-3:

[0144] Accurately weigh compound 5-2 (16.0 g, 54.2 mmol) and dissolve it in ultradry THF (80 mL), displace nitrogen three times, drip n-BuLi (2.5 M, 43.2 mL, 108.4 mmol) at -70 °C, stir for 2 h, then at -70 °C, drip trimethyltin chloride (38.8 g, 119.2 mmol), keep stirring for 1 h, and naturally return to room temperature and stir overnight. After the reaction is completed, pour the reaction solution into an aqueous potassium fluoride solution to quench and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, distill off the excess solvent under reduced pressure to obtain about 29.3 g of compound 5-3, with a yield of 92.6%. MS: 583.52.

[0145] Synthesis of compound 5-4:

[0146] Accurately weigh compound 5-3 (11.7 g, 20 mmol) and compound 1-1 (2.0 g, 5 mmol) and dissolve them in anhydrous toluene (20 mL) in turn, displace nitrogen three times, then add tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol), and displace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 2.86 g of compound 5-4, with a yield of 69.1%. MS: 827.49.

[0147] Synthesis of compound M-5:

[0148] Accurately weigh compound 5-4 (827 mg, 1.0 mmol) and dissolve it in chloroform (10 mL). At -5 °C, add NBS (355 mg, 2.0 mmol) dissolved in chloroform (10 mL) dropwise to the reaction solution, keep warm and stir in the dark for 2 h. After the reaction is completed, pour the reaction solution into an aqueous sodium sulfite solution to quench it and extract with dichloromethane. Dry the combined organic phases with anhydrous MgSO4, distill off the excess solvent under reduced pressure, stir the sample with silica gel for column chromatography, and the eluent is PE:DCM = 2:1 (volume ratio) to obtain about 753 mg of compound M-5, with a yield of 76.4%. MS: 985.26.

[0149] Polymer Synthesis Example 1: Synthesis of Polymer (P1)

[0150]

[0151] Accurately weigh monomers N-1 (235 mg, 0.25 mmol) and M-1 (232 mg, 0.25 mmol) and add them successively to a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL), blow nitrogen for 5 min, then add tetrakis(triphenylphosphine)palladium (28 mg, 0.025 mmol), continue to blow nitrogen for 10 min, and stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction, and wash the filter cake successively with methanol, n-hexane, and chloroform in a Soxhlet extractor. After concentrating the last washing solution, drop it into methanol, precipitate a solid, filter by suction, and dry the filter cake under vacuum to obtain about 194 mg of polymer (P1), with a yield of 56.2%. Mn: 44.6 KDa, PDI: 2.64.

[0152] Polymer Synthesis Example 2: Synthesis of Polymer (P3)

[0153]

[0154] Accurately weigh monomers N-2 (243 mg, 0.25 mmol) and M-1 (232 mg, 0.25 mmol) and add them successively to a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL), blow nitrogen for 5 min, then add tetrakis(triphenylphosphine)palladium (28 mg, 0.025 mmol), continue to blow nitrogen for 10 min, and stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction, and wash the filter cake successively with methanol, n-hexane, and chloroform in a Soxhlet extractor. After concentrating the last washing solution, drop it into methanol, precipitate a solid, filter by suction, and dry the filter cake under vacuum to obtain about 215 mg of polymer (P3), with a yield of 60.9%. Mn: 42.7 KDa, PDI: 2.93.

[0155] Polymer Synthesis Example 3: Synthesis of Polymer (P8)

[0156]

[0157] Accurately weigh the monomers N-1 (376 mg, 0.4 mmol) and M-2 (383 mg, 0.4 mmol) and add them successively into a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL). After purging with nitrogen for 5 min, add palladium tetrakis(triphenylphosphine) (40 mg, 0.03 mmol), and continue purging with nitrogen for 10 min. Stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction. The filter cake is washed thoroughly with methanol, n-hexane, and chloroform successively in a Soxhlet extractor. The last washing solution is concentrated and then dropped into methanol to precipitate a solid. After the filter cake is filtered by suction and dried in vacuo, about 328 mg of polymer (P8) is obtained, with a yield of 58.2%. Mn: 38.4 KDa, PDI: 2.56.

[0158] Polymer Synthesis Example 4: Synthesis of Polymer (P11)

[0159]

[0160] Accurately weigh the monomers N-1 (376 mg, 0.4 mmol) and M-3 (394 mg, 0.4 mmol) and add them successively into a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL). After purging with nitrogen for 5 min, add palladium tetrakis(triphenylphosphine) (40 mg, 0.03 mmol), and continue purging with nitrogen for 10 min. Stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction. The filter cake is washed thoroughly with methanol, n-hexane, and chloroform successively in a Soxhlet extractor. The last washing solution is concentrated and then dropped into methanol to precipitate a solid. After the filter cake is filtered by suction and dried in vacuo, about 358 mg of polymer (P11) is obtained, with a yield of 62.3%. Mn: 46.0 KDa, PDI: 2.01.

[0161] Polymer Synthesis Example 5: Synthesis of Polymer (P15)

[0162]

[0163] Accurately weigh the monomers N-1 (376 mg, 0.4 mmol) and M-4 (349 mg, 0.4 mmol), and sequentially add them into a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL), purge with nitrogen for 5 min, then add tetrakis(triphenylphosphine)palladium (40 mg, 0.03 mmol), continue to purge with nitrogen for 10 min, and stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction. The filter cake is thoroughly washed successively with methanol, n-hexane, and chloroform in a Soxhlet extractor. The last washing solution is concentrated and then dropped into methanol to precipitate a solid. After the filter cake is filtered by suction and dried under vacuum, about 290 mg of polymer (P15) is obtained, with a yield of 54.7%. Mn: 35.9 KDa, PDI: 2.75.

[0164] Polymer Synthesis Example 6: Synthesis of Polymer (P16)

[0165]

[0166] Accurately weigh the monomers N-1 (376 mg, 0.4 mmol) and M-5 (394 mg, 0.4 mmol), and sequentially add them into a 25 mL thick-walled pressure-resistant tube. Add ultra-dry toluene (10 mL), purge with nitrogen for 5 min, then add tetrakis(triphenylphosphine)palladium (40 mg, 0.03 mmol), continue to purge with nitrogen for 10 min, and stop heating after reacting at 110 °C for 12 h. Cool the reaction solution to room temperature, drop it into methanol, precipitate a solid, filter by suction. The filter cake is thoroughly washed successively with methanol, n-hexane, and chloroform in a Soxhlet extractor. The last washing solution is concentrated and then dropped into methanol to precipitate a solid. After the filter cake is filtered by suction and dried under vacuum, about 297 mg of polymer (P16) is obtained, with a yield of 51.7%. Mn: 36.4 KDa, PDI: 2.31.

[0167] Fabrication of Large-Area OPV Device Modules (the effective area of the device is 18.7 cm 2 , and the number of sub-cells is 7) and Characterization

[0168] This example is given according to the preparation implementation method and characterization of the organic photovoltaic device (OPV) provided by the present invention, but the present invention is not limited to the following examples.

[0169] Device Example 1

[0170] a. Provide conductive glass containing ITO, etch an insulating trench on the ITO by 20 nanosecond green light, wherein the insulating trench extends through the ITO layer to the glass substrate, and then clean the ITO conductive glass with the insulating trench with a detergent, rinse it, and then ultrasonically clean it with deionized water, acetone, and isopropanol 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.

[0171] b. Preparation of anode buffer layer: PEDOT:PSS (Clevios TM P VP Al 4083) was evenly spin-coated on ITO to obtain an anode buffer layer with a thickness of about 20 nm.

[0172] c. Preparation of photoactive layer: The photoactive layer solution was evenly spin-coated on the anode buffer layer in air to obtain an active material layer with a total thickness of about 100 nm.

[0173] Preparation method of photoactive layer material: dissolve the active layer donor material polymer (P1) and the active layer acceptor material L8-BO in the organic solvent toluene, wherein the concentration of the donor material polymer (P1) in toluene is 6 mg / mL, and the concentration of the acceptor material L8-BO in toluene is 7.2 mg / mL.

[0174] d. Preparation of cathode buffer layer: After the device with the photoactive layer spin-coated was thermally annealed on a hot plate at 100°C for 10 min, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 1.5 mg / mL) was evenly spin-coated on the photoactive layer to obtain a cathode buffer layer with a thickness of about 10 nm.

[0175] e. Etching a connection channel: A connection channel is etched on the cathode buffer layer using a green nanosecond laser, and the connection channel penetrates the cathode buffer layer, the photoactive layer, and the anode buffer layer to the ITO layer.

[0176] f. Preparation of cathode layer: In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at a pressure of 400 mbar to form a cathode layer with a thickness of about 100 nm at a rate of 4 angstroms per second.

[0177] g. Etching a partition channel: etching a partition channel on the cathode layer using a green nano-laser, wherein the partition channel at least penetrates the cathode layer.

[0178] h. Packaging: The device is packaged with ultraviolet curing resin in a nitrogen glove box, and the upper packaging cover is selected from glass.

[0179] Device Examples 2-6

[0180] The preparation method of Device Examples 2-6 is the same as that of Device Example 1, except for the selection of the donor material of the active layer. Specifically, the donor material polymer (P1) is replaced with polymer (P3), polymer (P8), polymer (P11), polymer (P15), and polymer (P16) respectively.

[0181] Device Comparative Examples 1-2

[0182] The preparation method of Device Comparative Examples 1-2 is the same as that of Device Example 1, except for the selection of the donor material of the active layer. Specifically, the donor material polymer (P1) is replaced with polymer (Ref-1) and polymer (Ref-2) respectively.

[0183]

[0184] Wherein: the Mn of polymer (Ref-1) is 41.2 and the PDI is 2.47; the Mn of polymer (Ref-2) is 45.4 and the PDI is 2.69.

[0185] Perform performance tests on the prepared organic photovoltaic cell modules. Under the irradiation of standard sunlight simulator AM1.5 light, test the current-voltage curve of the battery and calculate the photoelectric conversion efficiency, as shown in Table 1.

[0186] Table 1

[0187] Device embodiment Active layer donor-acceptor material Photovoltaic conversion efficiency (%) Device embodiment 1 Polymer (P1): L8-BO 14.77 Device embodiment 2 Polymer (P3): L8-BO 15.24 Device embodiment 3 Polymer (P8): L8-BO 16.22 Device embodiment 4 Polymer (P11): L8-BO 15.83 Device embodiment 5 Polymer (P15): L8-BO 14.15 Device embodiment 6 Polymer (P16): L8-BO 13.82 Comparative device embodiment 1 Polymer (Ref-1): L8-BO 11.39 Comparative device embodiment 2 Polymer (Ref-2): L8-BO 10.56

[0188] It can be seen from the characterization of the data in Table 1 that the organic photovoltaic polymer materials provided by the present invention have significantly improved photoelectric performance compared with Device Comparative Examples 1-2 when preparing large-area OPV device modules. The reason is that: by regulating the branching sites of the connecting unit of the alkyl chain, a larger intramolecular steric hindrance is generated in the alkane chain, thereby increasing the solubility of the molecule, enabling it to be better dissolved in non-halogen organic solvents, and preparing a more uniform and stable thin film, thereby effectively improving the photoelectric conversion performance of large-area organic photovoltaic devices.

[0189] Obviously, the above examples are only for clear illustration and not for limitation of the implementation mode. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to list all the implementation modes here. And the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. An organic photovoltaic polymer material, characterized in that: Contains a structure represented by the general formula (I): Wherein: Each occurrence of R1 and R2 is independently selected from unsubstituted or R-substituted straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms; # ; Each occurrence of R3 and R4 is independently selected from -H, -D, -F, -Cl, -CF3, -CN, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted by R # a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted by R Each occurrence of R5 is independently selected from unsubstituted or R # -substituted linear or branched alkyl groups having 1 to 20 carbon atoms; R # Each occurrence is independently selected from -D, -F, -Cl, or cycloalkyl having 3 to 10 carbon atoms; Each occurrence of Y is independently selected from O, S or Se; Each occurrence of m is independently selected from 1, 2 or 3; Each occurrence of R6 is independently selected from -H, -D, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, -F, -Cl, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by combining the above groups; n represents the number of repeating units and is selected from natural numbers greater than or equal to 2.

2. The organic photovoltaic polymer material according to claim 1, wherein: Contains a structure represented by the general formula (II-1), (II-2) or (II-3):

3. The organic photovoltaic polymer material according to claim 1 or 2, wherein: Each occurrence of R1 is independently selected from unsubstituted or R-substituted straight-chain alkyl groups having 2 to 6 carbon atoms; each occurrence of R2 is independently selected from unsubstituted or R-substituted straight-chain alkyl groups having 4 to 8 carbon atoms. # # ​ 4. The organic photovoltaic polymer material according to claim 1 or 2, characterized in that: Each occurrence of R3 and R4 is independently selected from -H, -D, -CH3, -CD3, -C2H5, -C4H9, -C6H 13 , -F, -Cl, -CF3 or -CN.

5. The organic photovoltaic polymer material according to claim 1 or 2, characterized in that: Each occurrence of R5 is independently selected from a branched-chain alkyl group having 8-20 carbon atoms that is unsubstituted or substituted by -D.

6. The organic photovoltaic polymer material according to claim 1 or 2, characterized in that: R6 is selected from -H, methyl, ethyl or methoxy.

7. The organic photovoltaic polymer material according to claim 1, characterized in that: The organic photovoltaic polymer material is selected from any of the following structures:

8. A mixture, characterized in that: The mixture contains the organic photovoltaic polymer material according to any one of claims 1-7.

9. A composition, characterized in that: The composition contains the organic photovoltaic polymer material according to any one of claims 1-7 or the mixture according to claim 8, and at least one organic solvent.

10. An organic photovoltaic device, the organic photovoltaic device comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, characterized in that: The photoactive layer material contains the organic photovoltaic polymer material according to any one of claims 1-7 or the mixture according to claim 8, or is prepared from the composition according to claim 9.

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