Polymer, mixture and application thereof

Abstract

The invention relates to the field of organic semiconductor materials, in particular to a polymer as shown in a general formula (I), *-O-R2 is introduced into an electron-withdrawing A unit, so that the energy level and solubility of a polymer donor material are optimized, and the polymer shows excellent photoelectric properties when being applied to a module.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor materials, and more specifically to a polymer, a mixture thereof, and its applications. Background Technology

[0002] Solar energy is an ideal energy source for human sustainable development, and developing photovoltaic technology is an effective way to solve global energy shortages and environmental pollution. Compared with inorganic photovoltaics, organic photovoltaics (OPV) has advantages such as being lightweight, solution-processable, low-cost, and environmentally friendly, and is considered a promising next-generation photovoltaic technology.

[0003] Organic photovoltaic (PV) devices typically employ a sandwich structure, generally consisting of five parts: an anode, an anode buffer layer, an active layer, a cathode buffer layer, and a cathode. Their working principle is as follows: When sunlight passes through a transparent substrate and electrodes and strikes the active layer, the acceptor material absorbs photons with energy exceeding its band gap. 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 as bound excitons. 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 a built-in electric field, the free holes and electrons travel along continuous channels in 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. The core region where photoelectric reactions occur in organic photovoltaic devices is the photoactive layer. Therefore, by designing efficient active layer materials (donors and acceptors), device performance can be effectively improved.

[0004] Currently, most active layer donor materials are selected from DA copolymers based on alternating copolymerization of electron-donating and electron-deficient monomers. In the polymer structure design of DA copolymers, the selection of appropriate conjugated repeating units determines the polymer's energy levels, band gap, and solution processability. The conjugated backbone and side chains have a significant impact on the aggregation and intermolecular interactions of the active layer. At present, there are relatively few high-performance polymer donor materials, and most suffer from poor solubility, leading to poor device performance in large-area fabrication. Therefore, there is an urgent need to develop high-performance polymer donor materials suitable for large-area fabrication, thereby promoting the development of large-area organic photovoltaic technology. Summary of the Invention

[0005] Based on this, the present invention provides a novel polymer donor material. By introducing *-O-R2 into the electron-withdrawing A unit, the energy level and solubility of the polymer donor material are adjusted, enabling it to exhibit excellent photoelectric performance when applied in large-area organic photovoltaic modules.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

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

[0008]

[0009] in:

[0010] Ar1, Ar2, and Ar3 each time they appear, are independently selected from substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms, or substituted or unsubstituted aromatic groups having 6-20 carbon atoms.

[0011] Each time Z appears, it is independently selected from O, S, or Se;

[0012] Each occurrence of R1 is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or substituted or unsubstituted aromatic groups having 6-10 carbon atoms.

[0013] Each time R2 appears, it is independently selected from a straight-chain alkyl group having 1-20 carbon atoms or a branched alkyl group having 3-20 carbon atoms;

[0014] The term "substituted or unsubstituted" indicates that the defined group is not substituted, or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -CN, -CF3, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, straight-chain alkathioyl having 1-20 carbon atoms, branched-chain alkathioyl having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0015] n represents the number of repeating units, selected from an integer greater than or equal to 2.

[0016] In an alternative embodiment, Z is selected from S.

[0017] In an alternative embodiment, each occurrence of Ar3 is independently selected from substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms.

[0018] Furthermore, each occurrence of Ar3 is independently selected from substituted or unsubstituted N-containing heteroaromatic groups having 5-6 ring atoms.

[0019] In an alternative embodiment, the polymer has a structure as described in general formula (II):

[0020]

[0021] Wherein: each time Y appears, it is independently selected from O, S or Se.

[0022] In one alternative embodiment, Y is selected from S.

[0023] In one embodiment, each occurrence of R2 is independently selected from straight-chain alkyl groups having 1-12 carbon atoms or branched alkyl groups having 3-12 carbon atoms.

[0024] Furthermore, each occurrence of R2 is independently selected from methyl (-CH3), ethyl (-C2H5), n-butyl (-C4H9), and n-hexyl (-C6H5). 13 ), n-octyl (-C8H) 17 ),

[0025] In one embodiment, each occurrence of Ar1 and Ar2 is independently selected from substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or substituted or unsubstituted aromatic groups having 6-10 carbon atoms.

[0026] Furthermore, each occurrence of Ar1 and Ar2 is independently selected from any of the following groups:

[0027]

[0028] Wherein: W is selected independently from O, S or Se each time it appears;

[0029] R3, R4, R5, R6, and R7 are each independently selected from -H, -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-20 carbon atoms, branched-chain alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched-chain alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, or branched-chain alkylthio with 3-20 carbon atoms.

[0030] In a preferred embodiment, W is selected from S.

[0031] When W is selected from S, the S atom and the O on the adjacent alkoxy group form S---O non-covalent interactions, thereby improving the coplanarity of the main chain.

[0032] Furthermore, the polymer has a structure as described in general formula (III):

[0033]

[0034] In one embodiment, each occurrence of R3 and R4 is independently selected from -H, -D, a straight-chain alkyl group having 6-20 carbon atoms, a branched alkyl group having 6-20 carbon atoms, a straight-chain alkoxy group having 6-20 carbon atoms, or a branched alkoxy group having 6-20 carbon atoms.

[0035] Furthermore, each occurrence of R3 is independently selected from straight-chain alkyl groups having 6-20 carbon atoms or branched-chain alkyl groups having 6-20 carbon atoms.

[0036] Furthermore, each occurrence of R3 is independently selected from n-hexyl (-C6H) 13 ), n-octyl (-C8H) 17 ),

[0037] In an alternative embodiment, R4 is selected from -H.

[0038] In one embodiment, the general formula (III) described Selected from

[0039]

[0040] Furthermore, the aforementioned Choose from any of the following structures, but not limited to:

[0041]

[0042] In an alternative embodiment, each occurrence of R1 is independently selected from the one affected by R. a Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or R a Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted; the R a Each occurrence is independently selected from -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-20 carbon atoms, branched-chain alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched-chain alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched-chain alkylthio with 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0043] Furthermore, each occurrence of R1 is independently selected from... The R8, R9, R 10 R 11 R 12 R 13 Each occurrence is independently selected from -H, -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-12 carbon atoms, branched-chain alkyl with 3-12 carbon atoms, straight-chain alkoxy with 1-12 carbon atoms, branched-chain alkoxy with 3-12 carbon atoms, straight-chain alkylthio with 1-12 carbon atoms, branched-chain alkylthio with 3-12 carbon atoms, or a group formed by a combination of the above groups.

[0044] In one embodiment, the R 10 Each occurrence is independently selected from branched alkyl groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups, branched alkoxy groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups, and branched alkylthio groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups.

[0045] In one embodiment, each occurrence of R8 and R9 is independently selected from -H, -D, -F, -Cl, -CN, -CF3, unsubstituted or substituted with one or more -D linear alkyl groups having 1-12 carbon atoms, or unsubstituted or substituted with one or more -D branched alkyl groups having 3-12 carbon atoms.

[0046] In one embodiment, the R 12 Each occurrence is independently selected from branched alkyl groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups, branched alkoxy groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups, and branched alkylthio groups having 3-12 carbon atoms that are unsubstituted or substituted with one or more -D groups.

[0047] In one embodiment, the R 11 R 13 Each occurrence is independently selected from -H, -D, -F, -Cl, -CN, -CF3, unsubstituted or substituted with one or more -D straight-chain alkyl groups having 1-12 carbon atoms, or unsubstituted or substituted with one or more -D branched alkyl groups having 3-12 carbon atoms.

[0048] In one specific embodiment, each occurrence of R1 is independently selected from any of the following groups, but is not limited thereto:

[0049]

[0050] In an alternative embodiment, the polymer according to the invention is selected from any of the following structures, but is not limited thereto:

[0051]

[0052]

[0053] In one embodiment, the polymer according to the present invention has a number-average molecular weight (Mn) selected between 10,000 and 1,000,000. Further, the number-average molecular weight (Mn) of the polymer is selected between 10,000 and 100,000. Further, the number-average molecular weight (Mn) of the polymer is selected between 20,000 and 80,000.

[0054] In one embodiment, the polymer according to the present invention preferably has a molecular weight distribution (PDI) value ranging from 1 to 10; more preferably from 1 to 6; and more preferably from 1 to 4.

[0055] The present invention further relates to a mixture comprising the polymer as described above and at least another organic functional material.

[0056] Preferably, the other organic functional material is selected from non-fullerene acceptor materials.

[0057] Specifically, the non-fullerene receptor may be selected from one or more of the following: ITIC-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, PY-DT, etc.; but not limited to these.

[0058] The present invention further relates to an organic photovoltaic cell comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, wherein the photoactive layer material comprises a polymer or mixture as described above.

[0059] Furthermore, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material, wherein the photoactive layer donor material comprises the polymer described above.

[0060] The receptor material may be selected from one or more of the following: ITIC-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.; but not limited to these. For details, please refer to Chem. Rev. 2022, 122, 18, 14180–14274.

[0061] The method for preparing the photoactive layer material solution is as follows: the photoactive layer donor material and acceptor material are dissolved in an organic solvent at a certain mass ratio, and the mixture is stirred until fully dissolved to obtain the photoactive layer solution.

[0062] The organic solvent is preferably selected from: tetrahydronaphthalene, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decahydronaphthalene, 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, monochloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,1,1-trichlorobenzene, etc. One or a mixture of two or more of the following: trichlorofluoroethane, 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, and hexamethylphosphoramide.

[0063] The above solution is used to prepare the photoactive layer by printing or coating methods. These printing or coating methods can include, but are not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, and slot-loaded extrusion coating. Slot-loaded coating, spin coating, and inkjet printing are preferred.

[0064] The preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:0.8 to 1:1.5; further, the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.5; the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.2.

[0065] 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.

[0066] Furthermore, the photoactive layer material solution may further include additives for adjusting viscosity, film-forming properties, and improving adhesion. The additives may 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 to these.

[0067] At least one of the anode and cathode is transparent or translucent to facilitate light incidence. The material used to prepare the electrode 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; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; and conductive polymers such as PEDOT:PSS, polypyrrole, and polyaniline; or materials with multilayer structures such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2, and Al:BaF2:Ba, but not limited to these.

[0068] In one embodiment, the organic photovoltaic cell comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially, wherein the photoactive layer comprises a polymer or mixture as described above.

[0069] Preferably, the cathode buffer layer material can be selected from low work function metal complexes, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, and titanium oxide (TiO2). x It can be zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be polymer materials, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited to these.

[0070] The anode buffer layer material is selected from PEDOT:PSS and molybdenum oxide (MoO). x ), vanadium oxide (V₂O₅), nickel oxide (NiO), tungsten oxide (WO₂) x Preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, etc., but not limited to these.

[0071] It should be noted that, in order to improve the performance of organic photovoltaic cell devices, the organic photovoltaic cell may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0072] In one embodiment, the organic photovoltaic cell is an organic photovoltaic module comprising m sub-cells (organic photovoltaic cell units), where m is greater than or equal to 2. The m sub-cells are electrically connected in series or in parallel.

[0073] Specifically, the number of neutron cells in the organic photovoltaic module can be selected according to the performance requirements of the product application.

[0074] Furthermore, organic photovoltaic cells also include a substrate.

[0075] In one embodiment, the substrate is disposed on the anode side and away from the photoactive layer. In another embodiment, the substrate is disposed on the cathode side and away from the photoactive layer.

[0076] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. 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), polyimide (PI), parylene, etc., and substrates commonly used in organic photovoltaic cells may also be used.

[0077] The organic photovoltaic cells described in this invention are mainly used in fields such as indoor photovoltaics, wearable devices, smart IoT, smart homes, smart agriculture, building photovoltaics, and new energy vehicles.

[0078] The polymer described in this invention has a DA copolymer structure. By introducing *-O-R2 at specific sites in the A unit, the energy level of the polymer is raised, and the band gap is widened. Furthermore, by introducing *-O-R2 into the A unit, the S-O non-covalent interaction between *-O-R2 and the π bridge improves the molecular morphology and planarity. *-O-R2 also further improves the solubility and crystallinity of the molecule, enabling it to exhibit excellent photoelectric conversion performance when used as a donor material in large-area organic photovoltaic cells. Attached Figure Description

[0079] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0080] Figure 1 The GPC spectrum of the polymer (P8) described in Polymer Synthesis Example 5 is shown.

[0081] Figure 2 This is a cross-sectional view of the organic photovoltaic cell structure in an embodiment of the device in this application.

[0082] Wherein: 10-substrate, 101-first electrode layer, 102-anodine buffer layer, 103-photoactive layer, 104-cathode buffer layer, 105-cathode layer, 20-upper cover plate layer, 30-adhesive layer Detailed Implementation

[0083] 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.

[0084] 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 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 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").

[0085] In this invention, organic photovoltaic devices, organic photovoltaic cells, organic solar cells, OPV, and OSC have the same meaning and can be used interchangeably.

[0086] In this invention, the terms "photoactive layer" and "active layer" have the same meaning and can be used interchangeably.

[0087] 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.

[0088] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0089] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., monocyclic compound, fused-ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. In aromatic groups, the ring atom number is the same as the carbon atom number; in heteroaromatic groups, the ring atom number is the carbon atom number plus the heteroatom number; for example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, the ring atom number of a quinoline ring is 10, the ring atom number of a thiophene group is 5, and the ring atom number of a thiophene is 8.

[0090] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbide ring. The aromatic group can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl; in other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated by carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated by carbon-carbon bonds can also be considered as aromatic groups in this application. Preferably, the aromatic group is selected from aromatic groups having 6-20 carbon atoms; further, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic group includes, but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluoranthracene, and their derivatives.

[0091] In this invention, a "heteroaromatic group" refers to a heteroaromatic ring or its derivative containing one, two, three, four, five, six or more heteroatoms, wherein the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl or a polycyclic heteroaryl. The term "heteroaromatic group" as used herein also includes groups formed by the fusion of one or more heteroaromatic groups with one or more aromatic rings, aliphatic rings or heterocycles. Preferably, the heteroaromatic group is selected from those having 5-20 ring atoms; more preferably, it is selected from those having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, selenophene, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridineyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thiophenolopyrrolyl, thiophenolothiophene, furanolopyrrolyl, furanolofuranyl, thiophenolofuranyl and their derivatives.

[0092] In this invention, the number of carbon atoms in a straight-chain alkyl group can be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms in a branched-chain alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight-chain alkyl groups include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), and n-pentyl (-C5H9). 11 ), n-hexyl (-C6H) 13 ), heptyl (-C7H) 15 ), n-octyl (-C8H) 17 ), non-nonyl (-C9H) 19 -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 33Non-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, branched alkyl groups containing 15 carbon atoms, and branched alkyl groups containing 16 carbon atoms.

[0093] 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.

[0094] 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 the "-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 the "-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.

[0095] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0096] 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.

[0097] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0098] 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.

[0099] In the description of this invention, it should be understood that the terms "upper," "lower," "between layers," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when organic solar cell devices are in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this invention.

[0100] The terms “combinations thereof,” “any combination thereof,” “any combination thereof,” and “combination” used in this invention include all suitable combinations of any two, any three, or any three or more groups listed.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] Polymer Synthesis Examples

[0105] The following embodiments are provided to facilitate a better understanding of the disclosure of this invention, but are not intended to limit it in any way. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the materials and reagents used are prior art and commercially available unless otherwise specified.

[0106] Synthesis of monomer M-1

[0107]

[0108] Synthesis of compounds 1-2:

[0109] Compound 1-1 (40.0 g, 152.0 mmol) was accurately weighed and dissolved in ultra-dry tetrahydrofuran (250 mL). Nitrogen gas was purged three times. n-BuLi (66.8 mL, 2.5 M, 167.2 mmol) was added dropwise at -78 °C, and the reaction was maintained at this temperature for 6 h. The temperature was then raised to -40 °C, and cuprous bromide (10.9 g, 76.0 mmol) and lithium bromide (13.2 g, 152.0 mmol) were added sequentially. After stirring uniformly for 5 min, oxaloyl chloride (9.64 g, 76.0 mmol) was added dropwise, and the reaction was maintained at -40 °C for 6 h. After the reaction was complete, the reaction solution was quenched in a saturated ammonium chloride aqueous solution and extracted with ethyl acetate (200 mL × 2). The combined organic phases were washed with a saturated NaCl solution (100 mL). The organic phase was dried over anhydrous MgSO4, the organic solvent was removed under reduced pressure, and silica gel column chromatography was performed to give approximately 25.83 g of compounds 1-2, with a yield of 80.5%. MS: 422.37.

[0110] Synthesis of compounds 1-3:

[0111] Compounds 1-2 (24.0 g, 56.8 mmol) and FeCl3 (36.8 g, 227.2 mmol) were accurately weighed and dissolved in dichloromethane (240 mL). The reaction was carried out overnight at room temperature. After the reaction was completed, the reaction solution was slowly poured into ice water to quench it and extracted with dichloromethane (200 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. The solution was then subjected to silica gel column chromatography with stirring to give approximately 21.62 g of compounds 1-3, with a yield of 90.4%. MS: 421.06.

[0112] Synthesis of compounds 1-4:

[0113] Accurately weigh 10.1 g (24.0 mmol) of compounds 1-3 and 5.0 g (72.0 mmol) of hydroxylamine hydrochloride were dissolved in anhydrous ethanol (200 mL), and the mixture was refluxed overnight. After the reactants 1-3 were consumed, the reaction mixture was cooled to room temperature, and Pd / C (0.10 g, 10% wt) was added. After stirring, the mixture was heated to 65 °C, and hydrazine hydrate (30.0 g, 600 mmol) was added dropwise. The mixture was refluxed for 24 h. After the reaction was complete, the mixture was filtered while hot, and the filtrate was collected. The organic solvent in the filtrate was removed under reduced pressure, and the mixture was subjected to silica gel column chromatography with stirring to obtain approximately 6.78 g of compounds 1-4, with a yield of 67.1%. MS: 420.84.

[0114] Synthesis of compounds 1-5:

[0115] Compounds 1-4 (4.2 g, 10.0 mmol) and triethylamine (3.54 g, 35.0 mmol) were accurately weighed and dissolved in chloroform (84 mL). Thionyl chloride (2.38 g, 20.0 mmol) was added dropwise at 0 °C. After the temperature was restored to room temperature for 1 h, the mixture was heated to reflux and reacted overnight. After the reaction was complete, the organic solvent was removed under reduced pressure, and the mixture was recrystallized from ethanol to give approximately 2.77 g of compounds 1-5, with a yield of 61.7%. MS: 449.15.

[0116] Synthesis of compounds 1-6:

[0117] Compounds 1-5 (2.5 g, 5.57 mmol) were accurately weighed and dissolved in chloroform (50 mL). Br2 (2.22 g, 13.9 mmol) was added dropwise, and the mixture was refluxed for 6 h. After the reaction was complete, the mixture was cooled to room temperature, quenched in an aqueous sodium sulfite solution, and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from dichloromethane yielded approximately 2.86 g of compounds 1-6, with a yield of 84.6%. MS: 606.72.

[0118] Synthesis of compounds 1-7:

[0119] Compounds 1-6 (2.0 g, 3.30 mmol) and (4-(2-butyloctyl)thiophen-2-yl)tributyltinane (7.14 g, 13.2 mmol) were accurately weighed and dissolved sequentially in anhydrous toluene (10 mL). Nitrogen gas was purged three times. Then, tetrakis(triphenylphosphine)palladium (76.2 mg, 0.066 mmol) was added, and nitrogen gas was purged three times. The reaction was carried out at 110 °C for 12 h, and heating was stopped after confirming the reaction was complete. After the reaction mixture cooled to room temperature, the reaction solution was quenched in an aqueous potassium fluoride solution and extracted with ethyl acetate (50 mL x 2). The combined organic phases were washed with saturated NaCl solution (50 mL). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed under reduced pressure. Silica gel column chromatography with stirring yielded approximately 2.05 g of compounds 1-7, with a yield of 65.4%. MS: 949.14.

[0120] Synthesis of compound M-1:

[0121] Compounds 1-7 (1.9 g, 2.0 mmol) were accurately weighed and dissolved in ultra-dry tetrahydrofuran (20 mL). NBS (747 mg, 4.2 mmol) dissolved in ultra-dry THF (10 mL) was added dropwise to the reaction mixture at -5 °C, and the mixture was stirred for 4 h. After the reaction was complete, the reaction mixture was quenched in an aqueous sodium sulfite solution and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from toluene and methanol yielded approximately 1.33 g of compound M-1, with a yield of 60.1%. MS: 1107.28.

[0122] Synthesis of monomer M-2

[0123]

[0124] Synthesis of compound 2-2:

[0125] Compounds 1-6 (606 mg, 1.0 mmol) and 2-1 (2.22 g, 4.0 mmol) were accurately weighed and dissolved sequentially in anhydrous toluene (3 mL). Nitrogen gas was purged three times. Then, tetraphenylphosphine palladium (23.1 mg, 0.02 mmol) was added, and nitrogen gas was purged three times. Subsequent synthetic steps followed the same procedure as for compounds 1-7, yielding approximately 603 mg of compound 2-2 in 61.7% yield. MS: 977.23.

[0126] Synthesis of compound M-2:

[0127] Compound 2-2 (500 mg, 0.51 mmol) was accurately weighed and dissolved in ultra-dry tetrahydrofuran (10 mL). NBS (190 mg, 1.07 mmol) dissolved in ultra-dry tetrahydrofuran (5 mL) was added dropwise to the reaction solution at -5 °C for 2 h. After the reaction was complete, the reaction solution was quenched in an aqueous sodium sulfite solution and extracted with dichloromethane (20 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from toluene and methanol gave approximately 360 mg of compound M-2, with a yield of 62.2%. MS: 1134.68.

[0128] Synthesis of monomer M-3

[0129]

[0130] Synthesis of compound 3-2:

[0131] Compound 3-1 (20.0 g, 85.0 mmol) was accurately weighed and dissolved in ultra-dry tetrahydrofuran (100 mL). Nitrogen gas was purged three times. n-BuLi (37.2 mL, 2.5 M, 93.4 mmol) was added dropwise at -78 °C for 3 h. The reaction was then raised to -40 °C, and cuprous bromide (6.1 g, 42.4 mmol) and lithium bromide (7.38 g, 85.0 mmol) were added sequentially. After stirring uniformly for 5 min, oxalyl chloride (5.38 g, 42.4 mmol) was added dropwise, and the reaction was continued at -40 °C for 3 h. After the reaction was complete, the reaction solution was quenched in a saturated ammonium chloride aqueous solution and extracted with ethyl acetate (200 mL × 2). The combined organic phases were washed with a saturated NaCl solution (100 mL). The organic phase was dried over anhydrous MgSO4, the organic solvent was removed under reduced pressure, and the sample was stirred on a silica gel column for chromatography, yielding approximately 12.83 g of compound 3-2, with a yield of 82.1%. MS: 366.97.

[0132] Synthesis of compound 3-3:

[0133] Compound 3-2 (10.0 g, 27.3 mmol) and FeCl3 (17.7 g, 109.2 mmol) were accurately weighed and dissolved in dichloromethane (100 mL). The reaction was carried out at room temperature for 6 h. After the reaction was completed, the reaction solution was slowly quenched in ice water and extracted with dichloromethane (100 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. The mixture was then subjected to silica gel column chromatography with stirring to give approximately 8.34 g of compound 3-3, with a yield of 83.8%. MS: 364.59.

[0134] Synthesis of compounds 3-4:

[0135] Compound 3-3 (8.02 g, 22.0 mmol) and hydroxylamine hydrochloride (4.58 g, 66.0 mmol) were accurately weighed and dissolved in anhydrous ethanol (100 mL), and the mixture was refluxed for 24 h. After the reactant 3-3 was completely consumed, the reaction mixture was cooled to room temperature, Pd / C (0.8 g, 10% wt) was added, and the temperature was raised to 65 °C. Then, hydrazine hydrate (27.5 g, 550 mmol) was added dropwise, and the mixture was refluxed for 24 h. After the reaction was completed, the mixture was filtered while hot, and the filtrate was collected. The organic solvent in the filtrate was removed under reduced pressure, and the mixture was subjected to silica gel column chromatography with stirring to obtain approximately 5.12 g of compound 3-4, with a yield of 63.8%. MS: 364.85.

[0136] Synthesis of compounds 3-5:

[0137] Compounds 3-4 (4.01 g, 11.0 mmol) and triethylamine (3.89 g, 38.5 mmol) were accurately weighed and dissolved in chloroform (80 mL). Thionyl chloride (2.62 g, 22.0 mmol) was added dropwise to the reaction flask at 0 °C. After reacting at room temperature for 1 h, the mixture was heated to reflux and reacted overnight. After the reaction was complete, the organic solvent was removed under reduced pressure, and the mixture was recrystallized from dichloromethane and ethanol to give approximately 2.78 g of compound 3-5, with a yield of 64.4%. MS: 392.41.

[0138] Synthesis of compounds 3-6:

[0139] Compound 3-5 (2.0 g, 5.10 mmol) was accurately weighed and dissolved in chloroform (40 mL). Br2 (2.03 g, 12.7 mmol) was added dropwise, and the mixture was heated to reflux for 6 h. After the reaction was complete, the mixture was cooled to room temperature, quenched in an aqueous sodium sulfite solution, and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from dichloromethane yielded approximately 2.42 g of compound 3-6, with a yield of 86.2%. MS: 550.12.

[0140] Synthesis of compounds 3-7:

[0141] Compounds 3-6 (2.00 g, 3.63 mmol) and (4-(2-butyloctyl)thiophen-2-yl)tributyltinane (7.14 g, 14.5 mmol) were accurately weighed and dissolved sequentially in anhydrous toluene (10.0 mL). Nitrogen gas was purged three times, and tetrakis(triphenylphosphine)palladium (83.9 mg, 0.072 mmol) was added and purged three times. The reaction was carried out at 110 °C for 12 h, and heating was stopped after confirming the reaction was complete. After cooling to room temperature, the reaction solution was quenched in an aqueous potassium fluoride solution and extracted with ethyl acetate (50 mL x 2). The combined organic phases were washed with saturated NaCl solution (50 mL). The organic phase was dried over anhydrous MgSO4, and excess solvent was removed under reduced pressure. Column chromatography with silica gel stirring yielded approximately 2.02 g of compound 3-7, with a yield of 62.3%. MS: 893.07.

[0142] Synthesis of compound M-3:

[0143] Compound 3-7 (1.61 g, 1.80 mmol) was accurately weighed and dissolved in ultra-dry tetrahydrofuran (20 mL). NBS (672 mg, 3.78 mmol) dissolved in ultra-dry tetrahydrofuran (10 mL) was added dropwise to the reaction solution at -5 °C, and the reaction was carried out at -5 °C for 4 h. After the reaction was complete, the reaction solution was quenched in an aqueous sodium sulfite solution and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from toluene and methanol gave approximately 1.21 g of compound M-3, yield 64.0%. MS: 1050.96.

[0144] Synthesis of monomer M-3

[0145]

[0146] Synthesis of compound 4-1:

[0147] Prepare a clean, anhydrous 25 mL sealed container. Accurately weigh compound 1-3 (3.0 g, 7.13 mmol), hydroxylamine hydrochloride (1.98 g, 28.5 mmol), and anhydrous ethanol (10 mL) into the container. React at 140 °C for 72 h. After the reaction is complete, cool the container to room temperature, remove the organic solvent under reduced pressure, and perform silica gel column chromatography to obtain approximately 1.85 g of compound 4-1, with a yield of 59.9%. MS: 433.01.

[0148] Synthesis of compound 4-2:

[0149] Compound 4-1 (1.70 g, 3.93 mmol) was accurately weighed and dissolved in chloroform (34 mL). Br2 (1.57 g, 9.82 mmol) was added dropwise, and the mixture was heated to reflux for 6 h. After the reaction was complete, the mixture was cooled to room temperature, quenched in an aqueous sodium sulfite solution, and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from dichloromethane yielded approximately 1.95 g of compound 4-2, with a yield of 84.1%. MS: 589.64.

[0150] Synthesis of compound 4-3:

[0151] Compound 4-2 (1.80 g, 3.05 mmol) and (4-(2-butyloctyl)thiophen-2-yl)tributyltinane (6.60 g, 12.2 mmol) were accurately weighed and dissolved sequentially in anhydrous toluene (10.0 mL). Nitrogen gas was purged three times. Then, tetrakis(triphenylphosphine)palladium (70.5 mg, 0.061 mmol) was added, and nitrogen gas was purged three times. The reaction was carried out at 110 °C for 2 h, and heating was stopped after confirming the reaction was complete. After the reaction mixture cooled to room temperature, the reaction solution was quenched in an aqueous potassium fluoride solution and extracted with ethyl acetate (50 mL x 2). The combined organic phases were washed with saturated NaCl solution (50 mL). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed under reduced pressure. Silica gel column chromatography with stirring was performed to give approximately 1.72 g of compound 4-3, yield 60.4%. MS: 934.28.

[0152] Synthesis of compound M-4:

[0153] Compound 4-3 (1.50 g, 1.60 mmol) was accurately weighed and dissolved in ultra-dry tetrahydrofuran (20 mL). NBS (598 mg, 3.36 mmol) dissolved in ultra-dry tetrahydrofuran (10 mL) was added dropwise to the reaction solution at -5 °C, and the reaction was carried out at -5 °C for 4 h. After the reaction was complete, the reaction solution was quenched in an aqueous sodium sulfite solution and extracted with dichloromethane (50 mL x 2). The combined organic phases were dried over anhydrous MgSO4, and excess solvent was removed by vacuum distillation. Recrystallization from toluene and methanol gave approximately 1.15 g of compound M-4, with a yield of 65.8%. MS: 1090.74.

[0154] Polymer Synthesis Example 1: Synthesis of Polymer (P2)

[0155]

[0156] Accurately weigh monomer N-1 (235 mg, 0.25 mmol) and compound M-1 (277 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL), and purge with nitrogen six times. Add Pd2(dba)3 (5.0 mg, 0.005 mmol), and purge with nitrogen six more times. React at 110 °C for 24 h, then stop heating. Cool the reaction solution to room temperature, dilute with chlorobenzene (5 mL), and add dropwise to methanol (250 mL). A solid precipitates, which is filtered. The filter cake is washed thoroughly in a Soxhlet extractor with dichloromethane, trichloromethane, and chlorobenzene sequentially. The final washing liquid is concentrated and added dropwise to methanol, precipitating a solid. Filter the filter cake and dry it under vacuum to obtain approximately 201 mg of polymer (P2), with a yield of 51.5%. Mn: 36.8 kDa, PDI: 2.84.

[0157] Polymer Synthesis Example 2: Synthesis of Polymer (P3)

[0158]

[0159] Monomer N-2 (243 mg, 0.25 mmol) and compound M-1 (277 mg, 0.25 mmol) were accurately weighed and added sequentially to a 25 mL thick-walled pressure-resistant tube. Tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL) were added. After purging with nitrogen six times, Pd2(dba)3 (5.0 mg, 0.005 mmol) was added, and nitrogen was purged again six times. The subsequent synthesis steps were the same as those for polymer (P2). Approximately 198 mg of polymer (P3) was obtained, with a yield of 49.7%. Mn: 39.1 kDa, PDI: 3.06.

[0160] Polymer Synthesis Example 3: Synthesis of Polymer (P5)

[0161]

[0162] Accurately weigh monomers N-1 (235 mg, 0.25 mmol) and M-2 (284 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After purging with nitrogen six times, add Pd2(dba)3 (5.0 mg, 0.005 mmol) and purge with nitrogen six more times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 221 mg of polymer (P5) was obtained, with a yield of 55.7%. Mn: 35.4 kDa, PDI: 2.65.

[0163] Polymer Synthesis Example 4: Synthesis of Polymer (P17)

[0164]

[0165] Accurately weigh monomers N-3 (241 mg, 0.25 mmol) and M-1 (277 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After fully purging with nitrogen six times, add Pd2(dba)3 (5.0 mg, 0.005 mmol) and continue to fully purge with nitrogen six times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 187 mg of polymer (P17) was obtained, with a yield of 47.2%. Mn: 40.3 kDa, PDI: 3.21.

[0166] Polymer Synthesis Example 5: Synthesis of Polymer (P8)

[0167]

[0168] Accurately weigh monomers N-1 (235 mg, 0.25 mmol) and M-3 (263 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After purging with nitrogen six times, add Pd2dba3 (5.0 mg, 0.005 mmol) and purge with nitrogen six more times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 205 mg of polymer (P8) was obtained, with a yield of 54.5%. Mn: 35.3 kDa, PDI: 2.02. GPC chromatogram is shown below. Figure 1 As shown.

[0169] Polymer Synthesis Example 6: Synthesis of Polymer (P9)

[0170]

[0171] Accurately weigh monomers N-2 (243 mg, 0.25 mmol) and M-3 (263 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After purging with nitrogen six times, add Pd2(dba)3 (5.0 mg, 0.005 mmol) and purge with nitrogen six more times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 192 mg of polymer (P9) was obtained, with a yield of 50.0%. Mn: 38.5 kDa, PDI: 2.34.

[0172] Polymer Synthesis Example 7: Synthesis of Polymer (P19)

[0173]

[0174] Accurately weigh monomers N-4 (226 mg, 0.25 mmol) and M-4 (273 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After purging with nitrogen six times, add Pd2(dba)3 (5.0 mg, 0.005 mmol) and purge with nitrogen six more times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 197 mg of polymer (P19) was obtained, with a yield of 52.3%. Mn: 42.3 kDa, PDI: 3.53.

[0175] Polymer Synthesis Example 8: Synthesis of Polymer (P20)

[0176]

[0177] Accurately weigh monomers N-1 (235 mg, 0.25 mmol) and M-4 (273 mg, 0.25 mmol) and add them sequentially to a 25 mL thick-walled pressure-resistant tube. Add tris(o-methylphenyl)phosphine (7.6 mg, 0.025 mmol) and ultra-dry o-xylene (15 mL). After fully purging with nitrogen six times, add Pd2(dba)3 (5.0 mg, 0.005 mmol) and continue to fully purge with nitrogen six times. The subsequent synthesis steps are the same as those for polymer (P2). Approximately 213 mg of polymer (P20) was obtained, with a yield of 55.1%. Mn: 40.1 kDa, PDI: 3.15.

[0178] Fabrication of organic photovoltaic cell devices (effective cell area 18.7 cm²) 2 (7 sub-cells) and characterization

[0179] This embodiment uses the organic photovoltaic cell (effective area 18.7 cm²) provided by the present invention. 2 The following is an example of the preparation and characterization of a battery with 7 sub-cells connected in series via insulating channels, connecting channels, and separating channels. However, the present invention is not limited to the following embodiments.

[0180] refer to Figure 2 The device embodiment 1 includes a substrate 10, an anode layer 101, an anode buffer layer 102, a photoactive layer 103, a cathode buffer layer 104, a cathode layer 105, an upper cover plate 20, and an adhesive layer 30, which are stacked in sequence.

[0181] Device Example 1

[0182] a. Provide conductive glass containing ITO, and etch insulating channels on the ITO using 20 nanosecond green light. The insulating channels extend through the ITO layer to the glass substrate. Then, clean the ITO conductive glass with insulating channels with detergent, rinse it clean, and then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes. Then, dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0183] b. Preparation of the anode buffer layer: PEDOT:PSS (Clevios) is placed in air... TM PVP Al 4083 was uniformly spin-coated onto ITO and dried at 150°C for 15 min to obtain an anode buffer layer with a thickness of approximately 20 nm.

[0184] c. Preparation of photoactive layer: The photoactive layer solution is uniformly spin-coated onto the anode buffer layer in air to obtain an active material layer with a total thickness of about 100 nm.

[0185] Preparation method of photoactive layer material: The donor material polymer (P2) and the acceptor material Y6-O of the active layer are dissolved in the organic solvent chloroform, wherein the concentration of the donor material polymer (P2) in chloroform is 5 mg / mL and the concentration of the acceptor material Y6-O in chloroform is 6 mg / mL.

[0186]

[0187] d. Preparation of cathode buffer layer: After the device with spin-coated photoactive layer is heat-annealed on a hot stage at 100°C for 10 min, the cathode buffer layer material PDINN (prepared by dissolving PDINN in methanol to a concentration of 1 mg / mL) is uniformly spin-coated onto the photoactive layer to obtain a cathode buffer layer with a thickness of about 10 nm.

[0188] e. Etching the connection channel: The connection channel is etched on the cathode buffer layer using a green nanosecond laser. The connection channel penetrates the cathode buffer layer, the photoactive layer, and the anode buffer layer to the ITO layer.

[0189] f. Cathode layer fabrication: under high vacuum (1×10⁻⁶) -6 Ag was deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of about 100 nm, at a deposition rate of 4 angstroms / second.

[0190] g. Etching isolation channels: Isolation channels are etched on the cathode layer using a green nano laser, and the isolation channels at least penetrate the cathode layer.

[0191] h. Encapsulation: The device is encapsulated in a nitrogen glove box using ultraviolet-cured resin, and the upper encapsulation cover is selected from glass.

[0192] Device Examples 2-5

[0193] The preparation methods of device examples 2-5 are the same as those of device example 1, except that the photoactive layer donor material is selected differently. Specifically, polymer (P2) is replaced with polymer (P3), polymer (P5), polymer (P8), and polymer (P9), respectively.

[0194] Device Comparison Example 1

[0195] The preparation method of the device in Comparative Example 1 is the same as that in Device Example 1, except that the active layer donor material is selected differently. Specifically, polymer (P2) is replaced with polymer D18.

[0196]

[0197] The prepared organic photovoltaic cell device was tested under indoor light. The cell current-voltage curve was tested under a 3000K LED light source (1000 lux) simulator, and the photoelectric conversion efficiency was calculated, as shown in Table 1.

[0198] Table 1

[0199] Device Examples Active layer for acceptor material Photoelectric conversion efficiency (%) Device Example 1 Polymer (P2): Y6-O 26.47 Device Example 2 Polymer (P3):Y6-O 25.82 Device Example 3 Polymer (P5): Y6-O 26.13 Device Example 4 Polymer (P8): Y6-O 26.34 Device Example 5 Polymer (P9): Y6-O 25.96 Device Comparison Example 1 D18:Y6-O 21.19

[0200] As can be seen from the characterization of the data in Table 1, the polymer described in this invention exhibits superior photoelectric conversion performance compared to D18. This is because the polymer of this invention introduces *-O-R2 into the electron-withdrawing unit A to give it a more suitable energy level and molecular morphology, and greatly improves the solubility of the polymer. When it is used as a donor material in combination with a suitable acceptor material (such as Y6-O) in the photoactive layer, the resulting photoactive layer film is more uniform and enhances the dissociation and transport of excitons. As a result, the organic photovoltaic module exhibits superior photoelectric conversion performance under indoor light.

[0201] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polymer, characterized in that: The polymer has a structure as described in general formula (I): in: Ar1, Ar2, and Ar3 each time they appear, are independently selected from substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms, or substituted or unsubstituted aromatic groups having 6-20 carbon atoms. Each time Z appears, it is independently selected from O, S, or Se; Each occurrence of R1 is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or substituted or unsubstituted aromatic groups having 6-10 carbon atoms. Each time R2 appears, it is independently selected from a straight-chain alkyl group having 1-20 carbon atoms or a branched alkyl group having 3-20 carbon atoms; The term "substituted or unsubstituted" indicates that the defined group is not substituted, or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -CN, -CF3, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, straight-chain alkathioyl having 1-20 carbon atoms, branched-chain alkathioyl having 3-20 carbon atoms, or a group formed by a combination of the above groups; n represents the number of repeating units, selected from an integer greater than or equal to 2.

2. The polymer according to claim 1, characterized in that: Z is selected from S.

3. The polymer according to claim 1, characterized in that: Each occurrence of Ar3 is independently selected from substituted or unsubstituted N-containing heteroaromatic groups having 5-6 ring atoms.

4. The polymer according to claim 3, characterized in that: The polymer has a structure as described in general formula (II): Wherein: each time Y appears, it is independently selected from O, S or Se.

5. The polymer according to claim 4, characterized in that: Each occurrence of R2 is independently selected from straight-chain alkyl groups having 1-12 carbon atoms or branched alkyl groups having 3-12 carbon atoms. Preferably, each occurrence of R2 is independently selected from methyl, ethyl, n-butyl, n-hexyl, n-octyl, 6. The polymer according to claim 4, characterized in that: Each occurrence of Ar1 and Ar2 is independently selected from substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or substituted or unsubstituted aromatic groups having 6-10 carbon atoms. Preferably, each occurrence of Ar1 and Ar2 is independently selected from any of the following groups: Wherein: W is selected independently from O, S or Se each time it appears; R3, R4, R5, R6, and R7 are each independently selected from -H, -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-20 carbon atoms, branched-chain alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched-chain alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, or branched-chain alkylthio with 3-20 carbon atoms.

7. The polymer according to claim 4, characterized in that: Each occurrence of R1 is independently selected from... The R8, R9, R 10 R 11 R 12 R 13 Each occurrence is independently selected from -H, -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-12 carbon atoms, branched-chain alkyl with 3-12 carbon atoms, straight-chain alkoxy with 1-12 carbon atoms, branched-chain alkoxy with 3-12 carbon atoms, straight-chain alkylthio with 1-12 carbon atoms, branched-chain alkylthio with 3-12 carbon atoms, or a group formed by a combination of the above groups.

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

9. A mixture, characterized in that: The mixture comprises the polymer as described in any one of claims 1-8.

10. An organic photovoltaic cell, the organic photovoltaic cell comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, characterized in that: The photoactive layer comprises the polymer as described in any one of claims 1-8, or a mixture as described in claim 9.

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