Additive for organic solar cell, composition and application

Abstract

The invention relates to an additive for an organic solar cell, a composition and application. The additive provided by the invention is a solid additive and has an asymmetric structure, and when the additive is used as the additive in an optical active layer of the organic solar cell, the morphology of the active layer can be optimized, so that the photovoltaic performance of the organic solar cell is improved.

Description

Technical Field

[0001] The present invention relates to the field of organic solar cell materials, in particular to an additive, a composition and an application thereof for an organic solar cell. Background Art

[0002] Organic photovoltaics (OPV) is a solar cell technology made from organic materials. Compared to traditional silicon-based photovoltaic technology, OPV uses organic molecules or polymers with semiconductor properties as light-absorbing layers to convert solar energy into electricity.

[0003] The photoelectric conversion process of organic solar cells is mainly divided into five steps: 1) Under illumination, the photoactive layer material absorbs photons to generate excitons; 2) Excitons diffuse to the donor-acceptor interface; 3) Excitons dissociate into free electrons and holes at the donor-acceptor interface; 4) Free carriers (electrons and holes) are transported in the donor and acceptor phases, respectively; 5) Electrons and holes are transported to the corresponding electrodes to complete charge collection. As an important component of organic solar cells, the photoactive layer is the key site for achieving photoelectric conversion. Achieving a blend film morphology with a suitable phase separation size is very important for realizing high-performance organic solar cells. In order to ensure the smooth and efficient completion of the photoelectric conversion process, in addition to developing new photoactive layer materials, regulating the microstructure, morphology and aggregation state of the active layer is crucial for further developing high-performance organic solar cells. Currently, common methods for regulating the morphology of the photoactive layer include thermal annealing, solvent annealing, and additives (solid / liquid).

[0004] During the solution preparation of the photoactive layer, a certain amount of additives is added to the solution of the active layer material to optimize the morphology of the photoactive layer film. Among various morphology optimization strategies, liquid additives such as 1,8-diiodooctane (DIO), diphenyl ether (DPE), diphenyl sulfide (DPS), 1-chloronaphthalene (CN), etc. have been shown to enhance molecular stacking and crystallinity, forming a film morphology with a suitable phase separation size, thereby improving light absorption, promoting charge separation and transport, and ultimately improving the photovoltaic performance of organic solar cells. However, the disadvantage of these liquid additives is that they have relatively high boiling points and are therefore not easy to volatilize during the processing process. They usually act as residual solvents, affecting the nanoscale morphology of the active layer and thus destroying the long-term stability. In particular, during large-area coating, these liquid additives easily aggregate during the film drying process, which seriously affects the film morphology and leads to reduced solar cell efficiency.

[0005] Therefore, it is necessary to develop a new solid additive to optimize the morphology of the photoactive layer of organic solar cells and thus improve the device performance of organic solar cells. Summary of the Invention

[0006] The present invention aims to provide a novel solid additive for use in the photoactive layer of an organic solar cell. The additive is easily soluble in an organic solvent and can significantly improve the device efficiency of the organic solar cell.

[0007] The technical solutions for achieving the purpose of the present invention are:

[0008] The first aspect of the present invention provides an additive for an organic solar cell, wherein the additive has a structure as described in general formula (I):

[0009]

[0010] in:

[0011] X is selected from O, S or C=O;

[0012] R1 is selected from -Cl, -Br, -I;

[0013] R2 is selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a straight-chain alkoxy group having 1 to 6 carbon atoms, a branched or cyclic alkoxy group having 3 to 6 carbon atoms, a straight-chain alkylthio group having 1 to 6 carbon atoms, a branched or cyclic alkylthio group having 3 to 6 carbon atoms, -CN, -OH, phenyl, a heteroaromatic group having 5 to 6 ring atoms, or a group formed by a combination of these groups;

[0014] The additive is selected from solid additives.

[0015] Accordingly, the second aspect of the present invention provides a composition comprising an active layer donor material, an active layer acceptor material, an additive and at least one organic solvent; wherein the additive comprises an additive for an organic solar cell as provided in the first aspect of the present invention.

[0016] Accordingly, the third aspect of the present invention provides an organic solar cell device, which comprises at least a cathode, an anode, and a photoactive layer located between the cathode and the anode, wherein the photoactive layer is prepared from the composition described in the second aspect or comprises the additive for an organic solar cell as described in the first aspect.

[0017] Compared with the prior art, the present invention has the following significant advantages: the present invention provides a solid additive with an asymmetric structure Its structure contains halogens, which have a large electronegativity, giving the additive a certain dipole moment. The enhancement of the dipole moment is conducive to more ordered molecular stacking and more favorable phase separation of the donor and acceptor molecules, resulting in enhanced charge transfer and reduced carrier recombination, thus significantly improving device efficiency.

[0018] At the same time, the solid additive according to the present invention has good solubility in the active layer solvent. When used as an additive in the photoactive layer of an organic solar cell, it can optimize the morphology of the active layer, thereby improving the photovoltaic performance of the organic solar cell.

[0019] Especially when preparing large-area organic solar cell devices, the addition of liquid additives often causes excessive molecular aggregation, affecting the morphology of the active layer and leading to reduced device performance. Conversely, the addition of the solid additive provided by the present invention not only inhibits excessive solution aggregation, optimizes film morphology, and improves device performance, but also improves device stability to a certain extent. This provides a new approach for the industrial application of organic solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Schematic diagram of the structure of an organic solar cell in an embodiment of the device of the present invention;

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

[0022] Figure 2 This is a morphology diagram of the photoactive layer film of device embodiment 10 (solid additive T-3) of the present invention.

[0023] Figure 3 This is a morphology diagram of the photoactive layer film of comparative example 11 (liquid additive DPE) of the device of the present invention.

[0024] Figure 4 This is a morphology diagram of the photoactive layer film of comparative example 12 (without additives) of the device of the present invention. DETAILED DESCRIPTION

[0025] To make the purpose, technical solutions, and effects of this application clearer and more explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are merely used to explain this application and are not intended to limit this application. Based on the described embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this invention.

[0026] The terms "and / or", "or / and", and "and / or" used herein include any one of two or more related listed items, and also include any and all combinations of the related listed items, wherein the arbitrary and all combinations include any combination of two related listed items, any more related listed items, or 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 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 of all being 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 four-item combination of A, B, C, and D (that is, the technical solution of all being connected by "logical AND").

[0027] In the present invention, when the position of the substituent on the group is not fixed, it means that any connecting site in the group can be used as a connecting site. Can represent or

[0028] In the present invention, organic photovoltaic device, organic solar cell and OPV have the same meaning and can be interchanged.

[0029] In the present invention, active layer and photoactive layer have the same meaning and can be interchanged.

[0030] In the present invention, "alkyl" may refer to a linear, branched, and / or cyclic alkyl group. The number of carbon atoms in a linear alkyl group may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, 1 to 6, or 1 to 4; the number of carbon atoms in a branched alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4; the number of carbon atoms in a cyclic alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4. Non-limiting examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; non-limiting examples of branched alkyl groups include isopropyl, tert-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, isopentyl, neopentyl, and tert-pentyl; non-limiting examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0031] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above connected to another group via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in the "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, 1 to 6, or 1 to 4; the branched-chain alkoxy group means that the alkyl group in the "-O-alkyl" is selected from a branched-chain alkyl group, wherein the number of carbon atoms of the branched-chain alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4; the cyclic alkoxy group means that the alkyl group in the "-O-alkyl" is selected from a cyclic alkyl group, wherein the number of carbon atoms of the cyclic alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4.

[0032] The term "alkylthio" refers to a group having the structure "-S-alkyl", i.e., an alkyl group as defined above attached to another group via a sulfur atom. A straight-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a straight-chain alkyl group, wherein the number of carbon atoms in the straight-chain alkyl group may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, 1 to 6, or 1 to 4; a branched-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a branched-chain alkyl group, wherein the number of carbon atoms in the branched-chain alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4; a cyclic alkylthio group means that the alkyl group in "-S-alkyl" is selected from a cyclic alkyl group, wherein the number of carbon atoms in the cyclic alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4.

[0033] "Alkoxycarboxyl" refers to a group having the structure The group, i.e. the alkyl group as defined above, is The number of carbon atoms in the linear alkoxycarboxyl group may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the number of carbon atoms in the branched alkoxycarboxyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6; and the number of carbon atoms in the cyclic alkoxycarboxyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0034] In the present invention, the "number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) formed by atoms 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 atoms. The "number of ring atoms" described below is also the same 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 a quinoline ring is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of a thienothiophene group is 8.

[0035] "Aryl" or "aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, and can be selected from monocyclic compounds and condensed ring compounds. Preferably, the number of carbon atoms is selected from 6 to 20; further, the number of carbon atoms is selected from 6 to 10. Suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, and their derivatives.

[0036] "Heteroaryl" or "heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, such as B, O, N, P, Si, Se, or S. Preferably, the number of ring atoms is selected from 5 to 20; further, the number of ring atoms is selected from 5 to 10; further, the number of ring atoms is selected from 5 to 8. Suitable examples include, but are not limited to, thienyl, furanyl, thiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, thienothiphenyl, thienothienothienyl, quinolyl, isoquinolyl, furofuranyl, and derivatives thereof.

[0037] In the present invention, one or more groups “independently selected” means that when one or more groups appear simultaneously in multiple places in a compound, they are all independently selected and may be the same or different.

[0038] In the present invention, the terms "combination thereof", "any combination thereof", "any combination thereof", "combination" and the like are used to indicate all suitable combinations of any two, three, four or more of the listed groups.

[0039] In the present invention, “further”, “further”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of the present invention.

[0040] In the present invention, the terms "optionally," "optional," and "optional" mean optional or dispensable, i.e., they refer to either option being selected from two parallel options: "with" or "without." If a technical solution contains multiple "optional" clauses, each "optional" clause is independent unless otherwise specified and there are no conflicts or constraints.

[0041] In the process of describing the structural elements of the present invention, the words "include" or "comprise" or "at least one" and the like used in the present invention mean that the device or material appearing before the word covers the devices or materials listed after the word and their equivalents, but does not exclude other devices or materials.

[0042] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0043] The technical solution of the present invention is described in detail below with reference to the accompanying drawings.

[0044] The first aspect of the present invention provides an additive for an organic solar cell, wherein the additive has a structure as described in general formula (I):

[0045]

[0046] in:

[0047] X is selected from O, S or C=O;

[0048] R1 is selected from -Cl, -Br, -I;

[0049] R2 is selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a straight-chain alkoxy group having 1 to 6 carbon atoms, a branched or cyclic alkoxy group having 3 to 6 carbon atoms, a straight-chain alkylthio group having 1 to 6 carbon atoms, a branched or cyclic alkylthio group having 3 to 6 carbon atoms, -CN, -OH, phenyl, a heteroaromatic group having 5 to 6 ring atoms, or a group formed by a combination of these groups;

[0050] The additive is a solid additive.

[0051] In one embodiment, the additive is selected from any one of the general formulas (II-1), (II-2) or (II-3):

[0052]

[0053] In one embodiment, R1 is selected from -Cl.

[0054] In another embodiment, R1 is selected from -Br.

[0055] In another embodiment, R1 is selected from -I.

[0056] In one embodiment, R2 is selected from -H (hydrogen), -D (deuterium), methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methoxy, methylthio, -OH, phenyl, pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, or a combination of these groups.

[0057] In one embodiment, R2 in Formula (II-1), (II-2) or (II-3) is selected from -H.

[0058] In another embodiment, R2 in Formula (II-1), (II-2) or (II-3) is selected from methyl.

[0059] In another embodiment, R2 in formula (II-1), (II-2) or (II-3) is selected from methoxy.

[0060] In another embodiment, R2 in Formula (II-1), (II-2) or (II-3) is selected from phenyl.

[0061] In a preferred embodiment, the additive is selected from any one of the general formulas (III-1) to (III-9):

[0062]

[0063] In a specific embodiment, the additive for an organic solar cell according to the first aspect of the present invention is selected from any one of structures (T-1) to (T-17), but is not limited thereto:

[0064]

[0065] In a preferred embodiment, according to the additive for an organic solar cell of the present invention, the melting point of the additive is greater than or equal to 35°C; further, the melting point of the additive is greater than or equal to 40°C; further, the melting point of the additive is greater than or equal to 50°C.

[0066] In one embodiment, the concentration of the additive for an organic solar cell provided by the present invention in an organic solvent is selected from 0.1 mg / mL to 30 mg / mL; further, the concentration is selected from 1 mg / mL to 20 mg / mL; further, the concentration is selected from 1 mg / mL to 10 mg / mL.

[0067] Preferably, the organic solvent is selected from the group consisting of dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indane, methyl benzoate, ethyl benzoate, and mesitylene, or a mixture of two or more thereof.

[0068] In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0069] In one embodiment, the additive for an organic solar cell according to the first aspect of the present invention is used in a photoactive layer of an organic solar cell.

[0070] The second aspect of the present invention provides a composition comprising an active layer donor material, an active layer acceptor material, an additive and at least one organic solvent; wherein the additive comprises the additive for an organic solar cell as described in the first aspect.

[0071] Furthermore, according to the above composition, the additive comprises any one of the structures (T-1) to (T-17).

[0072] In one embodiment, the active layer donor material is selected from polymer donor materials. Further, the active layer donor material is selected from the structure of formula (IV-1) or (IV-2):

[0073]

[0074] wherein: Ar1 and Ar2, at each occurrence, are independently selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic heterocycle having 5 to 30 ring atoms;

[0075] Each occurrence of R3, R4, R5, R6, R7, R8, and R9 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a straight-chain alkoxycarboxyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkoxycarboxyl group having 3 to 20 carbon atoms, or a group formed by a combination of the foregoing groups;

[0076] The term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more R, wherein each occurrence of R is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a straight-chain alkoxycarboxyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkoxycarboxyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups;

[0077] n represents the number of repeating units and is an integer greater than 1.

[0078] In one embodiment, the Ar1 is selected from any of the following groups:

[0079]

[0080] Among them, R 10 、R 11 、R 12 、R 13 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain alkoxycarboxyl having 3-20 carbon atoms, or a group formed by a combination of the foregoing groups;

[0081] * indicates the attachment site.

[0082] In one embodiment, R 10 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms. 10 Each occurrence is independently selected from a straight chain alkyl group having 1 to 16 carbon atoms, or a branched chain alkyl group having 3 to 16 carbon atoms. 10 Each occurrence is independently selected from

[0083] In one embodiment, R 11 Each occurrence is independently selected from -H, -D, a straight chain alkyl group having 1 to 20 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms; further, R 11 Each occurrence is independently selected from -H, -D, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched chain alkyl group having 3 to 10 carbon atoms; further, R 11 Each occurrence is independently selected from -H, -D, a straight chain alkyl group having 1 to 6 carbon atoms, or a branched chain alkyl group having 3 to 6 carbon atoms.

[0084] In one embodiment, R 12Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, straight-chain alkoxycarboxyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, branched-chain alkylthio having 3-10 carbon atoms, branched-chain alkoxycarboxyl having 3-10 carbon atoms, or a group formed by a combination of the above groups; further, each occurrence of R12 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, and nitro.

[0085] In one embodiment, each occurrence of R13 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a straight-chain alkoxycarboxyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a branched-chain alkoxycarboxyl group having 3-10 carbon atoms, or a combination thereof.

[0086] In a specific embodiment, the Ar1 is selected from the following groups:

[0087]

[0088] In one embodiment, each occurrence of R4 and R5 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a linear alkyl group having 1-10 carbon atoms, or a branched or cyclic alkyl group having 3-10 carbon atoms.

[0089] In one embodiment, each occurrence of R3 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight-chain alkyl group having 1-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, a branched-chain alkyl group having 3-16 carbon atoms, a branched-chain alkoxy group having 3-16 carbon atoms, and a branched-chain alkylthio group having 3-16 carbon atoms.

[0090] Furthermore, each occurrence of R3 is independently selected from a branched alkyl group having 3 to 16 carbon atoms, a branched alkoxy group having 3 to 16 carbon atoms, or a branched alkylthio group having 3 to 16 carbon atoms. Furthermore, each occurrence of R3 is independently selected from

[0091] In one embodiment, Each occurrence is independently selected from any of the following groups:

[0092]

[0093] In one embodiment, each occurrence of R6 and R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-20 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, a straight-chain alkoxycarboxyl group having 1-16 carbon atoms, a branched-chain alkyl group having 3-16 carbon atoms, a branched-chain alkoxy group having 3-16 carbon atoms, a branched-chain alkylthio group having 3-16 carbon atoms, a branched-chain alkoxycarboxyl group having 3-16 carbon atoms, or a combination thereof.

[0094] In one embodiment, Each occurrence is independently selected from any of the following groups:

[0095]

[0096] In one embodiment, Ar2 is selected from any of the following groups:

[0097]

[0098] wherein each occurrence of R14, R15, R16, R17, R18, and R19 is independently selected from: -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a straight-chain alkoxycarboxyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkoxycarboxyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups.

[0099] In one embodiment, each occurrence of R14 and R15 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight-chain alkyl group having 1-10 carbon atoms, or a branched or cyclic alkyl group having 3-10 carbon atoms.

[0100] In one embodiment, each occurrence of R16 is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight-chain alkyl group having 1-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, a branched-chain alkyl group having 3-16 carbon atoms, a branched-chain alkoxy group having 3-16 carbon atoms, and a branched-chain alkylthio group having 3-16 carbon atoms.

[0101] Furthermore, each occurrence of R16 is independently selected from a branched alkyl group having 3 to 16 carbon atoms, a branched alkoxy group having 3 to 16 carbon atoms, or a branched alkylthio group having 3 to 16 carbon atoms.

[0102] Furthermore, each occurrence of R16 is independently selected from the following structures:

[0103]

[0104] In a specific embodiment, Each occurrence is independently selected from any of the following groups:

[0105]

[0106] In one embodiment, each occurrence of R17 is independently selected from: -H, -D, -F, -Cl, -Br, -I, cyano, or nitro.

[0107] In one embodiment, each occurrence of R18 and R19 is independently selected from the group consisting of: -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, a straight-chain alkoxycarboxyl group having 1-16 carbon atoms, a branched-chain alkyl group having 3-16 carbon atoms, a branched-chain alkoxy group having 3-16 carbon atoms, a branched-chain alkylthio group having 3-16 carbon atoms, a branched-chain alkoxycarboxyl group having 3-16 carbon atoms, a phenyl group, a thienyl group, or a combination thereof.

[0108] Furthermore, each occurrence of R18 and R19 is independently selected from: -H, -D, -F, -Cl, -Br, -I, a straight-chain alkyl group having 1-10 carbon atoms, a branched-chain alkyl group having 3-10 carbon atoms, a straight-chain alkoxy group having 1-10 carbon atoms, a branched-chain alkoxy group having 3-10 carbon atoms, a straight-chain alkylthio group having 1-10 carbon atoms, a branched-chain alkylthio group having 3-10 carbon atoms, a phenyl group, a thienyl group, a furyl group, or a group formed by a combination of the above groups.

[0109] In one embodiment, each occurrence of R8 and R9 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1-20 carbon atoms, a linear alkoxy group having 1-16 carbon atoms, a linear alkylthio group having 1-16 carbon atoms, a linear alkoxycarboxyl group having 1-16 carbon atoms, a branched alkyl group having 3-16 carbon atoms, a branched alkoxy group having 3-16 carbon atoms, a branched alkylthio group having 3-16 carbon atoms, a branched alkoxycarboxyl group having 3-16 carbon atoms, or a combination thereof. Furthermore, each occurrence of R8 and R9 is independently selected from -H, -D, or a linear alkoxycarboxyl group having 1-10 carbon atoms.

[0110] Specifically, the active layer donor material is preferably selected from one, two or more of the following structures:

[0111]

[0112]

[0113] In one embodiment, the active layer acceptor material is selected from a non-fullerene acceptor material or a fullerene derivative acceptor material; further, the non-fullerene acceptor material is selected from the structure described in Formula (V-1) or Formula (V-2):

[0114]

[0115] Where: R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, branched alkoxycarboxyl having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of these groups;

[0116] n is the number of repeating units and n is an integer greater than 1.

[0117] In one embodiment, R 20 、R 21 、R 22 、R 23 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1 to 16 carbon atoms, a straight-chain alkoxy group having 1 to 16 carbon atoms, a straight-chain alkylthio group having 1 to 16 carbon atoms, a branched or cyclic alkyl group having 3 to 16 carbon atoms, a branched or cyclic alkoxy group having 3 to 16 carbon atoms, a branched or cyclic alkylthio group having 3 to 16 carbon atoms, a phenyl group, a thienyl group, a thienothiphenyl group, or a group formed by a combination of these groups.

[0118] Furthermore, R 20 、R 21 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1 to 16 carbon atoms, a straight-chain alkoxy group having 1 to 16 carbon atoms, a straight-chain alkylthio group having 1 to 16 carbon atoms, a branched-chain alkyl group having 3 to 16 carbon atoms, a branched-chain alkoxy group having 3 to 16 carbon atoms, a branched-chain alkylthio group having 3 to 16 carbon atoms, a phenyl group, a thienyl group, or a group formed by combining a phenyl group with a branched-chain alkyl group having 3 to 16 carbon atoms, or a group formed by combining a thienyl group with a branched-chain alkyl group having 3 to 16 carbon atoms.

[0119] Furthermore, R 22 、R 23 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight chain alkyl group having 1 to 16 carbon atoms, or a branched chain alkyl group having 3 to 16 carbon atoms.

[0120] In one embodiment, R 24 、R 25 、R 26 、R 27 、R 28 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, -CF3, straight chain or branched chain alkyl having 1 to 10 carbon atoms.

[0121] In one embodiment, R 29 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl having 1 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, straight-chain alkoxycarboxyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, branched alkoxycarboxyl having 3 to 10 carbon atoms, or a group formed by a combination of these groups.

[0122] In one embodiment, the non-fullerene acceptor material is selected from one, two or more of the following structures:

[0123]

[0124]

[0125] The fullerene derivative acceptor material is selected from C60 derivatives or C70 derivatives, and the fullerene derivative acceptor material includes but is not limited to: one, two or three or more of PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc.

[0126] Preferably, the mass ratio of the active layer donor material to the active layer acceptor material in the composition is 0.8:1.8 to 1.8:0.8; in one embodiment, the mass ratio of the active layer donor material to the active layer acceptor material is 1:1 to 1:1.8; further, the mass ratio is 1:1 to 1:1.5; further, the mass ratio is 1:1 to 1:1.2.

[0127] In one embodiment, the total concentration of the active layer donor material in the organic solvent is 3-15 mg / mL; further, the total concentration of the active layer donor material in the organic solvent is 3-10 mg / mL.

[0128] In one embodiment, the total mass concentration of the active layer donor material and the acceptor material in the organic solvent is 7-30 mg / mL; further, the total mass concentration in the organic solvent is 7-20 mg / mL.

[0129] Preferably, the organic solvent is selected from the group consisting of dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indane, methyl benzoate, ethyl benzoate, and mesitylene, or a mixture of two or more thereof.

[0130] In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0131] The third aspect of the present invention relates to an organic solar cell device, wherein the organic solar cell comprises at least a cathode, an anode, and a photoactive layer located between the cathode and the anode, and the photoactive layer is prepared from the composition described in the second aspect or comprises the additive for the organic solar cell described in the first aspect.

[0132] In a preferred embodiment, the organic solar cell device according to the present invention further comprises an anode buffer layer, wherein the anode buffer layer is located between the anode and the active layer.

[0133] Furthermore, the anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoOx), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WOx, preferably, x is selected from 2 or 3), etc., but is not limited thereto.

[0134] In a preferred embodiment, the organic solar cell device according to the present invention further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the active layer.

[0135] Furthermore, the cathode buffer layer material is selected from metal oxides or polymers. The metal oxide may be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc. The polymer may be PFN-Br, PFN, PDINN, PDINO, PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited thereto.

[0136] The materials used to prepare the cathode and anode 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 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 are not limited thereto.

[0137] The organic solar cell device of the present invention further comprises a substrate. In one embodiment, the substrate is located below the anode layer, and the active layer is located on the other side of the anode layer; in another embodiment, the substrate is located below the cathode layer, and the active layer is located on the other side of the cathode layer.

[0138] Specifically, the substrate can use a substrate with excellent transparency, surface smoothness, ease of handling and water resistance. For example, a glass substrate, a film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in the form of a single layer or multiple layers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto, and substrates commonly used for organic solar cells may also be used.

[0139] In the description of the present invention, it should be understood that the terms "upper", "lower", "between layers", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which organic solar cell devices are conventionally placed when in use, or are the orientations or positional relationships conventionally understood by those skilled in the art. These terms are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation. Therefore, they should not be understood as limiting the present invention.

[0140] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0141] Preparation of organic solar cell devices

[0142] Device Example 1-Device Example 9, Device Comparative Example 1-Device Comparative Example 4 The devices prepared are small-area devices, with a device area of ​​0.06 cm 2 .

[0143] Device Example 1

[0144] The active layer of the organic solar cell comprises an active layer donor material PM6, an active layer acceptor material A-13, an active layer acceptor material A-21, and a solid additive (T-3). The specific structure is as follows:

[0145]

[0146] The specific preparation method comprises the following steps:

[0147] 1) ITO substrate cleaning:

[0148] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 15 minutes. It was then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0149] 2) Preparation of anode buffer layer

[0150] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 3000-4000 rpm, and annealed at 150° C. for 15 min to obtain an anode buffer layer with a thickness of 20 nm.

[0151] 3) Preparation of photoactive layer

[0152] In a glove box (inert gas atmosphere), the photoactive layer material was evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of 100 nm.

[0153] Preparation method of photoactive layer material: dissolve the active layer donor material PM6, the active layer acceptor material A-13, the active layer acceptor material A-21, and the solid additive (T-3) in the organic solvent chloroform, wherein the concentration of the donor material PM6 in chloroform is 7.5 mg / mL, the concentration of the acceptor material A-13 in chloroform is 6.75 mg / mL, the concentration of the acceptor material A-21 in chloroform is 2.25 mg / mL, and the concentration of the solid additive in chloroform is 8 mg / mL.

[0154] 4) Preparation of cathode buffer layer

[0155] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINO (PDINO was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the active layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of 10 nm.

[0156] 5) Cathode layer preparation

[0157] 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 100 nm at a rate of 4 angstroms / second.

[0158] 6) Packaging

[0159] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0160] Device Example 2:

[0161] The preparation method of device example 2 is the same as that of device example 1, except that the solid additive (T-3) of the photoactive layer material in device example 1 is replaced by a solid additive (T-5):

[0162]

[0163] Device Example 3:

[0164] The preparation method of device example 3 is the same as that of device example 1, except that the solid additive (T-3) of the photoactive layer material in device example 1 is replaced by a solid additive (T-6):

[0165]

[0166] Device Example 4:

[0167] The preparation method of device example 4 is the same as that of device example 1, except that the solid additive (T-3) of the photoactive layer material in device example 1 is replaced by a solid additive (T-12):

[0168]

[0169] Device Example 5:

[0170] The preparation method of device example 5 is the same as that of device example 1, except that the solid additive (T-3) of the photoactive layer material in device example 1 is replaced by a solid additive (T-13):

[0171]

[0172] Device Example 6:

[0173] The preparation method of device example 6 is the same as that of device example 1, except that the solid additive (T-3) of the photoactive layer material in device example 1 is replaced by a solid additive (T-16):

[0174]

[0175] Device Comparative Example 1:

[0176] The preparation method of device comparison example 1 is the same as that of device example 1, except that the preparation method of the photoactive layer is different and the selection of additives is different. Specifically, the photoactive layer material is evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm in a glove box (inert gas atmosphere) to obtain an active material layer with a total thickness of 100 nm.

[0177] The photoactive layer material preparation method is as follows: dissolving the active layer donor material PM6, the active layer acceptor material A-13, and the active layer acceptor material A-21 in the organic solvent chloroform, wherein the concentration of the donor material PM6 in chloroform is 7.5 mg / mL, the concentration of the acceptor material A-13 in chloroform is 6.75 mg / mL, and the concentration of the acceptor material A-21 in chloroform is 2.25 mg / mL; after sufficient dissolution, the liquid additive FPE is added to the aforementioned active layer solution at a volume ratio of 3%, where the volume ratio is the volume of the additive / the volume of the organic solvent.

[0178]

[0179] Device Comparative Example 2:

[0180] The preparation method of device comparative example 2 is the same as that of device comparative example 1, except that the liquid additive FPE in the photoactive layer is replaced by a liquid additive DPE:

[0181]

[0182] Device Comparative Example 3:

[0183] The preparation method of Device Comparative Example 3 was the same as that of Device Comparative Example 1, except that no additives were added to the photoactive layer. Specifically, the active layer donor material PM6, the active layer acceptor material A-13, and the active layer acceptor material A-21 were dissolved in the organic solvent chloroform at a mass ratio of 1:0.9:0.3, wherein the concentration of the donor material PM6 in chloroform was 7.5 mg / mL, the concentration of the acceptor material A-13 in chloroform was 6.75 mg / mL, and the concentration of the acceptor material A-21 in chloroform was 2.25 mg / mL. After dissolution and thorough mixing, the photoactive layer materials were evenly spin-coated on the anode buffer layer at a speed of 1800-4000 rpm in a glove box (inert gas atmosphere), resulting in an active material layer with a total thickness of 100 nm.

[0184] The performance of the prepared organic solar cell device was tested. Under the irradiation of the AM 1.5G standard light of the solar simulator, the battery current-voltage curve was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 1:

[0185] Table 1

[0186] Active layer donor / acceptor materials Active layer additives Photoelectric conversion efficiency (%) Device Example 1 PM6:A-13:A-21 T-3 18.53 Device Example 2 PM6:A-13:A-21 T-5 18.25 Device Example 3 PM6:A-13:A-21 T-6 17.68 Device Example 4 PM6:A-13:A-21 T-12 18.01 Device Example 5 PM6:A-13:A-21 T-13 17.82 Device Example 6 PM6:A-13:A-21 T-16 17.49 Device Comparative Example 1 PM6:A-13:A-21 FPE 17.10 Device Comparative Example 2 PM6:A-13:A-21 DPE 17.22 Device Comparative Example 3 PM6:A-13:A-21 / 16.89

[0187] The device data in Table 1 demonstrate that the solid additives described herein exhibit excellent device performance when used in organic solar cell devices. This has two significant advantages: First, the prior art FPE and DPE additives are both liquid additives. When used in large-area fabrication, these additives are prone to molecular aggregation, resulting in poor device reproducibility and reduced long-term stability, making them particularly unfavorable for the fabrication of large-area organic solar cell devices. In contrast, the additives described herein are solid additives that are readily soluble in organic solutions, resulting in more stable performance in the fabrication of large-area organic solar cells.

[0188] Second, the solid additive with an asymmetric structure developed by the present invention enables the additive to have a certain dipole moment. The enhancement of the dipole moment is conducive to the donor and acceptor molecules to exhibit more ordered molecular stacking and more favorable phase separation, resulting in enhanced charge transfer and reduced carrier recombination, thereby having a significant effect on improving device efficiency.

[0189] Device Example 7

[0190] The active layer of the organic solar cell comprises an active layer donor material PTQ10, an active layer acceptor material A-20, and a solid additive (T-3). The specific structure is as follows:

[0191]

[0192] The specific preparation method comprises the following steps:

[0193] 1) ITO substrate cleaning:

[0194] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 15 minutes. It was then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0195] 2) Preparation of anode buffer layer

[0196] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 3000-4000 rpm, and annealed at 150° C. for 15 min to obtain an anode buffer layer with a thickness of 20 nm.

[0197] 3) Preparation of photoactive layer

[0198] In a glove box (inert gas atmosphere), the photoactive layer material was evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of 100 nm.

[0199] Preparation method of photoactive layer material: dissolve the active layer donor material PTQ10, the active layer acceptor material A-20, and the solid additive (T-3) in the organic solvent chloroform, wherein the concentration of the donor material in chloroform is 8 mg / mL, the concentration of the acceptor material in chloroform is 9.6 mg / mL, and the concentration of the solid additive in chloroform is 8 mg / mL.

[0200] 4) Preparation of cathode buffer layer

[0201] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINO (PDINO was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the active layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of 10 nm.

[0202] 5) Cathode layer preparation

[0203] 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 100 nm at a rate of 4 angstroms / second.

[0204] 6) Packaging

[0205] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0206] Device Example 8

[0207] The preparation method of device example 8 is the same as that of device example 7, except that the solid additive (T-3) of the photoactive layer material in device example 7 is replaced by the solid additive (T-2):

[0208]

[0209] Device Example 9

[0210] The preparation method of device example 9 is the same as that of device example 7, except that the solid additive (T-3) of the photoactive layer material in device example 7 is replaced by a solid additive (T-17):

[0211]

[0212] Device Comparative Example 4:

[0213] The preparation method of device comparison example 4 is the same as that of device example 7, except that no additives are added to the photoactive layer. Specifically, the photoactive layer material is evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm in a glove box (inert gas atmosphere) to obtain an active material layer with a total thickness of 100 nm.

[0214] The photoactive layer material preparation method is as follows: the active layer donor material PTQ10 and the active layer acceptor material A-20 are dissolved in the organic solvent chloroform at a mass ratio of 1:1.2, wherein the concentration of the donor material in chloroform is 8 mg / mL, and the concentration of the acceptor material in chloroform is 9.6 mg / mL.

[0215] The performance of the prepared organic solar cell device was tested. Under the irradiation of the AM 1.5G standard light of the solar simulator, the battery current-voltage curve was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 2:

[0216] Table 2

[0217] Active layer donor and acceptor materials Active layer additives Photoelectric conversion efficiency (%) Device Example 7 PTQ10:A-20 T-3 18.12 Device Example 8 PTQ10:A-20 T-2 17.78 Device Example 9 PTQ10:A-20 T-17 17.51 Device Comparative Example 4 PTQ10:A-20 / 16.75

[0218] It can be seen from the device data in Table 2 that when the solid additive according to the present invention is used in an organic solar cell device, the photoelectric conversion efficiency of the device is significantly improved compared with that of the device in Comparative Example 4.

[0219] It can be seen from the device characterization data in Tables 1 and 2 that the solid additive according to the present invention has a positive effect when used in photoactive layer receptor systems of different systems. Therefore, the solid additive according to the present invention has universal applicability.

[0220] Device Example 10 (Method for preparing a large-area OPV device, device area: 16.8 cm 2 )

[0221] 1) ITO substrate cleaning:

[0222] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 15 minutes. It was then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0223] 2) Preparation of anode buffer layer

[0224] PEDOT:PSS(Clevios TM VP Al 4083) was evenly coated on the ITO with a scraper height of 150 μm from the substrate and a scraper speed of 10 mm / s, and annealed at 150° C. for 15 min to obtain an anode buffer layer with a thickness of about 20 nm.

[0225] 3) Preparation of photoactive layer

[0226] 90 mL of the active layer solution was scraped onto the anode buffer layer in air with a scraper at a height of 150 μm from the substrate and a scraper speed of 8 mm / s, to obtain an active material layer with a total thickness of about 100 nm.

[0227] Preparation method of photoactive layer material: dissolve the active layer donor material PM6, the active layer acceptor material A-13, and the solid additive (T-3) in the organic solvent toluene, wherein the concentration of the donor material PM6 in toluene is 6 mg / mL, the concentration of the acceptor material A-13 in toluene is 7.2 mg / mL, and the concentration of the solid additive (T-3) in toluene is 1 mg / mL.

[0228] 4) Preparation of cathode buffer layer

[0229] After the coated active layer was thermally annealed on a hot plate at 100°C for 10 minutes, 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 coated on the active layer with a scraper height of 150 μm from the substrate and a scraper speed of 5 mm / s, resulting in a cathode buffer layer with a thickness of approximately 10 nm.

[0230] 5) Cathode layer preparation

[0231] 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 / second.

[0232] 6) Packaging

[0233] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0234] Among them: The morphology of the photoactive layer is as follows: Figure 2 shown.

[0235] Device Example 11 (Method for preparing a large-area OPV device, device area: 16.8 cm 2 )

[0236] The preparation method of device embodiment 11 is the same as that of device embodiment 10, except that the preparation method of the photoactive layer material is different.

[0237] Preparation method of photoactive layer material: The active layer donor material PM6 and the active layer acceptor material A-13 are dissolved in the organic solvent toluene, wherein the concentration of the donor material PM6 in toluene is 6 mg / mL, and the concentration of the acceptor material A-13 in toluene is 7.2 mg / mL. After sufficient dissolution, the liquid additive DPE is added to the aforementioned active layer solution at a volume ratio of 1.5%, and the volume ratio is the volume of the additive / the volume of the organic solvent.

[0238]

[0239] Among them: The morphology of the photoactive layer is as follows: Figure 3 shown.

[0240] Device Example 12 (Method for preparing a large-area OPV device, device area: 16.8 cm 2 )

[0241] The preparation method of device embodiment 12 is the same as that of device embodiment 10, except that the preparation method of the photoactive layer material is different and the photoactive layer material does not contain additive materials. The specific preparation method is as follows:

[0242] Preparation method of photoactive layer material: dissolve the active layer donor material PM6 and the active layer acceptor material A-13 in the organic solvent toluene, wherein the concentration of the donor material PM6 in toluene is 6 mg / mL, and the concentration of the acceptor material A-13 in toluene is 7.2 mg / mL.

[0243] Among them: The morphology of the photoactive layer is as follows: Figure 4 shown.

[0244] from Figure 2 It can be seen that the film morphology prepared by the solid additive of the present invention is more uniform and no coffee ring is produced; Figure 3 It can be seen that the film prepared by liquid additives causes excessive molecular aggregation, resulting in coffee rings, which affects the stability and photoelectric conversion performance of the device.

[0245] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. An additive for an organic solar cell, characterized in that: The additive has a structure as described in general formula (I): in: X is selected from O, S or C=O; R1 is selected from -Cl, -Br, -I; R2 is selected from -H, -D, a straight-chain alkyl group having 1-6 C atoms, a branched or cyclic alkyl group having 3-6 carbon atoms, a straight-chain alkoxy group having 1-6 C atoms, a branched or cyclic alkoxy group having 3-6 carbon atoms, a straight-chain alkylthio group having 1-6 C atoms, a branched or cyclic alkylthio group having 3-6 carbon atoms, -CN, -OH, phenyl, a heteroaromatic group having 5-6 ring atoms, or a group formed by a combination of these groups; The additive is a solid additive.

2. The additive for organic solar cells according to claim 1, characterized in that: The general formula (I) is selected from any one of the general formulas (II-1), (II-2) or (II-3):

3. The additive for organic solar cells according to claim 2, characterized in that: R2 is selected from -H, -D, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methoxy, methylthio, -OH, phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furyl, or a group formed by a combination of these groups.

4. The additive for organic solar cells according to claim 1, characterized in that: The additive is selected from any of the following structures:

5. The additive for organic solar cells according to claim 1, characterized in that: The melting point of the additive is greater than or equal to 35°C.

6. A composition comprising an active layer donor material, an active layer acceptor material, an additive and at least one organic solvent, characterized in that: The additive comprises the additive for an organic solar cell according to any one of claims 1 to 5.

7. The composition according to claim 6, characterized in that: The active layer donor material is selected from polymer donor materials; and / or, the active layer acceptor material is selected from non-fullerene acceptor materials or fullerene derivative acceptor materials.

8. The composition according to claim 6 or 7, characterized in that: The active layer donor material is selected from the structure shown in general formula (IV-1) or (IV-2): Wherein: Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, and substituted or unsubstituted non-aromatic heterocycles having 5 to 30 ring atoms at each occurrence; R3, R4, R5, R6, R7, R8, R9, each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain alkoxycarboxyl having 3-20 carbon atoms, or a group formed by a combination of the above groups; The term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more R, wherein each occurrence of R is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a straight-chain alkoxycarboxyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkoxycarboxyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups; n represents the number of repeating units and is an integer greater than 1.

9. The composition according to claim 8, characterized in that: The Ar1 is selected from any of the following groups: Among them, R 10 , R 11 , R 12 , R 13 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain alkoxycarboxyl having 3-20 carbon atoms, or a group formed by a combination of the foregoing groups; * indicates the attachment site.

10. The composition according to claim 8, characterized in that: The Ar2 is selected from any of the following groups: Where: R 14 , R 15 , R 16 , R 17 , R 18、 R 19 Each occurrence is independently selected from: -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain alkoxycarboxyl having 3-20 carbon atoms, aromatic groups having 6-20 carbon atoms, heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of the foregoing groups; * indicates the attachment site.

11. The composition according to claim 8, characterized in that: The active layer donor material is selected from one, two or more of the following structures:

12. The composition according to claim 7, characterized in that: The non-fullerene acceptor material is selected from the structure described in formula (V-1) or formula (V-2): Where: R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, branched alkoxycarboxyl having 3-20 carbon atoms, aromatic groups having 6-20 carbon atoms, heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of these groups; n is the number of repeating units and n is an integer greater than 1.

13. The composition according to claim 11, characterized in that: The non-fullerene acceptor material is selected from one, two or more of the following structures:

14. An organic solar cell device comprising at least a cathode, an anode, and a photoactive layer located between the cathode and the anode, characterized in that: The photoactive layer is prepared from the composition according to any one of claims 6 to 13 or comprises the additive for an organic solar cell according to any one of claims 1 to 5.

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